paired carbon isotopic analysis of ordovician bulk carbonate δ 13 c carb and organic matter δ 13 c org spanning the great ordovician biodiversification event abstract paired measurements of bulk carbonate 13ccarb organic matter 13corg and their difference 13c can be used to estimate changes in isotopic fractionation through time as a function of o2 co2 in the atmosphere however because local scale processes can also affect 13c it is essential to compare sections from widely separated water masses here we present new 13corg data from ordovician carbonate rocks from the great basin oklahoma and appalachian basin and compare with published 13ccarb records from these sections and paired 13c values from other carbonate successions around north america these new data complement previous studies that focused on upper ordovician 13ccarb excursions and now provide a composite ordovician 13corg record new lower ordovician tremadocian stage 13corg data range from ca 26 to 28 decreasing throughout the lower middle ordovician floian dapingian stages to ca 29 to 31 13corg values remain at their lowest throughout the sandbian and are similar to other published upper ordovician sandbian katian 13corg data from north america 13c values from well preserved intervals generally vary between 26 to 28 throughout the lower to middle ordovician tremadocian to early darriwilian but increase to 31 during the mid late darriwilian and mid sandbian similar to published data from younger late ordovician positive 13c excursions known as the guttenberg gice and hirnantian hice events the overall 13c trend shows a 3 increase throughout the early middle ordovician and coincides with a previously interpreted period of ocean cooling and some of the earliest pulses of global biodiversity of marine invertebrates and planktonic organisms modeling studies predict that pco2 decreased during this time suggesting that the effect of pco2 on 13c may have been overwhelmed by other controls such as an in increase in po2 or a higher o2 co2 ratio during this biodiversification event

widespread prolonged late middle to late ordovician upwelling in north america a proxy record of glaciation late middle to late ordovician subtidal ramp carbonates of new mexico texas and oklahoma contain abundant spiculitic chert to 70 chert by volume and phosphate 1 5 wt indicating that these rocks formed in an extensive upwelling zone upwelling began in the late middle ordovician ca 454 ma and persisted until the end of the ordovician late ordovician cherty carbonates also occur along the u s cordilleran margin in board of organic rich graptolitic shale and chert the widespread occurrence of late ordovician cherty and phosphatic carbonates on southern and western laurentia in addition to phosphate rich cool water carbonates over much of the north american midcontinent suggests vigorous thermohaline circulation related to prolonged 10 14 ma gondwana glaciation

distribution and characteristics of adirondack class basalt as observed by mini tes in gusev crater mars and its possible volcanic source abstract we identified 104 unique rock targets belonging to the olivine rich adirondack class using mini tes data rare rocks on the west spur of the columbia hills and on the plains east of the hills also belong to this class we present evidence that adirondack class basaltic lavas may have had their origin at apollinaris tholus linear modeling of adirondack class rock spectra shows only minor variations in mineralogy and the primary phases identified are consistent with olivine basalt having an average olivine composition of fo 45 we used factor analysis and target transformation to identify variability within a single class of rocks for the first time and we find that olivine abundance varies independently of a basaltic matrix a spectral component previously attributed to downwelling radiance is proposed here to be attributable to optically thin dust on rocks which has a greater effect on mini tes spectra than previously recognized but can explain the sloping continuum observed in adirondack class rock spectra as well as the apparent distortion of an olivine absorption spectral mixing is not completely linear leading to the overestimation of sulfate and olivine fractions and the underestimation of plagioclase feldspar although linear mixing appears to successfully replicate the majority of the observed signal published tes spectra of low albedo low dust cover olivine bearing materials do not exhibit the spectral telltales of non linear behavior probably because orbital spectra represent mostly mobile regolith that has not accumulated a sufficient dust cover over 3 6 km areas

carbon isotope geochemistry of the frasnian famennian transition abstract carbon isotope records for inorganic and total organic carbon toc as well as for individual organic biomarkers show two positive excursions in the late frasnian with comparable shape and amplitude in 13c the positive shifts in 13c can be correlated with the deposition of the kellwasser horizons the inorganic carbon isotope excursions are explained by an enhanced organic carbon burial that is expected to lower the concentration of oceanic dissolved co2 toc 13c values do not exhibit a larger shift than that recorded by inorganic carbon 13c values this is unexpected since a decrease in the dissolved co2 concentration should result in lower carbon isotope fractionation during photosynthesis ep 13c values of presumed algal biomarkers low molecular weight n alkanes pristane phytane although offset by 2 5 exhibit essentially identical records as toc and confirm this unexpected result it is proposed that high atmospheric and oceanic co2 concentrations during the devonian resulted in maximum photosynthetic fractionation any change in the co2 concentration would thus not affect ep as such 13c of primary organic carbon and 13ccarb will exhibit parallel excursions the data imply that carbon isotopes and the relationship between ep and co2 will not be effective to study changes in pco2 levels during the devonian since co2 concentrations were too high

