sulfur record of rising and falling marine oxygen and sulfate levels during the lomagundi event carbonates from approximately 2 3 2 1 billion years ago show markedly positive 13c values commonly reaching and sometimes exceeding 10 traditional interpretation of these positive 13c values favors greatly enhanced organic carbon burial on a global scale although other researchers have invoked widespread methanogenesis within the sediments to resolve between these competing models and more generally among the mechanisms behind earth s most dramatic carbon isotope event we obtained coupled stable isotope data for carbonate carbon and carbonate associated sulfate cas cas from the lomagundi interval shows a narrow range of 34s values and concentrations much like those of phanerozoic and modern marine carbonate rocks the 34s values are a close match to those of coeval sulfate evaporites and likely reflect seawater composition these observations are inconsistent with the idea of diagenetic carbonate formation in the methanic zone toward the end of the carbon isotope excursion there is an increase in the 34s values of cas we propose that these trends in c and s isotope values track the isotopic evolution of seawater sulfate and reflect an increase in pyrite burial and a crash in the marine sulfate reservoir during ocean deoxygenation in the waning stages of the positive carbon isotope excursion

sample scale carbon isotopic variability and diverse biomass in the paleoproterozoic zaonega formation russia abstract the stratigraphic record of organic matter in the c 1 97 ga zaonega formation zf onega basin northwestern russia exhibits a distinct negative 13c excursion 13corg from 25 to 40 vpdb which was previously interpreted either to reflect a disturbance in the global carbon cycle after the great oxidation event or to have been caused by an increase in basinal methanotrophic activity in order to assess the nature of primary biomass and the effects of post depositional alteration we here report the sample scale carbon isotopic characteristics of organic matter in two drill cores from the zf covering 500 m of stratigraphy by using secondary ion mass spectrometry sims the results confirm that the organic matter has to a large extent preserved the primary isotopic signatures whereas secondary effects are limited

a short term post lomagundi positive c isotope excursion at c 2 03 ga recorded by the wooly dolomite western australia it is generally accepted that carbon isotope variations in seawater were muted between c 2 06 ga after the end of the lomagundi carbon isotope excursion lcie and c 1 3 ga evidence is presented here that c 30 myr after the end of the lcie the biogeochemical cycle of carbon experienced a short term c 2 myr high amplitude up to 8 4 v pdb perturbation recorded in the horseshoe rift basin western australia the basin was initiated at c 2 03 ga with deposition of fluvial and shallow marine sandstones followed by the eruption of flood basalt and culminated with the deposition of platform carbonates and accompanying volcaniclastic and siliciclastic sediments wooly dolomite the horseshoe rift basin during deposition of the wooly dolomite was fault compartmentalized but connected to an ocean six depositional sequences make up the wooly dolomite sequence 1 records establishment of a carbonate platform conformably on basalt and coevally with volcaniclastic sedimentation all other sequences have dominant carbonate platform deposits and are unconformity bounded sequence 3 contains a c 57 m thick section with 13 c enriched carbonates bracketed between carbonates with close to 0 carbon isotope values further high resolution chemostratigraphic studies may reveal a more complex pattern of carbon isotope variations during the boring billion years but without precise geochronology similar short term carbon isotope excursions in carbonate successions could be incorrectly correlated to the lcie supplementary material table 2 including chemical and isotopic data sample locations and their position in figure 8 is available at https doi org 10 6084 m9 figshare c 2868055

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

the lomagundi jatuli carbon isotopic event recorded in the marble of the tandilia system basement rio de la plata craton argentina abstract the lomagundi jatuli event corresponds to the most important 13c positive anomaly 5 globally reported in palaeoproterozoic marine carbonates between 2 30 and 2 06 ga in the tandilia system argentina rio de la plata craton this event was recorded in the basement marble of the san miguel area the calcite diopside marble hosted by biotite gneiss and intruded by 2 12 ga garnet leucogranite was metamorphosed in amphibolite facies during the transamazonian cycle paas normalised rare earth elements ree and y for the carbonate rocks are hree enriched and display positive eu and y anomalies typical of primary precipitates from a mixed hydrothermal marine environment carbonate additionally a truly negative ce anomaly for all the samples indicates that the depositional environment was oxidising positive 13c values ranging from 5 90 to 4 30 v pdb and 18o from 17 45 to 13 84 v smow were determined in this marble both gradually decreasing towards the contact with the leucogranites these values indicate that devolatilization reactions took place during the crystallisation of a wollastonite vesuvianite grossular diopside skarn generated by the leucogranite intrusions into the marble 18o values obtained from diopside and calcite crystals in the marble sectors furthest from the contacts with leucogranite allowed a 663 623 c formation temperature to be calculated considering oxygen in a calcite diopside geothermometric pair these temperatures are consistent with the metamorphic degree amphibolite facies reached in this portion of the basement although the san miguel marble shows petrographic and mineralogical evidence of regional and contact metamorphism important geochemical and isotopic characteristics together with its estimated palaeoproterozoic age indicate that the marble protolith was a marine carbonate deposited during the lomagundi jatuli event

atmospheric weathering of scandinavian alum shales and the fractionation of c n and s isotopes abstract subaerial exposure and oxidation of organic carbon c org rich rocks is believed to be a key mechanism for the recycling of buried c and s back to earth s surface importantly processes coupled to microbial c org oxidation are expected to shift new biomass 13 c org composition towards more negative values relative to source however there is scarcity of information directly relating rock chemistry to oxidative weathering and shifting 13 c org at the rock atmosphere interface this is particularly pertinent to the sulfidic c org rich alum shale units of the baltoscandian basin believed to constitute a strong source of metal contaminants to the natural environment following subaerial exposure and weathering consistent with independent support we show that atmospheric oxidation of the sulfidic c org rich alum shale sequence of the cambrian devonian baltoscandian basin induces intense acid rock drainage at the expense of progressive oxidation of fe sulfides sulfide oxidation takes priority over microbial organic matter decomposition enabling quantitative massive erosion of c org without producing a 13 c shift between acid rock drainage precipitates and shale moreover 13 c enrichment in inorganic carbon of precipitates does not support microbial c org oxidation as the predominant mechanism of rock weathering upon exposure instead a 34 s 34 s shale 34 s precipitates 0 accompanied by elevated s levels and the ubiquitous deposition of acid rock drainage sulfate minerals in deposited efflorescent precipitates relative to shales provide strong evidence for quantitative mass oxidation of shale sulfide minerals as the source of acidity for chemical weathering slight 15 n depletion in the new surface precipitates relative to shale coincides with dramatic loss of n from shales collectively the results point to pyrite oxidation as a major driver of alum black shale weathering at the rock atmosphere interface indicating that quantitative mass release of c org n s and key metals to the environment is a response to intense sulfide oxidation consequently large scale acidic weathering of the sulfide rich alum shale units is suggested to influence the fate and redistribution of the isotopes of c n and s from shale to the immediate environment

shallow stratification prevailed for 1700 to 1300 ma ocean evidence from organic carbon isotopes in the north china craton abstract the late paleoproterozoic to early mesoproterozoic from 1700 ma to 1300 ma was highlighted by the assembly of the nuna supercontinent expansion of euxinic marine environments and apparent stasis in the diversity of eukaryotes the isotopic composition of carbonate carbon 13ccarb was surprisingly constant during this interval but little is known about the secular variation in the organic carbon isotopic composition 13corg here we report 13corg data from the latest paleoproterozoic 1650 ma to early mesoproterozoic 1300 ma succession in north china the 13corg values range from 25 to 34 and are dependent on sedimentary facies in subtidal and deeper environments 13corg values are low and constant ca 32 but relatively enriched and more variable in shallower intertidal and supratidal environments we attribute the facies dependent variation in 13corg to the presence of a shallow chemocline a probable result of a shallow chemocline is that it supported significant contributions of organic matter produced by chemoautotrophic and or anaerobic photoautotrophic microbes in relatively deep environments from the latest paleoproterozoic to early mesoproterozoic continental shelf of north china

two step deoxygenation at the end of the paleoproterozoic lomagundi event abstract the ca 2 1 ga francevillian group of gabon was deposited in the aftermath of the great oxidation event goe and records the lomagundi event le which is the most pronounced and long lived carbon isotope excursion in the geologic record moreover the sedimentary succession contains putative evidence for the earliest appearance of macro eukaryotes an emerging paradigm is that the end of the le was accompanied by a deoxygenation event that preceded the apparent stability of environmental and redox conditions as well as the carbon cycle characteristic of the mesoproterozoic however the processes that led to deoxygenation some 300 to 200 ma after the beginning of the goe are not well understood here we present a multi proxy stable isotope 34 s 33 s 36 s 98 mo 13 c org 13 c carb and 18 o carb study of the francevillian group we suggest that sedimentation of the lower part of the francevillian group took place during the le in oxygenated shallow waters with elevated sulfate concentrations two episodes of anoxic water shoaling during deposition of the upper francevillian group correspond with broader marine deoxygenation and a contraction of the seawater sulfate reservoir this shoaling of anoxic conditions may be linked to intense submarine hydrothermal and volcanic activity that led to sedimentary manganese deposits we propose that increased concentrations of aqueous hydrothermally sourced reductants drove oxygen consumption during the first deoxygenation event and established a sulfidic oxygen minimum zone at the margin of the shallow shelf carbonates with positive 13 c carb values characteristic of the le precipitated during this first stage of deoxygenation the second deoxygenation separated from the previous event by a period of well oxygenated conditions was marked by a stronger contraction of the seawater sulfate reservoir and coincided with the end of the le during this time widespread euxinic conditions were established in shallow above storm wave base marine environments the presence of a shallow water redoxcline points to a generally low oxygen atmosphere ocean system further the negative co variation between 34 s and 13 c values in sediments of the francevillian group and other sedimentary successions of similar age worldwide suggests that the inferred two step deoxygenation corresponding to the end of the le reflects global rather than local events that likely occurred between 2 1 and 2 05 ga ago

precise u pb titanite age constraints on the emplacement of the bushveld complex south africa the c 2 06 ga bushveld complex intrudes the transvaal supergroup south africa calcsilicate xenoliths within the mafic phase of the bushveld complex rustenburg layered suite or rls preserve calcsilicate xenoliths with high temperature c 1200 c mineralogies that were later metasomatized by hydrous retrograde c 600 700 c fluids whose timing has been unconstrained new u pb isotope data from newly grown titanite within a completely retrogressed xenolith indicates that retrogression occurred at 2058 9 0 8 ma this suggests that retrogression was due to hydrothermal circulation associated with the cooling rls and not slightly later bushveld related granites the new data place a tight constraint on the minimum age of emplacement of the rls

nitrogen isotope evidence for stepwise oxygenation of the ocean during the great oxidation event abstract the earth s oxygenation represents one of the most important environmental drivers of life s evolution with the first rise known as the great oxidation event goe corresponding to unpreceded accumulation of atmospheric o2 changes in the flux of marine nutrients and possibly global glaciations however the detailed evolution of the goe is still debated as for instance the accumulation trends of oceanic versus atmospheric oxygen and the nature of biogeochemical responses to oxygenation here we combine organic carbon and bulk nitrogen isotope compositions with major element concentrations and iron speciation data of sedimentary rocks recovered from two drill cores t2 and t3 in the early paleoproterozoic turee creek group western australia to track the redox evolution of marine conditions during the goe t2 core samples of the kungarra formation which consists of clastic sedimentary rocks overlaid by the glaciogenic meteorite bore member were deposited 2 31 ga ago t3 core intercepts from bottom to top quartzite of the koolbye formation and shales and stromatolitic carbonates of the kazput formation which were deposited around 2 25 ga samples from t2 show minor variations of 13corg avg 34 5 1 7 n 30 with no significant difference between siliciclastic and glaciogenic sedimentary rocks in contrast t3 samples display an increase in 13corg from 32 0 to 24 8 n 54 from shales to carbonates in both t2 and t3 cores 13corg values are inversely correlated with al2o3 suggesting a strong petrological control on 13corg values inferred here as resulting from variable contributions of detrital organic matter bulk n contents are low from 13 5 to 56 7 ppm and 15 7 to 53 4 ppm in t2 and t3 samples respectively the 15n values show a bimodal distribution with one mode at 2 6 in t2 and another at 8 8 in t3 independent from lithological variations this 15n values shift between t2 and t3 is interpreted as reflecting a change from dominating n2 fixers to no3 assimilating organisms this implies an increase of no3 availability and thus of o2 concentration during the time interval separating the deposition of t2 and t3 sediments dissolved no3 and o2 concentrations of the turee creek marine basin are estimated from two models using n isotope data the dissolved no3 concentration has an upper limit ranging from 1 91 to 3 04 m about one order of magnitude below the average value of modern oceans the lower limit for dissolved oxygen concentration ranges from 1 8 to 4 4 m which is two orders of magnitude lower than modern oceans together with previous studies the present data place quantitative constraints on the redox changes associated with the great oxidation event and illustrate a stepwise increase of no3 bioavailability between 2 31 to 2 25 ga in relation with increasing o2 level

evidence for paleoproterozoic cap carbonates in north america the early paleoproterozoic snowy pass supergroup of the medicine bow mountains and sierra madre wyoming usa and huronian supergroup ontario canada were deposited along the present day southern flank of the wyoming and superior cratons whereas three discrete levels of glacial diamictite are developed in both successions carbonate strata are known only directly above the middle diamictite vagner and bottle creek formations in medicine bow mountains and sierra madre respectively and espanola formation in southern ontario in these thick correlative siliciclastics dominated strata the carbonates from each succession record negative 13 c values 4 0 to 0 8 v pdb and attenuated carbon isotopic difference between organic and inorganic phases oxygen in carbonates is strongly depleted in 18 o suggesting exchange with hot fluids which is consistent with pervasive recrystallization of carbonates and remobilization of elements however the stratigraphic coherence of carbon isotopic compositions and the general lack of correlation between 13 c and either 18 o values or trace element concentrations supports a primary origin for 13 c depleted carbonates which are interpreted here to reflect anomalous oceanic compositions the intimate association of thick carbonate units containing abundant carbonate debris flows with immediately underlying glacial strata indicates that chemical precipitation resulted from a rapid flux of carbonate alkalinity onto ocean margins during post glacial transgression although these early paleoproterozoic carbonates are similar to neoproterozoic cap dolomites in stratigraphic position and carbon isotopic compositions the older post glacial accumulations begin with limestone and lack many of the sedimentary structures typical of neoproterozoic deposits furthermore it is not understood why carbonates only occur above the middle of the three glacial horizons whereas these deposits are ubiquitous above neoproterozoic diamictites the differences might reflect lower overall carbonate saturation in early paleoproterozoic oceans which contrasts sharply with archean and later paleoproterozoic intervals and higher siliciclastic inputs in rift environments which shut down carbonate deposition geological and geochemical indicators suggest a stepwise increase in atmospheric oxygen across the paleoproterozoic glacial epoch the tempo and mode of atmospheric oxygen rise has significant consequences for the abundance of the important greenhouse gases ch4 and co2 and hence for oceanic acidity if we accept that atmospheric oxidation of methane to carbon

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

geochronology geochemistry and tectonic significance of the dashizhai ophiolitic melange belt southeastern xing an mongolia orogenic belt the xing an mongolia orogenic belt places at the southeastern margin of the central asian orogenic belt is important for unraveling the tectonic evolution of the accretionary orogens the validity of existing models that account for the development and closure of the paleo asian ocean critically depends on the assumed initial configuration and evolution process of the various microcontinents that were separated by the ophiolitic belts or suture zones and deep faults in this work we present a newly discovered dashizhai ophiolitic melange belt in the ulanhot region and systematically investigate the occurrence through petrology and geochronology of this ophiolitic melange the dashizhai ophiolitic melange belt is a typical ssz type ophiolitic melange has a block in matrix structure the blocks include ophiolitic ultramafic rock volcanic rock siliceous rock and gabbro in a matrix of deformed early permian slate our new geochronology data suggest that the dashizhai ophiolitic melange belt should form in the early permian or younger and emplaced before the late permian deposition by focusing on the regional geologic history of the southeastern xing an mongolia orogenic belt the dashizhai ophiolitic melange belt together with northeast migrating hehei fault zone were suggested as the tectonic boundary between the xing an and songliao xilinhot blocks

temporal constraints on the paleoproterozoic lomagundi jatuli carbon isotopic event the paleoproterozoic lomagundi jatuli positive 13c excursion in sedimentary carbonates represents an event whose magnitude and duration is unique in earth history although precise absolute chronology of this event remains poorly constrained in northeastern fennoscandia an 1300 m thick sedimentary volcanic succession of the pechenga greenstone belt records decline of this isotopic excursion zircons from sedimentary rocks that occur within the decline have yielded 207pb 206pb dates at 2058 2 ma 6 ma including u decay constant uncertainties and provide the first maximum age constraint on the termination of the lomagundi jatuli event combined with existing constraints these data indicate an 140 m y interval characterized by 13c rich carbonate accumulation

microbenthic distribution of proterozoic tidal flats environmental and taphonomic considerations silicified carbonates of the late mesoproterozoic to early neoproterozoic society cliffs formation baffin island contain distinctive microfabrics and microbenthic assemblages whose paleo environmental distribution within the formation parallels the distribution of these elements through proterozoic time in the society cliffs formation restricted carbonates including microdigitate stromatolites laminated tufa and tufted microbial mats consist predominantly of synsedimentary cements these facies and the cyanobacterial fossils they contain are common in paleoproterozoic successions but rare in neoproterozoic and younger rocks less restricted tidal flat facies in the formation are composed of laminated microbialites dominated by micritic carbonate lithified early yet demonstrably after compaction these strata contain cyanobacteria that are characteristic in neoproterozoic rocks within the formation the facies dependent distribution of microbial populations reflects both the style and timing of carbonate deposition because of the strong substrate specificity of benthic cyanobacteria a reasonable conclusion is that secular changes in microbenthic assemblages through proterozoic time reflect a decrease in the overall representation of rapidly lithified carbonate substrates in younger peritidal environments as well as concomitant changes in the taphonomic window of silicification through which early life is observed

primitive os and 2316 ma age for marine shale implications for paleoproterozoic glacial events and the rise of atmospheric oxygen abstract re os dating of synsedimentary to early diagenetic pyrite from carbonaceous shale that straddles the boundary between the rooihoogte and timeball hill formations transvaal supergroup south africa provides a precise isochron age of 2316 7 ma 4 statistical uncertainty if error on decay constant is excluded and a chondritic initial 187os 188os ratio of 0 1121 0 0012 these units were deposited between what are interpreted as the second and third of three paleoproterozoic global glacial events and thus provide minimum and maximum ages respectively for these events the rooihoogte formation is correlative with the duitschland formation which records previously undated carbon isotope excursions because the pyrite samples show no evidence of mass independent fractionation of sulfur and have highly negative 34s values the rise of atmospheric oxygen most likely began prior to 2 32 ga the chondritic initial 187os 188os ratio requires that primitive hydrothermal sources of os dominated the os budget of seawater at 2 32 ga os is mobile only under oxidizing conditions therefore the chondritic initial 187os 188os ratio may reflect atmospheric oxygen levels too low to introduce sufficient riverine flux of dissolved radiogenic os to offset the primitive hydrothermal magmatic flux even if atmospheric oxygen levels had increased significantly by 2 32 ga anoxic conditions throughout the archean most likely limited os enrichment in archean marine shales so that their subsequent exposure and weathering was unable to provide a significant amount of radiogenic os to paleoproterozoic seawater

a widespread positive 13ccarbanomaly at around 2 33 2 06 ga on the fennoscandian shield a paradox carbon isotope measurements carried out on 201 carbonate samples from the early proterozoic of the kola peninsula n karelia and norway yield 13c pdb spanning 20 5 to 11 a general 13c secular trend shows that prior to 2 33 ga values are typically normal marine averaging around 3 0 between 2 33 and 2 06 ga in jatulian time there follows a rapid excursion to positive 13c of around 6 post jatulian time is characterized by 13c of sedimentary carbonates fluctuating between 5 and 3 also it is remarkable for the first pronounced development of diagenetic carbonates which have 13c between 14 and 6 the c 6 positive 13c shift with a duration of about 270 myr coincides with a maximum in the diversity and abundance of stromatolites and with widespread development of red beds but does not coincide with the maximum of buried corg mass the fennoscandian shield represents the largest isotoically anomalous carbonate province yet reported and the positive 13c excursion together with a series of major global palaeoenviromental changes seems to be more intense than the precambrian cambrian transition events however it is still not clear what kind of mechanism this phenomenon could be attributed to an increase of the ronov ratio and or broecker ratio and other possible models are discussed as the target for future investigations

the ongeluk basaltic andesite formation in griqualand west south africa submarine alteration in a 2222 ma proterozoic sea abstract the ongeluk lavas form part of the palaeoproterozoic transvaal griqualand west supracrustal sequence of the archaean kaapvaal craton of south africa they form a thick shallow marine volcanic sequence of pillow lava massive flows and hyaloclastite which together with their comagmatic subaerial hekpoort correlate once covered most of the craton in this study the magmatic composition and alteration features of ongeluk samples were distinguished using geochemistry and radiogenic isotopes the ongeluk hekpoort magma was a basaltic andesite derived from anomalous kaapvaal craton lithosphere with a long history of high u pb high rb sr and chur like sm nd ratios little evidence for magmatic fractionation was found although contamination of the lower lavas with cr rich material is evident in both hekpoort and ongeluk sequences the alteration of ongeluk lavas is characterised using diagrams which compare pillow core rim pairs hyaloclastite and massive lava samples with the estimated original magma composition alteration is ascribed to a shallow 87 sr 86 sr ratios decreased from magmatic 0 7071 towards seawater 0 7025 during submarine alteration the rb sr system also reveals a much later 1200 ma phase of ca and rb mobility in a few samples in contrast the submarine alteration affected pb isotope ratios so little that a 2222 13 ma isochron age is regarded as a refinement of earlier dates for the ongeluk hekpoort extrusion the ongeluk hyaloclastites acted as a sink for k and rb in the overlying sea while the mn and ca entering the sea could have contributed to the overlying kalahari manganese deposits