organic matter source variation and the expression of a late middle ordovician carbon isotope excursion the carbon isotopic composition of organic matter is a powerful tool in the study of organic carbon burial and p co 2 through the geologic record however the organic matter source can affect total organic carbon 13 c values and may complicate interpretation of environmental conditions we examined the influence of organic matter source variations on a late middle ordovician positive 13 c excursion in strata of the united states midcontinent in a core from iowa the magnitude of the excursion recorded by carbonate carbon is 2 5 whereas the excursion recorded by total organic carbon is nearly 8 although this difference could arise from a profound decrease in surface water co 2 concentrations association of the organic walled microfossil gloeocapsomorpha prisca with 13 c enriched total organic carbon toc in this interval suggests that the excursion could also record a shift from normal marine to g prisca dominated organic matter carbon isotope analyses of individual biomarkers indicate that both of these explanations are required to explain the data compounds inferred to be of g prisca origin are enriched in 13 c by 7 relative to compounds derived from other algal sources furthermore compounds exclusively from either g prisca or other sources exhibit a positive shift of only 3 5 thus the large excursion recorded by toc reflects in part a change in the proportional contribution of g prisca to toc that all compounds exhibit a positive carbon isotopic shift indicates that independent of contributions from g prisca a positive organic 13 c excursion occurred and records a change in environmental conditions such as co 2 aq concentrations the 3 5 shift is similar in magnitude to that observed for toc in correlative units from pennsylvania suggesting that this event has broad geographic significance this work illustrates that organic matter source variations as well as environmental conditions govern the toc 13 c values and shows how compound specific isotope analyses can resolve these multiple controls

high resolution isotope stratigraphy of the lower ordovician st george group of western newfoundland canada implications for global correlation the lower ordovician st george group of western newfoundland consists mainly of shallow marine platform carbonates 500 m thick it is formed from bottom to top of the watts bight boat harbour catoche and aguathuna formations the top boundary of the group is marked by the regional st george unconformity outcrops and a few cores from western newfoundland were sampled at high resolution and the extracted micritic materials were investigated for their petrographic and geochemical criteria to evaluate their degree of preservation the d13c and d18o values of wellpreserved micrite microsamples range from 4 2 to 0 vpdb and from 11 3 to 2 9 vpdb respectively the d13ccarb profile of the st george group carbonates reveals several negative shifts which vary between 2 and 3 and are generally associated with unconformities disconformities or thin shale interbeds thus reflecting the effect of or link with significant sea level changes the st george unconformity is associated with a negative d13ccarb shift 2 on the profile and correlated with major lowstand around the end of arenig on the local sea level reconstruction and also on those from the baltic region and central australia thus suggesting that the st george group unconformity might have likely had an eustatic component that contributed to the development enhancement of the paleomargin other similar d13ccarb shifts have been recorded on the st george profile but it is hard to evaluate their global extension due to the low resolution of the documented global lower ordovician tremadoc middle arenig d13ccarb profile

did cooling oceans trigger ordovician biodiversification evidence from conodont thermometry the ordovician period long considered a supergreenhouse state saw one of the greatest radiations of life in earth9s history previous temperature estimates of up to 70 c have spawned controversial speculation that the oxygen isotopic composition of seawater must have evolved over geological time we present a very different global climate record determined by ion microprobe oxygen isotope analyses of early ordovician silurian conodonts this record shows a steady cooling trend through the early ordovician reaching modern equatorial temperatures that were sustained throughout the middle and late ordovician this favorable climate regime implies not only that the oxygen isotopic composition of ordovician seawater was similar to that of today but also that climate played an overarching role in promoting the unprecedented increases in biodiversity that characterized this period