bushveld aged fluid flow peak metamorphism and gold mobilization in the witwatersrand basin south africa constraints from in situ shrimp u pb dating of monazite and xenotime in situ u pb dating of monazite and xenotime in gold reefs and unmineralized greenschist facies sedimentary rocks from the witwatersrand basin south africa reveals two episodes of tectonothermal activity a major event between 2 06 and 2 03 ga is recorded in the wit watersrand and transvaal supergroups in the northwestern and central basin and broadly coincides with the ca 2 06 ga bushveld event in the central and southern basin a previously unrecognized event has been dated between 2 14 and 2 12 ga the widespread geographic and stratigraphic occurrence of bushveld aged monazite and xenotime including both auriferous reefs and unmineralized strata indicates that metamorphism and fluid flow associated with magmatism was pervasive affecting most of the succession 10 km thick in the central and northern parts of the basin the metamorphic phosphate dates which are younger away from the complex indicate a lag of 20 30 m y between emplacement and phosphate growth in the central basin 100 km south suggesting that heat related to magmatism was transferred southward at an average rate of 3 5 mm yr 1 the absence of 2 06 2 03 ga phosphates in the welkom goldfield at the southern end of the basin implies that bushveld related heating and fluid flow did not affect this part of the basin the intergrowth of ca 2 045 ga monazite with gold in quartz pebble conglomerate from the west rand goldfield indicates that fluid flow related to the bushveld event caused mobilization of gold in the witwatersrand basin

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

natural nuclear fission reactors time constraints for occurrence and their relation to uranium and manganese deposits and to the evolution of the atmosphere abstract knowledge of the formation conditions of francevillian uranium and manganese ore deposits as well as natural fission reactors sheds light on the early evolution of the atmosphere between 1950 and 2150 ma ago the model explaining the formation of the oklo uranium deposits suggests that at the time of sediment deposition in the franceville basin 2150 million years ago the oxygen deficient atmosphere would have inhibited uranium dissolution dissolution of uranium was only possible during later diagenesis approximately 1950 ma reduction reactions in the presence of hydrocarbons allowed precipitation of dissolved uranium to u4 forming deposits with high enough uranium contents to trigger subsequent nuclear fission reactions such a model is in agreement with earlier suggestions that oxygen contents in atmosphere increased during a transition phase some 2450 2100 ma ago the manganese deposits were formed before the uranium deposits during the deposition of the black shales and very early diagenesis and thus at a time when oxygen content in atmosphere was very low carbon isotopes data of organic matter show decrease of 13c upward in the francevillian series 20 to 46 pdb reflecting the high ch4 and low o2 contents in the atmosphere during sediment deposition this favoured anoxic conditions during deposition of the basinal fb black shales and likewise the migration of mn over long distances the manganese precipitated first as mn oxides at the shallow edges of the franceville basin in photic zones where photosynthetic organisms flourished mn oxides were then reduced in the black shales forming mn carbonates when conditions became more reducing during transgression episodes and or the first stages of burial in the black shales reducing conditions prevailed until recent weathering allowing the good preservation of organic matter and the mn deposits the present day alteration is responsible for the dissolution of mn carbonates and precipitation of mn oxides at the water table to form the high grade mn ore 45 50 mn development of photosynthesizing organisms a volcanic source of the mn and favourable palaeogeography of the francevillian basins are all important parameters for the formation of the mn deposits for the occurrence of the natural nuclear reactors the age of 2 0 ga is the main parameter that controls the abundance of fissile 235u and the critical mass before 2 0 ga the 235u 238u ratio was sufficiently high for fission reactions to occur but conditions favourable for forming high grade uranium ores were not achieved then after 2 0 ga the increase of oxygen in the atmosphere commonly led to the formation of high grade uranium ores in which the 235u 238u ratio was too low to support criticality

transvaal supergroup carbonates implications for paleoproterozoic δ18o and δ13c records abstract the paleoproterozoic interval is characterized by the first evidence for incontrovertibly free oxygen in the ocean atmosphere system in this study carbonates from the transvaal group the silverton lucknow rooinekke and particularly the duitschland formations were analyzed for isotopes of carbon oxygen and strontium in order to constrain models dealing with the patterns of seawater evolution although the trace element data showed variable alteration of the carbonate samples selected samples with a lesser degree of alteration yielded interpretable results the best measured 87sr 86sr isotope value of 0 7031 at 2 35 ga ago fits well with the published curve for precambrian seawater confirming that paleoproterozoic budget of sr was dominated by input from continental sources during the paleoproterozoic times carbonates with 13c values of about 10 are known to have been present worldwide and they have been studied also during this research the observation that in the duitschland formation such high isotope values and normal marine values were both present within a single formation indeed within its single beds suggested that the large spread of 13c values reflects local or regional rather than global phenomena the oxygen isotope data show a large spread of values from 3 to 16 while their corresponding 13c signals are almost unchanged over this entire range with the lucknow and silverton formations clustering around 10 and the rooinekke formation around 2 the duitschland formation has a bimodal distribution with both 13c populations present the last formation also contains samples with 18o as low as 20 particularly in the vicinity of the bushveld intrusive body these highly 18o depleted samples show homogenization of 13c values towards 5 modelling suggests that the trends could have resulted from post depositional alteration by basinal fluids at near surface to about 50 c temperatures in a rock buffered system the duitschland formation samples particularly at duitschland farm the locality closest to the bushveld complex were then further altered at temperatures up to about 80 c in response to this intrusion

paleoproterozoic high δ13c dolomites from the lastoursville and franceville basins se gabon stratigraphic and synsedimentary subsidence implications abstract new data for the isotopic composition of carbon in shallow marine sedimentary carbonates in southeastern gabon franceville and lastoursville sub basins indicate that the seawater value of 13 c in these sediments underwent a large positive excursion around 2 1 ga these carbonate rocks belong to the fc formation of the francevillian group deposited along the margin of the archean chaillu craton in open marine shelf and evaporite settings and experienced locally lower greenschist facies metamorphism four microfacies mf1 mf4 are recognized from subtidal cyanobacterial dolobindstones to inter and supratidal collapse breccias mf4 the dolomites exhibit elevated 13 c values most values are above 0 50 the highest value is 9 74 and the average value is near 4 vs vpdb consistent with deposition during the large worldwide positive excursion between 2 22 and 2 06 ga these positive 13 c values are independent of the microfacies type such high 13 c values are also recorded in reworked carbonates dolomites embedded in coarse grained sandstones and conglomerates interstratified in the black shales of the underlying fb formation suggesting that the dolomites were at least stratigraphically equivalent to the black shale deposits interaction between early structural development and sediment fill lead to the formation of several sub basins with distinct differences in terms of amount and timing of subsidence the 13 c enriched dolomites are probably linked to high burial rate of organic carbon starting with the deposition of the fb sediments in this extensional geotectonic context as a consequence the cherty and dolomitic fc formation cannot longer be considered as a marker interval the end of the positive excursion is located near the top of the francevillian series i e fe and could be used in future studies as a potential chemostratigraphic tool in the paleoproterozoic

comparison of isotopic and geochemical characteristics of sediments from a gas and liquids prone wells in marcellus shale from appalachian basin west virginia abstract the middle devonian age marcellus shale contains one of the largest shale gas plays in north america hydrocarbon production in the eastern part of the play is mostly dry gas consisting of essentially pure methane production of natural gas liquids condensate increases toward the west which is the area currently being targeted by developers two marcellus shale cores from west virginia were analyzed to compare the isotopic and geochemical characteristics of a liquids prone well wv 7 in wetzel county with a gas prone well wv 6 in monongalia county the contrasts between the cores indicate that the conditions of the marcellus shale deposition were different between the two sites the dominant organic matter preserved in each core is isotopically different 13corg values are lighter on average in wv 6 compared with wv 7 a possible explanation is that a larger fraction of terrestrial organic matter was preserved in the wv 6 core whereas wv 7 may contain a greater percentage of marine organic matter clastic influx proxies e g ti al ca al and mg al also suggest that the wv 6 core site received a higher siliciclastic input compared to wv 7 consistent with a more proximal location to dry land and the delivery of greater amounts of terrestrial organic matter depleted 13ccarb values low concentrations of redox sensitive elements e g v cr ni and u and high variability 15n values in the wv 6 core all suggest the presence of higher dissolved oxygen concentration and short term shifts in an oxic anoxic boundary near the sediment water interface during deposition these lines of evidence indicate that the depositional conditions were favorable for the accumulation of predominantly gas prone type iii kerogen in the marcellus shale at the wv 6 site in contrast the marcellus shale at the wv 7 site was deposited in a more distal area that received a low terrestrial sediment supply organic matter primarily derived from marine algae and bottom water conditions that were dominantly anoxic such conditions were favorable for the accumulation of type ii kerogen that has a greater capacity to generate liquid hydrocarbons differences between the liquids prone and gas prone parts of the marcellus shale play have been largely ascribed to depth of burial and thermal maturation history this study indicates that depositional environment and sedimentary facies may have played significant roles as well

terminal proterozoic mid shelf benthic microbial mats in the centralian superbasin and their environmental significance abstract a combined sedimentological and biogeochemical study has been conducted on several terminal proterozoic mid shelf microbial mat facies from the centralian super basin isotopic and organic geochemical analysis of the bitumen and kerogen indicated that two sources of organic matter from planktonic and benthic microbial mat populations contributed to the sediment the planktonic source provided a suite of n alkanes with c20 whereas the benthic source contributed an overlay of n alkanes c20 with a strong even preference together with mid chain methyl alkanes kerogen and biomarkers derived from the microbial mat were found to be depleted in 13c relative to planktonic material pyrite in the micorbial mats was also found to be depleted in 34s compared to surrounding facies the combination of these observations suggested that the mats may have been at least partly composed of sulfide oxidising bacteria these organisms have specific environmental tolerances that set limits on palaeo environment their requirement for oxygen indicates that the water column above the mid shelf could not have been anoxic accordingly from the results and age determinations reported here it would appear that mid shelf environments of the centralian superbasin of australia were seeing significant levels of oxygen through the ediacarian

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

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

a 3 800 million year isotopic record of life from carbon in sedimentary rocks an increased ratio of 12c to 13c an indicator of the principal carbon fixing reaction of photosynthesis is found in sedimentary organic matter dating back to almost four thousand million years ago a sign of prolific microbial life not long after the earth s formation partial biological control of the terrestrial carbon cycle must have been established very early and was in full operation when the oldest sediments were formed

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

the origin of decoupled carbonate and organic carbon isotope signatures in the early cambrian ca 542 520 ma yangtze platform abstract the early cambrian ca 542 520 ma strata in south china record two prominent negative carbonate carbon isotope 13ccarb excursions of early nemakit daldynian n d and early tommotian ages across each of these excursions carbonate and organic carbon isotopes 13ccarb and 13corg are strongly decoupled regional correlation across a shelf to basin transect shows lateral heterogeneity of 13corg during the early middle n d but more homogenized 13corg values across the basin during the late n d and tommotian the temporal and lateral variations in 13corg suggest that decoupled 13ccarb and 13corg across the n d 13ccarb excursion were possibly caused by diagenetic alteration of organic matter and or amplification of detrital organic carbon isotope signature in low toc carbonates in contrast decoupled 13ccarb and 13corg of the upper n d and tommotian were likely resulted from chemoautotrophic methanotrophic biomass contribution to toc in organic rich black shale and carbonates the decoupled 13ccarb 13corg pattern from the lower n d strata ca 542 ma shows striking similarities with those from the basal ca 635 ma and upper ca 551 ma doushantuo formation in all three cases decoupled 13ccarb 13corg are seen in organic poor carbonates toc 0 1 and coupled 13ccarb 13corg occur in organic rich black shale and carbonates at the end of the negative 13ccarb excursion these similarities suggest that the shift from decoupled to coupled 13ccarb 13corg has no causal link with the terminal oxidation of a large oceanic doc reservoir given the pervasive anoxia euxinia in ediacaran early cambrian oceans local doc rich environments may have been common but a large oceanic doc reservoir capable of buffering the 13c of marine organic matter requires independent evidence

initialization and simulation of a landfalling hurricane using a variational bogus data assimilation scheme abstract the bogus data assimilation bda scheme designed by zou and xiao to specify initial structures of tropical cyclones was tested further on the simulation of a landfalling hurricane hurricane fran 1996 the sensitivity of the simulated hurricane track and intensity to the specified radius of maximum wind of the bogus vortex the resolution of the bda assimilation model and the bogus variables specified in the bda are studied in addition the simulated hurricane structures are compared with the available observations including the surface wind analysis and the radar reflectivity captured onshore during fran s landfall the sensitivity study of the bda scheme showed that the simulations of the hurricane track and intensity were sensitive to the size of the specified bogus vortex hurricanes with a larger radius of maximum sea level pressure gradient are prone to a more westward propagation the larger the radius the weaker the predicted hurricane results of the hurricane initial structures an

structure and dynamics of sheared mantle plumes 1 an extensive series of laboratory experiments is used to investigate the behavior of sheared thermal plumes the plumes are generated by heating a small circular plate on the base of a cylindrical tank filled with viscous fluid and then sheared by rotating a horizontal lid at the fluid surface the motion of passive tracers in the plumes is visualized by the release of several dye streams on the hot plate we systematically examine the dependence of the convective flow on four dimensionless numbers a velocity ratio a rayleigh number the viscosity ratio and an aspect ratio we identify and delineate two transitions in the convective behavior from a regime where the plume can spread upstream against the shear to a regime where the entire plume is advected downstream and from a regime of negligible cross stream circulation to a regime with significant cross stream circulation and thermal entrainment our analysis of the steady profiles of the plumes shows that they initially rise with a constant vertical rise velocity this rise velocity depends on the buoyancy flux and ambient viscosity but is almost independent of the centerline plume viscosity which suggests that most of the thermal plume has a viscosity that is much closer to the ambient viscosity than the centerline viscosity as the plumes approach the lid they decelerate as the viscous drag on them steadily increases the lateral spreading of the plumes under the lid is found to be well described by similarity solutions derived for the spreading of compositional plumes on a rigid surface if the effective viscosity of the thermal plumes is taken to be the ambient viscosity rather than the centerline viscosity a similar theoretical model is found to roughly predict the upstream spreading of thermal plumes at low shear but it breaks down at moderate to high shear where the entire plumes are advected downstream when our results are applied to the earth we find that mantle plumes are mostly divided into only two flow regimes in the upper mantle plumes under slow moving plates experience upstream flow and negligible cross stream circulation while plumes under faster moving plates including all pacific plumes experience significant cross stream circulation and are advected downstream we also demonstrate that geochemical heterogeneities in a plume s source region will result in an azimuthally zoned plume and in an asymmetric geographical distribution of geochemical heterogeneities in the erupted hot spot basalts as is seen in the hawaiian galapagos marquesas and tahiti society island chains for individual mantle plumes we determine their diameter and vertical rise velocity as well as the extent of upstream spreading and the rate of lateral spreading under the lithosphere

u pb geochronology of monazite in precambrian tuffs reveals depositional and metamorphic histories abstract uranium lead geochronology of zircon in felsic tuffs plays a key role in the development of chronostratigraphic frameworks for sedimentary successions this is particularly true for precambrian basins where biostratigraphy is of limited use for age determination or stratigraphic correlation although zircon is widely used to date tuffs it can yield null results due to the presence of xenocrystic populations or isotopic resetting other potential u pb chronometers such as monazite which also crystallize from felsic magmas are largely unreported from felsic tuff layers consequently there has been a lack of studies to evaluate the potential of monazite for u pb isotope geochronology of tuffs we present results of in situ u pb ion microprobe dating of monazite that co exists with zircon in felsic tuffs from two precambrian basins the earaheedy basin frere formation in western australia and the bushveld basin lephala formation in southern africa we show that 207pb 206pb ages from monazite in felsic tuffs from the frere formation 1891 9 ma and the lephala formation 2307 9 ma are identical to zircon ages from the respective tuffs also monazite in the bushveld tuff preserves additional information including a chronological fingerprint of the volcanic source 2 4 2 5 ga xenocrysts and the timing of low grade metamorphism 2 16 ga overgrowths the ca 2 16 ga low grade metamorphism identified in the bushveld basin is reminiscent of that widely recorded in the pilbara craton western australian lending support to arguments for a connection between the kaapvaal and pilbara cratons igneous and low grade metamorphic monazites are readily distinguished based on texture and chemistry our study demonstrates that monazite can be used to accurately date felsic tuffs offering a powerful tool for constraining depositional and metamorphic histories of precambrian sedimentary basins

spatial and temporal trends in precambrian nitrogen cycling a mesoproterozoic offshore nitrate minimum abstract fixed nitrogen is an essential nutrient for eukaryotes as n 2 fixation and assimilation of nitrate are catalyzed by metalloenzymes it has been hypothesized that in mesoproterozoic oceans nitrate was limited in offshore environments by low trace metal concentrations and high rates of denitrification in anoxic and episodically euxinic deep water masses restricting eukaryotes to near shore environments and limiting their evolutionary innovation to date this hypothesis has only been tested in the belt supergroup 1 4 ga with results that support an onshore offshore nitrate gradient as a potential control on eukaryote ecology here we present bulk nitrogen and organic carbon isotopic data from non isochronous cross basinal facies across the bangemall 1 5 ga and the roper 1 4 1 5 ga basins to better understand the extent and variability of onshore offshore nitrogen isotope gradients in the mesoproterozoic both basins show an average 1 2 enrichment in 15 n bulk from deep to shallow facies with a maximum range from 1 offshore to 7 5 onshore unlike the belt basin the bangemall and roper basins show some offshore 15 n bulk values that are enriched beyond the isotopic range associated with biological n 2 fixation alone this suggests a mixture of aerobic and anaerobic metabolisms offshore in shallow waters where 15 n bulk enrichment peaks an aerobic nitrogen cycle was evidently operating even though isotopic signatures of aerobic nitrogen cycling are seen in all parts of the bangemall and roper basins our data are consistent with a lateral gradient in nitrate availability within the photic zone with higher concentrations in near shore environments than offshore the variability in 15 n bulk values in each depositional environment and the consistently low 15 n bulk values from mesoproterozoic units compared to the paleoproterozoic and neoproterozoic suggest that nitrate concentrations in the global ocean were likely low this trend is now seen in all three mesoproterozoic basins so far examined and contrasts with the paleoproterozoic and neoproterozoic where nearly all 15 n bulk data plot above the n 2 fixation window thus we propose that the mesoproterozoic ocean was characterized by a nitrate minimum with the lowest concentrations in offshore environments this inference is consistent with a mesoproterozoic o 2 decline following a temporary paleoproterozoic o 2 peak and it further supports the idea that nitrate limitation offshore may have contributed to the restriction of photosynthetic eukaryotes to near shore environments delaying their rise to ecological dominance until the neoproterozoic era

the effectiveness of the paleoproterozoic biological pump a δ13c gradient from platform carbonates of the pethei group great slave lake supergroup nwt samples of carbonate cements collected along a depth transect of the pethei platform a 1 9 ga stromatolitic reef reveal a small 0 5 carbon isotope gradient between shallow and basinal facies the magnitude of this gradient would conventionally be interpreted as indicating low export of organic matter from ocean surface waters but steady state simulations using a two box model of the paleoproterozoic ocean suggest that the small carbon isotope gradient could instead be due to high partial pressures of carbon dioxide in the paleoproterozoic atmosphere which would increase the ocean9s dissolved inorganic carbon content and damp the effects of biological pumping if the paleoproterozoic atmosphere were indeed enriched in atmospheric co 2 in compensation for a less luminous sun these results indicate that the planktonic biota was a significant component of the precambrian global carbon and nutrient cycles affecting if not regulating as today the composition of both surface and deep ocean waters

on the consistency between dynamical and thermodynamic equations with prescribed vertical motion in an analytical tropical cyclone model in our earlier paper we presented an analytical model for intensifying tropical cyclones tcs in which the effects of all nonlinear terms in the horizontal momentum equations are retained this analytical model was obtained by prescribing the time evolution of the vertical motion in this paper we demonstrate that with the prescribed vertical motion the system of governing equations for geophysical flows can be separated into two subsystems one consisting of the horizontal momentum and continuity equations and the other including the vertical momentum and thermodynamical equations results show that the analytical solutions for the horizontal winds obtained from the first subsystem are consistent with the mass field in the second subsystem such as the thermal wind relationship in tcs furthermore we show that use of any functional form for the mean vertical motion will not affect our previous major conclusions about the different growth rates either between the secondary and primary circulations or between the inner and outer regions in tcs copyright 2010 royal meteorological society