sedimentary corg p ratios paleocean ventilation and phanerozoic atmospheric po2 the corg p ratios of organic rich facies tocn1 exhibit considerable variation through the phanerozoic from b10 1 in the permian phosphoria formation to n1000 1 in some devonian black shales relative to the composition of phytoplankton c p 106 1 which provide the bulk of organic c and p to organic rich marine sediments the range of phanerozoic sedimentary corg p ratios largely reflects the influence of benthic redox conditions on diagenetic pathways of c and p remobilization enhanced preservationoforganiccatlowerredoxpotentials combinedwithenhancedsedimentaryretentionofremineralizedorganicpathigher redox potentials results in a strong relationship between benthic redox conditions and sedimentary corg p ratios the strong secular coherence of the phanerozoic corg p record i e limited variation within narrow time slices suggests that these ratios are controlled primarily by factors influencing benthic redox conditions on a global scale such as atmospheric po2 inversion and scaling of the phanerozoic corg p record yields a new atmospheric po2 model that has strong similarities to existing models based on elemental and isotopic mass balances yet differs in some potentially significant respects in particular the new model suggests that atmospheric po2 wasmarkedlylowerduringtheearlytomiddlepaleozoicthanpreviouslyinferred duringmostofthedevonian atmospherico2levels mayhavebeensufficientlylow b13 astopreventthesustainedcombustionofplantmaterial thisfeatureofthemodelmayaccount for ananomalous gapinthefossilcharcoalrecordduringthedevonian theredox dependentburialofpintheoceanresults inpositive and negative feedback mechanisms that tend to stabilize atmospheric oxygen concentrations on geologic timescales temporal variations in the burial of p relative to c suggest that the strength of these feedback mechanisms varied over the phanerozoic 2007 elsevier b v all rights reserved

strontium and carbon isotope stratigraphy of the llandovery early silurian implications for tectonics and weathering abstract a high resolution 87sr 86sr curve and paired 13c carbonate organic data set is generated for the llandovery series from the ikla drill core in estonia a 13c carbonate curve is also presented from the pancake range in nevada observed 87sr 86sr values in the ikla drill core are at a minimum in the early llandovery rhuddanian stage 0 7079 to 0 7080 and then trend to more radiogenic ratios in the basal part of the telychian stage an 87sr 86sr high near 0 7084 is observed in the telychian at the top of the studied section the range of values is in general agreement with the data from previous sample sets of brachiopods and conodonts recovered from localities in north america and europe that record a rising trend in the 87sr 86sr ratio throughout the llandovery from approximately 0 7080 to 0 7084 the major increase in the 87sr 86sr ratio during the late llandovery may be due to weathering of radiogenic source rocks that were uplifted during early silurian continent continent collisions the sr rise potentially coincides with the occurrence of an unusually thick sequence of k bentonite beds representing large magnitude ash falls in the early telychian a previously documented negative 13c excursion in marine carbonates in the lower telychian interval of the ikla core is quasi synchronous with the increase in 87sr 86sr our new organic matter 13c data from the ikla core confirm that this negative 13c carbonate excursion is not a result of diagenesis furthermore a negative 13c excursion in carbonates from the early telychian portion of the pancake range section in nevada seems to confirm the global scope of this carbon cycle perturbation

katian upper ordovician delta c 13 chemostratigraphy and sequence stratigraphy in the united states and baltoscandia a regional comparison delta c 13 values of numerous limestone samples from katian upper ordovician successions in oklahoma and the upper mississippi valley document the presence of at least three of the four positive excursions that have been recognized in the lower middle katian interval in the cincinnati region in ohio kentucky and indiana a comparison with estonia reveals that five out of the six positive excursions now recorded through the katian succession in the cincinnati region are present in the coeval stratigraphic intervals in estonia which suggests that these represent global perturbations in the carbon cycle a study of the relations between flooding events and delta c 13 excursions shows that only some of the excursions occur in transgressive intervals whereas other excursions are in regressive strata and hence this is in conflict with the idea that positive carbon isotope excursions are forced by rises in sea level part of a previously published attempt to use upper ordovician sequence stratigraphy for trans atlantic correlation is shown to be seriously out of phase with the biostratigraphy and chemostratigraphy several of the sequences recognized in the cincinnati region do not appear to have counterparts in estonia which suggests that they do not reflect eustatic but local conditions c 2010 elsevier b v all rights reserved less