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

sensitivity of the epeiric sea carbon isotope record to local scale carbon cycle processes tales from the mohawkian sea ancient marine carbon isotope records derived from epeiric sea carbonates can bear a strong influence of local scale carbon cycling processes across the late ordovician mohawkian sea of eastern laurentia the carbon isotope compositions d 13 c of contemporaneous sediments range from 2x in the interior of the sea to 2 5x along the margin here we use a box model to explore the relative importance of carbon fluxes within the mohawkian sea from a mass balance perspective in the model the mohawkian sea carbon reservoir is coupled to but distinct from the ocean and atmosphere carbon reservoirs at initial steady state conditions the residence time of carbon in the mohawkian sea is less than 10 years we find that to produce model d 13 c values representative of the range in d 13 c across the mohawkian sea we must divide the sea into an inner region and an outer region and limit dissolved inorganic carbon dic exchange between the two to 15 of the initial steady state unrestricted exchange rate it is also necessary to supply low d 13 c carbon 29x to the inner region of the sea at a rate of 17 4 10 12 mol c yr 1 the required flux of low d 13 c carbon could not have been sustained over the long term by remineralization of organic carbon stored in sediments of the inner region of the mohawkian sea and the geographic d 13 c pattern is unlikely to have been generated by upwelling along the sebree trough rather the low d 13 c flux might have been derived from bryophytedominated terrestrial ecosystems suggesting an important role for terrestrial carbon cycling prior to the advent of vascular plants aninterestingfeatureofthemodelisthattheisotopiccompositionsofboththeepeiric seaandthelargerocean atmospheresystem are sensitive to changes in exchange rates within the epeiric sea this has important implications for interpreting global d 13 c

pervasive aerobic nitrogen cycling in the surface ocean across the paleoproterozoic era abstract nitrogen isotope ratios in marine sedimentary rocks have become a widely used biogeochemical proxy that records information about nutrient cycling and redox conditions in earth s distant past while the past two decades have seen considerable progress in our understanding of the precambrian sedimentary nitrogen isotope record it is still compromised by substantial temporal gaps furthermore quantitative links between nitrogen isotope data marine redox conditions and nutrient availability are largely lacking in a precambrian context here we present new nitrogen isotope data from a suite of marine sedimentary rocks with ca 2 4 to 1 8 ga ages spanning the great oxidation event in the paleoproterozoic to better constrain the response of the nitrogen cycle to the first major redox transition in earth s history we further construct a simple box model to describe the major pathways that influenced the nitrogen isotope mass balance of the precambrian ocean and use this as a platform to evaluate the precambrian nitrogen isotope record within this framework we find that consistently positive nitrogen isotope values ranging from 1 1 to 7 7 across the early paleoproterozoic are strong evidence for an expansion of oxygenated surface waters since the isotopic signature of aerobic nitrogen cycling is recorded in the biomass of nitrate assimilating organisms this implicates widespread nitrate bioavailability in this time interval the decline in offshore nitrogen isotope ratios in the mesoproterozoic is consistent with the contraction of oxic waters which could have inhibited the expansion of nitrate fueled ecosystems to pelagic waters until the widespread oxygenation of the ocean in the latest neoproterozoic to early phanerozoic

correlation of paleoproterozoic glaciations based on u pb zircon ages for tuff beds in the transvaal and huronian supergroups abstract the rise in atmospheric oxygen between 2 45 and 2 2 ga has been linked to the demise of a methane rich atmosphere and the onset of multiple glaciations culminating in a possible snowball earth the glacial deposits represent possible global marker horizons however their correlation is uncertain because key sedimentary successions are undated hampering paleoenvironmental reconstructions three potentially global glaciations have been proposed based on the correlation of glacial deposits in southern africa with those in north america however it has also been suggested that there were four glaciations and that the youngest was a snowball earth event recorded only in south african successions in situ u pb zircon ages for tuffs in southern african and north american successions establish the existence of four glaciations between 2 45 and 2 22 ga geochronological and stratigraphic data demonstrate that the three oldest glaciations predate 2 31 ga and that the final glaciation which is only recognized in south africa occurred between 2 26 and 2 22 ga the new age calibrated correlations show that a rise in atmospheric oxygen inferred from sulfur isotope data occurred between the second and third glaciations at 2 31 ga the first marine sulfate evaporites were deposited contemporaneously with 13 c enriched carbonates indicating a direct link between perturbations of the carbon and sulfur cycles and rising atmospheric oxygen the appearance of red beds and oxidized palesols after the third glaciation signals a major increase in atmospheric oxygen levels which culminated with the fourth glaciation between 2 26 and 2 22 ga after which the atmosphere remained irreversibly oxygenated

chemostratigraphy of carbonates from the minas supergroup quadrilatero ferryifero iron quadrangle brazil a stratigraphic record of early proterozoic atmospheric biogeochemical and climactic change the ca 2 42 ga old gandarela formation overlies the finely laminated caue banded iron formation bif of the itabira group minas supergroup brazil and consists of red carbonate facies bif grading upsection into buff dolomites and limestones which are locally stromatolitic carbonates of the gandarela formation have 1 3 c values ranging narrowly from 1 6 to 0 4 permil versus pdb n 93 the cercadinho formation at the base of the overlying piracicaba group is a thick arenaceous succession with rare thin carbonates that have 1 3 c values ranging from 3 3 to 5 4 permil n 12 stromatolitic dolomites of the overlying fecho do funil formation have pb pb carbonate age 2 11 0 11 ga babinski and others 1995 that provide the minimum age for this unit and 1 3 c values ranging from 5 6 to 7 4 permil n 69 at present we find no evidence in brazil for the any of the three early paleoproterozoic glacial events recognized in 2 45 to 2 22 ga sedimentary successions in north america given the radiometric constraints however it is possible that geological and geochemical traces of these ice ages are missing along the unconformity between the gandarela and cercadinho formations if correct carbonates of the gandarela formation may provide a record of the carbon isotope composition of the seawater prior to any of the paleoproterozoic ice ages combined with other available 1 3 c data results from the gandarela formation suggest that seawater preceding the ice ages was not significantly enriched in 1 3 c on the other hand the carbon isotopic signature of the cercadinho carbonates and chemical composition of the cercadinho arenites are consistent with deposition after the end of the glacial epoch and likely during the early stage of ca 2 22 to 2 1 ga carbon isotope excursion the 1 3 c values of marine carbonates of the fecho do funil formation are consistent with carbon isotope record of contemporaneous carbonate successions worldwide providing additional evidence for a global biogeochemical anomaly at ca 2 22 to 2 1 ga these compositional and isotopic changes allow integration of the minas supergroup into the global record of the paleoproterozoic evolution as well as correlation with other successions of similar age

isotope stratigraphy of the ediacarian neoproterozoic iii of the adelaide rift complex australia and the overprint of water column stratification abstract this study establishes a high resolution 13c chemostratigraphic framework for the type ediacarian terminal proterozoic section in the adelaide rift complex a framework that contributes to the emerging global chronostratigraphic synthesis of a period that saw momentous changes in the earth s surface environment only 15 m of the 3 5 km thick type section consists of shallow water carbonates of the kind that have formed the basis of most previous studies of neoproterozoic chemostratigraphy however the organic 13corg record reveals a surprising richness of information and shows excellent utility in correlation between sections in the adelaide rift complex lateral variations in 13corg profiles correspond to expected diachronous patterns of basin fill with the addition of 87sr 86sr data correlation can also be made to the officer and amadeus basins consistent with known lithostratigraphic and sequence stratigraphic constraints sublittoral micritic carbonates of the upper nuccaleena formation cap dolostone and lower and middle wonoka formation show strong basinwide 13c depletion 13ccarb 3 to 10 despite compelling evidence for preservation of depositional 13ccarb such as good textural preservation evidence for sea floor lithification and in the wonoka formation pristine 87sr 86sr and low mn sr associated with the depleted carbonates are rare subaqueous evaporite relatively heavy 13corg and anomalously 13c depleted organic carbon of benthic microbial mat origin and a common cause salinity stratification of the water column is postulated the indicated palaeogeographic setting an evaporative mediterranean like basin tenuously connected to the world ocean is entirely consistent with previous suggestions of one or more messinian type desiccation events to explain very deep 1 km incised valleys or canyons in the adelaide rift complex and officer basin at horizons within the wonoka formation and correlates positive excursions in 13corg during basin stratification may in part be due to 12c depletion of surface waters by photosynthetic carbon fixation despite the proposed semi isolation of australian ediacarian basins from the world ocean major 13c excursions which can to some extent be differentiated by the monotonic rise in ediacarian marine 87sr 86sr appear to be correlatable to the upper windermere supergroup northwest canada

marine carbon reservoir corg ccarb coupling and the evolution of the proterozoic carbon cycle the post 2 0 ga proterozoic c isotope record reveals two distinct yet interrelated trends a stepwise increase in average 13c from 0 calculated with respect to the peedee belemnite isotope standard prior to ca 1 3 ga to 5 in the neoproterozoic and a concomitant increase in the magnitude of isotopic excursions steady state and non steady state models suggest that these fundamental changes are best explained by a combination of evolving burial fluxes and a secular decrease in the size of the marine dissolved inorganic carbon dic reservoir the dic reservoir size affects the sensitivity of the isotopic system to biogeochemical perturbation major rearrangements of carbon cycling during the proterozoic in part related to the evolving marine carbon reservoir permit elevated 13c values to be sustained for geologically long time spans recognition of this dependence on dic reservoir size provides for the first time a direct link between changing carbonate precipitation styles and the marine c isotope record and may help constrain estimates of proterozoic p co2

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

bioavailability of zinc in marine systems through time zinc is a marine nutrient that may have been limited in the early oceans estimates of marine zinc availability through time suggest that values were instead near modern during the proterozoic eon

u pb detrital zircon geochronology of the turee creek group hamersley basin western australia timing and correlation of the paleoproterozoic glaciations the early paleoproterozoic turee creek group tcg hamersley basin western australia records a continuous siliciclastic dominated sedimentary sequence across the great oxidation event goe and contains at least two glacial horizons showing many similarities with other paleoproterozoic glaciogenic deposits from north america huronian supergroup and south africa transvaal supergroup the correlation between these glacial events is uncertain however because of a lack of geochronological constraints contradictory stratigraphic correlations among di ff erent cratons and the occurrence of numerous sedimentary discontinuities in the transvaal and huronian successions in this study we performed in situ u pb dating of detrital zircons from drill core and surface samples of the tcg the underlying boolgeeda iron formation of the hamersley group and the overlying beasley river quartzite of the lower wyloo group over 1500 zircons analyzed by laser ablation coupled to icp ms yielded major age peaks spanning the archean eon at ca 2 45 ga 2 54 ga 2 68 ga and minor ones at 2 81 ga 2 96 ga and 3 14 ga a younger age of 2340 22 ma obtained at the base of the main glacial deposit of the meteorite bore member represents a maximum age for this glacial event a meter scale level of diamictite has previously been described in the boolgeeda formation at the boundary ridge locality located about 50 km to the east of the meteorite bore member succession and a similar horizon was newly identi fi ed in drill core samples from the hardey syncline area the youngest detrital zircons have an age of ca 2 45 ga in these dia mictites supporting the hypothesis that these horizons represent a di ff erent and older glacial event than the meteorite bore member considering that the tcg and underlying boolgeeda iron formation are in sedimentary continuity these results allow establishing a correlation with the other glaciogenic deposits recorded in the north america and southern africa basins and reconstructing the sequence of redox and climate changes at tending the early paleoproterozoic

a multiscale numerical study of hurricane andrew 1992 part iii dynamically induced vertical motion abstract in this study the vertical force balance in the inner core region is examined through the analysis of vertical momentum budgets using a high resolution explicit simulation of hurricane andrew 1992 three dimensional buoyancy and dynamically induced perturbation pressures are then obtained to gain insight into the processes leading to the subsidence warming in the eye and the vertical lifting in the eyewall in the absence of positive buoyancy it is found from the force balance budgets that vertical acceleration in the eyewall is a small difference among the perturbation pressure gradient force pgf buoyancy and water loading the azimuthally averaged eyewall convection is found to be conditionally stable but slantwise unstable with little positive buoyancy it is the pgf that is responsible for the upward acceleration of high e air in the eyewall it is found that the vertical motion and acceleration in the eyewall are highly asymmetric and closely related to the azimuthal distribution

a multiscale numerical study of hurricane andrew 1992 part ii kinematics and inner core structures despite considerable research understanding of the temporal evolution of the inner core structures of hurricanes is very limited owing to the lack of continuous high resolution observational data of a storm in this study the results of a 72 h explicit simulation of hurricane andrew 1992 with a grid size of 6 km are examined to explore the inner core axisymmetric and asymmetric structures of the storm during its rapid deepening stage based on the simulation a conceptual model of the axisymmetric structures of the storm is proposed most of the proposed structures confirm previous observations the main ingredients include a main inflow outflow in the boundary layer upper troposphere with little radial flow in between a divergent slantwise ascent in the eyewall a penetrative dry downdraft at the inner edge of the eyewall and a general weak subsiding motion in the eye with typical warming drying above an inversion located near an altitude of about 2 3 km the storm deepens as the axes of these features contract it is found that the inversion divides the eye of the hurricane vertically into two parts with a deep layer of warm dry air above and a shallow pool of warm moist air below the air aloft descends at an average rate of 5c m s 21 and has a residency time of several days in contrast the warm moist pool consists of air from the main inflow and penetrative downdrafts offset somewhat by the air streaming in a returning outflow into the eyewall in the lowest 2 km it is subject to the influence of the upward heat and moisture fluxes over the underlying warm ocean the warm moist pool appears to play an important role in supplying high ue air for deep convective development in the eyewall the penetrative downdraft is dry and originates from the return inflow in the upper troposphere and it is driven by sublimative evaporative cooling under the influence of the asymmetric radial inflow of dry cold air in the midtroposphere it penetrates to the bottom of the eye azimuthally downshear with a width often greater than 100 km in a radially narrow zone along the slantwise inner edge of the eyewall it is further shown that all the meteorological fields are highly asymmetric whereas the storm scale flow features a source sink couplet in the boundary layer and dual gyres aloft the inner core structures exhibit alternative radial inflow and outflow and a series of inhomogeneous updrafts and downdrafts all the fields tilt more or less with height radially outward and azimuthally downshear furthermore pronounced fluctuations of air motion are found in both the eye and the eyewall sometimes a deep layer of upward motion appears at the center of the eye all these features contribute to the trochoidal oscillation of the storm track and movement the main steering appears to be located at the midtroposphere 4 5 km and the deep layer mean winds represent well the movement of the hurricane

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

selenium isotopes record extensive marine suboxia during the great oxidation event abstract it has been proposed that an oxygen overshoot occurred during the early paleoproterozoic great oxidation event goe in association with the extreme positive carbon isotopic excursion known as the lomagundi event moreover it has also been suggested that environmental oxygen levels then crashed to very low levels during the subsequent extremely negative shunga francevillian carbon isotopic anomaly these redox fluctuations could have profoundly influenced the course of eukaryotic evolution as eukaryotes have several metabolic processes that are obligately aerobic here we investigate the magnitude of these proposed oxygen perturbations using selenium se geochemistry which is sensitive to redox transitions across suboxic conditions we find that 82 78se values in offshore shales show a positive excursion from 2 32 ga until 2 1 ga mean 1 03 0 67 selenium abundances and se toc total organic carbon ratios similarly show a peak during this interval together these data suggest that during the goe there was pervasive suboxia in near shore environments allowing nonquantitative se reduction to drive the residual se oxyanions isotopically heavy this implies o2 levels of 0 4 m in these settings unlike in the late neoproterozoic and phanerozoic when negative 82 78se values are observed in offshore environments only a single formation evidently the shallowest shows evidence of negative 82 78se this suggests that there was no upwelling of se oxyanions from an oxic deep ocean reservoir which is consistent with previous estimates that the deep ocean remained anoxic throughout the goe the abrupt decline in 82 78se and se toc values during the subsequent shunga francevillian anomaly indicates a widespread decrease in surface oxygenation

multiple sulfur and iron isotope composition of magmatic ni cu pge sulfide mineralization from eastern botswana we report here high precision multiple sulfur and iron isotope compositions for a series of mineralized samples from ni cu pge sulfide deposits in the archean tati greenstone belt and the phikwe complex of eastern botswana mineralized samples from the phoenix and selkirk ni cu pge deposits in the tati greenstone belt display slightly positive 34s isotope values ranging from 0 2 to 0 8 v cdt 33s values of sulfides at phoenix and selkirk are 0 01 to 0 08 v cdt suggesting either a dominantly mantle sulfur source or effective eradication of a crustal 33s anomaly through equilibration with large amounts of silicate melt in the selebi phikwe belt a granite gneiss terrane with abundant amphibolite lenses of either volcanic and or intrusive nature mineralized lower grade samples from the phikwe phokoje and dikoloti ni cu pge deposits have more variable 34s values ranging from 3 1 to 0 3 and display significant mass independent anomalies 33s values ranging from 0 89 to 0 27 suggesting that barren sulfides associated with distal or low temperature sea floor hydrothermal activity contributed sulfur to these deposits iron isotopes of sulfides from these deposits show a relatively small range of negative 56fe values 0 29 to 0 04 consistent with high temperature fractionations in magmatic systems with the exception of one sample from the dikoloti ni cu pge deposit of the selebi phikwe greenstone belt which shows a more negative 56fe value of 0 61 consistent with assimilation of sedimentary or hydrothermal sulfides rather than fractionations in high temperature magmatic systems data from this study highlight the complexity and variability that characterize ore forming processes in magmatic systems we suggest that the presence of sulfur bearing lithologic units in host rocks of mafic and ultramafic intrusions may not be essential toward the assessment of the prospectivity of a province to host orthomagmatic nickel sulfides geologic settings without any or little sulfur in the stratigraphy which have been traditionally neglected in terms of their prospectivity should thus be revisited and possibly reassessed considering the potential importance of external source of sulfur to generate ore deposits

a statistical analysis of the carbon isotope record from the archean to phanerozoic and implications for the rise of oxygen organic and inorganic carbon isotope records reflect the burial of organic carbon over geological timescales permanent burial of organic carbon in the crust or mantle oxidizes the surface environment atmosphere ocean and biosphere by removing reduced carbon it has been claimed that both organic and inorganic carbon isotope ratios have remained approximately constant throughout earth9s history thereby implying that the flux of organic carbon burial relative to the total carbon input has remained fixed and cannot be invoked to explain the rise of atmospheric oxygen schidlowski 1988 catling and others 2001 holland 2002 holland 2009 kump and others 2009 rothman 2015 however the opposite conclusion has been drawn from the same carbon isotope record des marais and others 1992 bjerrum and canfield 2004 to test these opposing claims we compiled an updated carbon isotope database and applied both parametric and non parametric statistical models to the data to quantify trends and mean level changes in fractional organic carbon burial with associated uncertainties and confidence levels we first consider a conventional mass balance model where carbon input to surficial reservoirs is balanced by burial of sedimentary carbonates and organic carbon for this model statistical analysis implies fractional organic burial has increased over earth history by a factor of 1 5 relative to organic burial at 3 6 ga with the 95 percent confidence interval ranging from factors of 1 2 to 2 0 an increase in organic burial by a factor of 1 2 cannot explain the rise of oxygen whereas an increase by a factor of 2 could conceivably explain the rise of oxygen there is however a highly significant and well constrained increase in organic burial from the proterozoic to the phanerozoic we also analyze changes in the difference between carbonate and organic carbon isotopic ratios over earth history there is a statistically significant increase in this difference from the early to late archean possibly caused by increased biological fractionation due to methanotrophic recycling this transition is consistent with the evolution of oxygenic photosynthesis at 2 8 ga or earlier finally we explore how these conclusions change if we modify the traditional mass balance model to include other carbon cycle fluxes specifically ocean crust carbonatization and authigenic carbonates because the size of these fluxes has a large poorly constrained range our statistical analysis with this uncertainty implies that the carbon isotope record does not constrain the history of organic burial at all however it remains possible that the magnitude of these additional processes has been inconsequential throughout geologic time in which case conclusions from the conventional model would be valid

carbon isotope record for the onset of the lomagundi carbon isotope excursion in the great lakes area north america carbonate units of the chocolay group in the lake superior area usa and the gordon lake formation of the correlative upper huronian supergroup ontario canada were deposited after the last paleoproterozoic glacial event and an episode of intense chemical weathering the huronian supergroup contains at the base 2 45 ga volcanics and is intruded by the 2 22 ga nipissing diabase dykes and sills while the chocolay group is bracketed in age between 2 29 and 2 20 ga the lomagundi 2 22 2 1 ga carbon isotope excursion started after the paleoproterozoic glacial epoch and before a plume breakout event at 2 22 ga therefore the chocolay and upper huronian carbonates were deposited either before or during the onset of the lomagundi event notably thin carbonates of the basal gordon lake formation and thick carbonate succession of the kona dolomite in the northeastern exposures of the chocolay group record 13 c values as high as 9 5 versus v pdb similar to other successions deposited during the lomagundi event both units contain pseudomorphs and molds after sulfates this observation suggests that seawater sulfate contents rose dramatically in association with the onset of the lomagundi event and the rise of atmospheric oxygen carbonates in the western and southern exposures of the chocolay group randville and bad river dolomites and saunders formation previously assumed to be equivalent to the gordon lake formation and kona dolomite have carbon isotope values close to 0 based on basin analysis we infer that these carbonate units were deposited during a negative carbon isotope excursion after the lomagundi event started and are slightly younger than the kona dolomite and gordon lake formation this interpretation implies that the carbonate platform in the great lakes area transgressed to the west over shallow marine and fluvial deposits the negative carbon isotope excursion in the lake superior area might correspond to similar 13 c values of the mooidraai dolomite in the griqualand west basin south africa supporting correlation between paleoproterozoic successions of north america and south africa and the notion of three global glaciations in the paleoproterozoic era carbonates of the mille lacs group trout lake glen township and denham formations in minnesota have 13 c values ranging from 1 2 to 2 5 combined with geochronologic constraints these data suggest that these units were deposited after the lomagundi excursion and are related to the rifting event that led to development of the so far unrecognized 2 0 ga passive margin in the lake superior area 2006 elsevier b v all rights reserved