the great ordovician biodiversification event gobe the palaeoecological dimension abstract the great ordovician biodiversification event gobe saw a spectacular increase in marine biodiversity at all taxonomic levels largely within the phyla established much earlier during the so called cambrian explosion the diversification was probably the result of a combination of several geological and biological processes and the positive feedbacks resulting from them the present paper reviews the palaeoecological dimension of the gobe it involved major increases in s and biodiversity largely associated with the rise of the paleozoic evolutionary fauna dominated by suspension feeders and involving a greater occupation of ecospace and more complex ecological structures in the ecological evolutionary units p1 and p2 in the benthos these include more complex food webs than those of the cambrian greater tiering especially above the sediment water interface and the development of guild structures indicating increased competition between taxa for particular resources the ordovician is characterized by a profound change in reef composition with a switch from microbial dominated reefs in the early and middle ordovician to metazoan dominated reefs in the late ordovician increases in complexity of deep water trace fossil assemblages began in the early ordovician and mark the increasing exploitation in that environment and the development of hardgrounds permitted bioerosion and encrusting strategies together with the appearance of cryptic communities within the water column the gobe involved a significant increase in the diversity of the phytoplankton and the development of a diverse zooplankton including planktotrophic larvae from a range of invertebrate clades this revolution in the plankton enabled the establishment of a diverse fauna of pelagic vertebrates molluscs and arthropods and promoted the rise of suspension feeders in the benthos an escalation amongst predators and thus community evolution may also have been a major driver of biodiversification

a melange of subduction temperatures evidence from zr in rutile thermometry for strengthening of the subduction interface abstract the catalina schist contains a spectacular km scale amphibolite facies melange zone thought to be part of a cretaceous convergent margin plate interface in this setting blocks ranging from centimeters up to 100 m in diameter are surrounded by finer grained matrix that is derived from the blocks blocks throughout the melange represent a diversity of protoliths derived from basalts cherts and other sediments and hydrated mantle but all contain assemblages consistent with upper amphibolite facies conditions suggesting a relatively restricted range of depths and temperatures over which material within the melange was metamorphosed this apparent uniformity of metamorphic grade contrasts with other melanges such as the franciscan complex where coexisting rocks with highly variable peak metamorphic grade suggest extensive mixing of materials along the subduction interface this mixing has been ascribed to flow of material within relatively low viscosity matrix the zr content of rutile in samples from across the amphibolite facies melange of the catalina schist was measured to determine peak metamorphic temperatures identify whether these temperatures were different among blocks and whether the spatial distribution of temperatures throughout the melange was systematic or random resolvably different zr contents between 290 and 720 10 40 ppm are found among the blocks corresponding to different peak metamorphic temperatures of 650 to 730 2 16 c at an assumed pressure of 1 gpa these results are broadly consistent with previous thermobarometric estimates no systematic distribution of temperatures was found however like other melange zones material flow within the catalina schist melange was likely chaotic but appears to have occurred on a more restricted scale compared to some other localities progressive metamorphism of melange matrix is expected to produce rheologically stiffer matrix minerals such as amphiboles and pyroxenes at the expense of weaker matrix minerals sheet silicates affecting the overall rheological behavior of the melange and dictating the scale of flow the catalina schist amphibolite facies melange matrix appears to provide a snapshot of hotter stiffer portions of a subduction interface perhaps more representative of rheological behavior at depths approaching the subarc than is found in some other exhumed melange zones

carbon isotope record of late cambrian to early ordovician carbonates of the argentine precordillera a more than 2000 m thick cambrian ordovician carbonate platform succession developed on the exotic argentine precordillera terrane during rifting from laurentia and drifting towards gondwana on base of these carbonates a carbon isotope curve could be developed for the cambrian ordovician we measured 13ccarb and 13corg values on bulk rocks selected components and diagenetic cements whereas the carbon isotope signals of intertidal and supratidal rocks are altered by diagenesis most subtidal carbonates exhibit primary marine values we can report reliable curves for the middle late cambrian transition and for the latest cambrian to earliest middle ordovician the 13c curve matches well with the published data from global cambrian ordovician boundary sections excursions and shifts in the carbon isotope curve correspond to events in sequence stratigraphy this indicates the interdependence on sea level which rules the productivity and or preservation of organic carbon and therefore the partition between corg and ccarb burial