a review of temporal constraints for the palaeoproterozoic large positive carbonate carbon isotope excursion the lomagundi jatuli event abstract the palaeoproterozoic lomagundi jatuli event is one of the largest magnitude and earliest known positive carbonate carbon isotope excursions preserving 13 c values between 5 and 16 and even higher it is recorded in sedimentary rocks on all continents bar antarctica and spans stratigraphic thicknesses ranging from several to many tens of metres this unique positive 13 c interval signals fundamental changes in the global carbon cycle and is a key event in earth system evolution following oxygenation of earth s atmosphere here we present a comprehensive review of the age constraints on the lomagundi jatuli event the first such effort in two decades this new chronology compilation focuses on the u pb and re os chronometers and demonstrates that global synchronicity of the lomagundi jatuli event is permissible an interpretation supported by the apparent wide dispersion of lomagundi jatuli event bearing successions in the most recent palaeoproterozoic plate reconstructions assuming the lomagundi jatuli event is synchronous worldwide then the bounds on its duration range from a maximum of 249 9 myr 2306 9 ma to 2057 1 ma to a minimum of 128 9 4 myr 2221 5 ma to 2106 8 ma

chemostratigraphy of paleoproterozoic carbonate successions of the wyoming craton tectonic forcing of biogeochemical change the archean wyoming craton is flanked on the south and east by belts of paleoproterozoic supracrustal successions whose correlation is complicated by lack of geochronologic constraints and continuous outcrop however carbonate units in these successions may be correlated by integrating carbon isotope stratigraphy with lithostratigraphy the 10 km thick paleoproterozoic snowy pass supergroup in the medicine bow mountains was deposited on the present day southern flank of the wyoming craton it contains three discrete levels of glacial diamictite correlative with those in the huronian supergroup on the southern margin of the superior craton the nash fork formation of the upper snowy pass supergroup is significantly younger than the uppermost diamictite and was deposited after the end of the paleoproterozoic glacial epoch carbonates at the base of the nash fork formation record remarkable 13 cenrichment up to 28 v pdb whereas those from overlying members of the lower nash fork formation have d 13 c values between 6 and 8 carbonates from the upper nash fork formation above the carbonaceous shale have carbon isotope values ranging between 0 and 2 5 the transition from high carbon isotope values to those near 0 in the nash fork formation is similar to that at the end of the ca 2 2 2 1 ga carbon isotope excursion in fennoscandia this chemostratigraphic trend and deposition of bifs mn rich lithologies carbonaceous shales and phosphorites at the end of the global ca 2 2 2 1 ga carbon isotope excursion are likely related to ocean overturn associated with the final breakup of the kenorland supercontinent correlative carbonates from the slaughterhouse formation in the sierra madre wy and from the whalen group in the rawhide creek area in the hartville uplift wy have highly positive carbon isotope values in contrast carbonates from other exposures of the whalen group in the hartville uplift and all carbonate units in the black hills sd have carbon isotope values close to 0 combined with existing geochronologic and stratigraphic constraints these data suggest that the slaughterhouse formation and the succession exposed in the rawhide creek area of the hartville uplift are correlative with the lower and middle nash fork formation and were deposited during the ca 2 2 2 1 ga carbon isotope excursion the estes and roberts draw formations in the black hills and carbonates from other exposures in the hartville uplift postdate the ca 2 2 2 1 ga

diabatic divergence profiles in western pacific mesoscale convective systems abstract heating in the atmosphere can be expressed as diabatic divergence d which is nearly equal to the actual horizontal divergence in tropical convection high quality profile measurements from airborne doppler radar purls in ten mesoscale convective systems mcs observed during toga coare are examined and the mean profile is compared with rawinsonde array measurements young convective features have strong near surface convergence while older cells with better developed downdrafts and stratiform precipitation areas have their peak convergence aloft in the mean then surface flow is only weakly convergent or oven divergent so that the main convergence into mcss is deep and peaked aloft with a sharp melting convergence at 0 c divergence prevails above 10 km altitude but was undersampled by the radar unusual but well sampled observations in the purl dataset include a persistent widespread profile feature in one well sampled mcs a cyclone rainband oscillatory reverberations c

the nature of the δ13c of periplatform sediments implications for stratigraphy and the global carbon cycle the carbon isotopic composition y 13 c of bulk carbonates obtained from a transect of sites drilled through platform and periplatform sediments of holocene to early miocene age has been compared to ascertain whether changes in the y 13 c can be correlated between sediments of equivalent ages and whether such changes can be related to global changes in the y 13 c of the dissolved inorganic carbon in the oceans over this time period five of the sites were drilled during leg 166 of the ocean drilling project 1003 1007 in a transect ranging from five km to 25 km away from the platform margin and penetrating sediments of holocene to oligocene age that are contained in 17 depositional sequences a q two shallow water sites clino and unda were situated on a extension of the same transect on great bahama bank in a water depth of 10 15 m with the exception of unda and clino the y 13 c of the carbonates ranges from 5x in the younger sequences to 1x in the early miocene in each of the sites the y 13 c is strongly positively correlated with the percentage of aragonite as a consequence the y 13 c of sequences a through f is strongly correlated reflecting the decreasing amount of aragonite with increasing depth in the two platform sites the y 13 c is significantly lower in the younger portions of the cores as a result of the influences of meteoric diagenesis during repeated exposure during the pleistocene although the y 13 c of the individual sequences can be correlated in most instances between the odp holes the changes are not related to global changes in the y 13 c of the oceans which in contrast to the y 13 c of the platform sediments become isotopically lower towards the present day instead variations in the y 13 c appear to be related to varying mixtures of y 13 c rich banktop sediments and pelagic material

pyrite multiple sulfur isotope evidence for rapid expansion and contraction of the early paleoproterozoic seawater sulfate reservoir abstract earth s oxygenation is often described in terms of two unidirectional steps at the beginning and end of the proterozoic eon separated by a long lived intermediate redox state recent work defines a more complicated path to oxygenation exemplified by an apparent drop in oxidation state following the early paleoproterozoic lomagundi carbon isotope excursion the timing of this proposed drop in oxidation state is not well constrained and it is not clear how it relates to redox conditions during the remainder of the proterozoic here we present a study of pyrite multiple sulfur isotopes supported by fe speciation and organic carbon isotopes from early paleoproterozoic black shales we find evidence for the rapid expansion of the seawater sulfate reservoir during the great oxidation event at ca 2 3 ga followed by a subsequent contraction in the size of the seawater sulfate reservoir at ca 2 05 ga this scenario is consistent with the emerging view of a rise and fall in surface oxidation state during the early paleoproterozoic comparison of our new data to other records of the seawater sulfate reservoir suggests that the elevated sulfate concentrations that characterize the early paleoproterozoic did not return until the late neoproterozoic

a multilayered water column in the ediacaran yangtze platform insights from carbonate and organic matter paired δ13c abstract large carbon isotope fluctuations have been systematically reported for ediacaran carbonate rocks the meaning of which remains controversial in order to better understand the mechanisms behind such variations we present new paired 13c data on carbonates 13ccarb and their associated organic matter 13corg from a shelf margin section yangjiaping of the doushantuo formation in this section the doushantuo formation starts with cap dolostones presenting 13ccarb values around 5 and 13corg values between 30 3 and 27 6 up section phased variations in 13ccarb and 13corg describe positive and negative excursions while their difference 13cdol org 13ccarb 13corg remains around 29 2 these new data allow the first reconstruction of lateral variations of 13ccarb 13corg and 13ccarb org for a shelf to basin cross section of the yangtze platform south china after integration with results reported previously for two other sections across the yangtze platform the isotope signals reveal strong lateral heterogeneities with complex variations of 13ccarb and 13cdol org in the inner shelf section phased variations in the shelf margin section with positive 13ccarb and 13cdol org close to 29 and dominantly negative 13ccarb with 13corg as low as 35 in the basin these variations are incompatible with the idea that the 13ccarb can systematically be used as a proxy of ocean surface waters assuming that 13ccarb are acquired in bottom waters and or upper sediments we show that the heterogeneous 13ccarb and 13cdol org are compatible with a stratified water column composed of up to three layers i an oxic surface layer where dissolved inorganic carbon dic is probably in isotope equilibrium with the atmosphere ii an intermediate euxinic layer with a lower 13cdic due to organic matter oxidation by ongoing sulphate reduction iii a bottom euxinic layer that seems to be restricted to the inner shelf lagoonal facies lacking sulphate containing methane and with a higher 13cdic due to dic production by methanogenesis if our model holds true it suggests that not only negative but also positive ediacaran carbon isotope excursions may reflect ocean stratification the positive excursion possibly recording a sulphate free methanogenic layer at the bottom of restricted basins

on the distribution of subsidence in the hurricane eye two hurricane eye features that have yet to be adequately explained are the clear air moat that forms at the outer edge of the eye and the hub cloud that forms near the circulation centre to investigate whether these features can be explained by the spatial distribution of the subsidence field we have derived an analytical solution of the sawyer eliassen transverse circulation equation for a three region approximation with an unforced central eye region of intermediate or high inertial stability a diabatically forced eyewall region of high inertial stability and an unforced far field of low inertial stability this analytical solution isolates the conditions under which the subsidence is concentrated near the edge of the eye the crucial parameter is the dimensionless dynamical radius of the eye defined as the physical radius of the eye divided by the characteristic rossby length in the eye when this dimensionless dynamical radius is less than 0 6 there is less than 10 horizontal variation in the subsidence rate across the eye when it is greater than 1 8 the subsidence rate at the edge of the eye is more than twice as strong as at the centre of the eye when subsidence is concentrated at the edge of the eye the largest temperature anomalies occur near there rather than at the vortex centre this warm ring structure as opposed to a warm core structure is often observed in the lower troposphere of intense hurricanes copyright 2007 royal meteorological society

exceptional preservation of expandable clay minerals in the ca 2 1 ga black shales of the francevillian basin gabon and its implication for atmospheric oxygen accumulation abstract clay minerals are exceptionally well preserved in marine black shale of the ca 2 1 ga francevillian group in southeastern gabon the fb formation of the francevillian group is characterized by smectite rich clay minerals including randomly ordered r0 type and ordered r1 type mixed layer illite smectite i s the preservation of r0 type clay minerals suggests unexpectedly slow mineral transformation and a moderate degree of diagenesis which is unique considering the paleoproterozoic age of the sedimentary rocks r0 and r1 type smectite rich particles occur in stratigraphic intervals with high organic carbon content and are associated with carbonaceous filamentous structures suggesting formation of clay organic matter complexes our data suggests that clay minerals may have enhanced organic matter preservation providing the oldest example where a link between clay minerals and organic matter sequestration can be established our findings are consistent with the hypothesis that clay minerals enhanced organic carbon burial and aided in atmospheric oxygen accumulation through time

molybdenum record from black shales indicates oscillating atmospheric oxygen levels in the early paleoproterozoic the early paleoproterozoic witnessed earth9s first major oxygenation referred to as the great oxidation event or goe the goe began around 2 45 billion years ago ga and progressed over hundreds of millions of years as evidenced by multiple redox indicators before coming to an abrupt end by ca 2 06 ga the details of the goe and the extent of oxygenation are still not resolved however and it is not clear how redox conditions across the goe compare with those during the middle proterozoic in order to investigate the evolution of deep ocean redox conditions during the goe we present mo concentration and isotope data together with fe speciation values for three key organic matter rich shale units of the early paleoproterozoic age 2 32 2 06 ga in addition we present a new graphical representation of modeling suggesting that the oceanic mo isotope system is highly sensitive to the balance between anoxic suboxic and euxinic conditions until deep ocean oxygenation similar in scale to modern ocean oxygenation is reached our approach indicates rising yet oscillating atmospheric oxygen at 2 32 ga leading to an abrupt increase in mo supply to the oceans and large mo isotope variations under non steady state conditions the low seawater 98mo value based on the ca 2 32 ga black shales 0 32 0 58 suggests that the oceans were still largely anoxic with locally developed euxinic conditions between 2 2 and 2 1 ga during the peak of the lomagundi carbon isotope excursion we observe higher 98mosw values 1 23 0 36 together with lower mo concentrations in euxinic shales mo 6 3 9 0 ppm we suggest that a decrease in the continental mo input flux in the later part of the goe was the main cause of this trend lower sulfide availability on the continents after protracted sulfide weathering associated with the early stages of the goe and efficient mo removal in poorly oxygenated oceans under weakly euxinic conditions would both have contributed to the contraction of the mo oceanic reservoir by ca 2 06 ga the mo isotope composition of seawater as inferred from euxinic black shale intervals became significantly lighter 0 70 0 21 reflecting an increased rate of quantitative mo removal due to the more widespread development of strongly euxinic conditions counterintuitively seawater mo concentrations recovered likely due to an increase in the mo input which in turn might reflect enhanced weathering of organic carbon rich shales deposited during the lomagundi event

fractionation between inorganic and organic carbon during the lomagundi 2 22 2 1 ga carbon isotope excursion article i nfo the lomagundi 2 22 2 1 ga positive carbon isotope excursion in shallow marine sedimentary carbonates has been associated with the rise in atmospheric oxygen but subsequent studies have demonstrated that the carbon isotope excursion was preceded by the rise in atmospheric oxygen the amount of oxygen released to the exosphere during the lomagundi excursion is constrained by the average global fractionation between inorganic and organic carbon which is poorly characterized because dissolved inorganic and organic carbon reservoirs were arguably larger in the paleoproterozoic ocean at a time of lower solar luminosity and lower ocean redox state decoupling between these two variables might be expected we determined carbon isotope values of carbonate and organic matter in carbonates and shales of the silverton formation south africa and in the correlative sengoma argillite formation near the border in botswana these units were deposited between 2 22 and 2 06 ga along the margin of the kaapvaal craton in an open marine deltaic setting and experienced lower greenschist facies metamorphism the prodelta to offshore marine shales are overlain by a subtidal carbonate sequence carbonates exhibit elevated 13 c values ranging from 8 3 to 11 2 vs vpdb consistent with deposition during the lomagundi positive excursion the total organic carbon toc contents range from 0 01 to 0 6 and 13 c values range from 24 8 to 13 9 thus the isotopic fractionation between organic and carbonate carbon was on average 30 3 2 8 n 32 in the shallow marine environment the underlying sengoma shales have highly variable toc contents 0 14 to 21 94 and 13 c values 33 7 to 20 8 with an average of 27 0 3 0 n 50 considering that the shales were also deposited during the lomagundi excursion and taking 13 c values of the overlying carbonates as representative of the 13 c value of dissolved inorganic carbon during shale deposition a carbon isotope fractionation as large as 37 appears to characterize the production of bulk organic matter in the deeper part of the pretoria basin at that time this enhanced fractionation relative to that observed in shallow water environments likely reflects heterotrophic secondary and chemotrophic productivity at and below a pronounced redoxcline consistent with the euxinic conditions inferred from independent evidence for the deeper part of the pretoria basin greater variability in organic carbon vs carbonate carbon isotopic values on the shallow marine carbonate platform suggests that the carbon cycling was dominated by a large dissolved inorganic carbon reservoir during the lomagundi excursion our study suggests that in contrast to the late neoproterozoic and phanerozoic when carbon isotope fractionation between carbonate and organic carbon in the open ocean was mostly controlled by primary producers in the paleoproterozoic redox stratified ocean heterotrophic and chemotrophic productivity overprinted a signal of primary productivity below the redoxcline this strong imprint of heterotrophic and chemotrophic productivity on organic carbon isotope records complicates the reconstruction of spatial patterns and secular trends in the 13 c values of dissolved inorganic carbon in the paleoproterozoic seawater

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

interpreting carbon isotope excursions carbonates and organic matter abstract variations in the carbon isotopic compositions of marine carbonate and organic carbon provide a record of changes in the fraction of organic carbon buried through time and may provide clues to changes in rates of weathering and sources of organic carbon paired carbonate and organic carbon isotope determinations provide a possibility of interpreting not only changes in the global carbon cycle through time but changes in atmospheric pco2 as well interpretations of these types of data are typically rather qualitative a quantitative basis is required to develop a better understanding of changes in the carbon cycle for this purpose we employ a simple model of the global carbon cycle which is subjected to a number of different perturbations each lasting 500 ky i e much longer than the residence times of carbon and phosphorus in the ocean atmosphere system in addition to standard considerations of carbon mass and isotopic fluxes to the ocean atmosphere system from weathering and volcanism and fluxes of organic carbon and carbonate carbon to sediments the model incorporates sensitivity of the photosynthetic carbon isotope effect to changes in pco2 the inclusion of this parameter leads to unexpected carbon isotope responses to forcing that causes increased rates of organic carbon burial a series of simple to more complex simulations illustrates the significant effects of varying differences between the carbon isotopic composition of sedimented carbonate and organic carbon b with constant b a 50 increase in organic carbon burial produces a parallel increase in carbonate and organic carbon isotopic compositions however the same simulation with b responsive to pco2 changes produces an initial parallel 13 c increase but this is followed by an even greater 13 c enrichment in organic carbon because pco2 falls in response to increased organic carbon burial the counterintuitive overall result of the enhanced organic carbon burial event is that the carbonate carbon isotopic composition actually decreases because of the more substantial increase in 13 c org in addition we illustrate the effects on carbon isotopic compositions of the oceanic inorganic carbon reservoir and buried organic matter of a 50 increase in volcanic co2 outgassing a 50 increase in weathering rate with coupled phosphate and riverine carbon flux responses a 50 decrease in shale associated organic carbon weathering a 50 decrease in silicate weathering rate and the possible effects of the rise in abundance of c4 plants in the late miocene to recent we compare the model simulated carbon isotopic responses for some of these experiments to paired carbonate and organic carbon records to illustrate how these records might be interpreted in light of the model response

stable isotope thermometry at high temperatures determination of accurate temperatures for geological events has been the grail of stable isotope geochemistry since the seminal 1947 paper by urey in theory this should be simple calibrated mineral pairs are common analysis is rapid and there is no significant pressure correction however in spite of widespread application the promise of reliable thermometry has been elusive stable isotope temperatures in metamorphic and igneous rocks are often controversial is the fractionation between two phases a thermometer speedometer rate dependant hygrometer p h2o dependant or chimera a number of factors have contributed to this uncertainty including incomplete and sometimes conflicting calibration of isotope fractionation factors limited understanding of the kinetics of mineral exchange and the lack of microanalytical techniques this situation has improved dramatically over the past decade permitting reliable and detailed thermal histories to be inferred in a landmark paper bottinga and javoy 1975 empirically calibrated the oxygen isotope fractionation factors among ten rock forming minerals at t 500 c their compilation shows that 84 of analyzed samples contain at least three minerals meeting a concordance test for equilibrium they concluded the great majority of igneous and metamorphic rocks has conserved a state of oxygen isotope exchange equilibrium if correct this bodes well for thermometry however this conclusion was contested by deines 1977 who critically examined the existing data and concluded that less than half of the rocks analyzed to date would yield concordant 18o derived temperatures while seeming irreconcilable both conclusions are based on fact all rocks contain some degree of disequilibrium but many also preserve a thermometric record it is the purpose of this review to discuss the new strategies for reliable isotope thermometry and to explore disequilibrium processes so they may be recognized and properly interpreted the organization of this paper will be to discuss the assumptions

extreme 13c depletions in seawater derived brines and their implications for the past geochemical carbon cycle extreme depletions in the 13c content of the total dissolved inorganic carbon ct were found in brines overlying microbial mat communities total alkalinity at and ct in the brines suggest that intense photosynthetic activity of the microbial mat communities depletes the ct from the brine we suggest that this depletion drives a large kinetic negative fractionation of carbon isotopes similar to that observed in highly alkaline solutions in brines of extreme salinity where microbial mat communities no longer exist the 13c content of the ct increases probably because photosynthesis no longer dominates the gas exchange processes this mechanism explains light carbon isotope compositions of carbonate rocks from evaporitic sections and bears on the interpretation of 13c values in bedded stromatolitic limestones that are ca 3 5 b y old

geochemistry of precambrian carbonates v late paleoproterozoic seawater in an effort to obtain better constrained data for the first and second order variations in the isotopic composition of late paleoproterozoic 1 8 0 2 ga seawater we report a study of mineralogy chemistry and isotopic composition of the coronation supergroup 1 9 ga nwt canada and the mcarthur group 1 65 ga nt australia petrologically both carbonate sequences are mostly dolostones the mcarthur population however contains more abundant textural features that attest to the former presence of sulfates and halite and the facies investigated herein probably represent ancient equivalents of modern evaporitic sabkhas and lacustrine playa lakes this is reflected in 18 o enrichment up to 2 9 pdb and high mn fe and sr concentrations nonetheless the available 18 o data indicate that the best estimate for the archean to late paleoproterozoic limestones is about 7 pdb with dolostones some 3 2 heavier the observed 18 o doiomitc calcite is thus within the range of the proposed fractionation factor for a cogenetic mineral pair this together with the consistency of isotopic patterns for sedimentological facies over almost 2 billion years from the late paleoproterozoic to the present suggest that dolomitization was an early diagenetic event and that the 18 o depletion of the archean to late paleoproterozoic carbonates is not an artefact ofpost depositional alteration the 13 c although within the range of other precambrian and phanerozoic carbonates indicates a possible secular evolution from 0 2 pdb at 1 9 ga ago to 1 1 5 at 1 65 ga ago the secular evolution for reflects the 87 sr increase from 0 7031 0 0008 at 3 5 0 1 ga ago through 0 7025 0 0015 at 2 8 0 2 ga 0 7033 at 2 5 ga 0 7050 at 2 25 0 25 ga 0 7047 at 1 91 to 0 706 at 1 65 ga ago

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