paired δ13ccarb and δ13corg records of upper ordovician sandbian katian carbonates in north america and china implications for paleoceanographic change late sandbian early katian marine carbonates from two sections in north america and one in south china were analyzed for paired 13ccarb and 13corg and revealed similar 13ccarb but varying trends in 13corg stratigraphy while all sections recorded a well known positive 13ccarb shift these 13corg records are the first through the guttenberg 13ccarb excursion gice in china oklahoma and west virginia in south china a positive excursion in 13corg is associated with the latter part of the positive 13ccarb excursion and closely resembles trends from iowa and pennsylvania that have been interpreted to reflect a lowering of atmospheric pco2 levels the 13corg trends from oklahoma and west virginia differ significantly from what is observed in china this likely indicates that local changes in nutrient cycling and phytoplankton growth rates were the dominant control on 12c fractionation in oklahoma and west virginia masking a possible global signal of lowered atmospheric pco2 levels observed in china

techniques for assessing spatial heterogeneity of carbonate δ13c values implications for craton wide isotope gradients the sedimentary record of carbonate carbon isotopes 13ccarb provides one of the best methods for correlating marine strata and understanding the long term evolution of the global carbon cycle this work focuses on the late ordovician guttenberg isotopic carbon excursion a ca 2 5 positive 13ccarb excursion that is found in strata globally substantial variability in the apparent magnitude and stratigraphic morphology of the guttenberg excursion at different localities has hampered high resolution correlations and led to divergent reconstructions of ocean chemistry and the biogeochemical carbon cycle this work investigates the magnitude spatial scale and sources of isotopic variability of the guttenberg excursion in two sections from missouri usa centimetre scale isotope transects revealed variations in 13ccarb and 18ocarb greater than 2 across individual beds linear 13ccarb to 18ocarb mixing lines together with petrographic and elemental abundance data demonstrate that much of the isotopic scatter in single beds is due to mixing of isotopically distinct components these patterns facilitated objective sample screening to determine the least altered data a 18ocarb filter based on empirical 18ocarb values of well preserved carbonate mudstones allowed further sample discrimination the resulting least altered 13ccarb profile improves the understanding of regional as well as continental scale stratigraphic relations in this interval correlations with other laurentian sections strongly suggest that i small scale variability in guttenberg excursion 13ccarb values may result in part from local diagenetic overprinting ii peak guttenberg excursion 13ccarb values of the midcontinent are not distinct from their taconic equivalents and iii no primary continental scale spatial gradient in 13ccarb for example arising from chemically distinct aquafacies is required during guttenberg excursion time this study demonstrates the importance of detailed petrographic and geochemical screening of samples to be used for 13ccarb chemostratigraphy and for enhancing understanding of epeiric ocean chemistry

dynamic sulfur and carbon cycling through the end ordovician extinction revealed by paired sulfate pyrite δ34s geochemical records of the end ordovician hirnantian stage show parallel positive excursions in the stable isotope compositions of sedimentary pyrite sulfur 34spyr organic carbon 13corg and carbonate carbon 13ccarb these isotope excursions coincide with the end ordovician glaciation and mass extinction a relative increase in pyrite burial fpyr attributed to marine anoxia has been invoked to explain the sulfur isotope excursion and link oceanic redox conditions to the extinction of marine fauna an increase in fpyr would necessarily generate a parallel excursion of equal magnitude in the isotopic composition of coeval marine sulfate 34sso4 34sso4 here we present new high resolution paired sulfur isotope data from carbonate associated sulfate 34scas and pyrite from the hirnantian stage of western anticosti island quebec canada these data document a positive 20 enrichment in 34spyr comparable in magnitude to previous reports but no parallel excursion in 34scas this pattern provides new constraints on the origin of the 34spyr excursion and the nature of carbon sulfur coupling through hirnantian time specifically these observations preclude enhanced pyrite burial as the cause of the hirnantian 34spyr excursion and suggest the possible role of anoxia in the mass extinction may need to be reevaluated rather the global 34spyr excursion is best explained by a transient reduction in the isotopic fractionations expressed during microbial sulfur cycling epyr the epyr record shows a strong inverse correlation with 13c suggesting a mechanistic link between carbon cycling and processes controlling epyr during the hirnantian changes in sea level or marine redox state associated with glaciation could further impact the expression of the biological fractionation e g through syndepositional sediment reworking and or chemocline migration and resultant restricted exchange of porewater sulfate the magnitude of isotopic fractionation during microbial sulfate reduction is partially controlled by metabolic rates which are sensitive to the abundance type and lability of metabolically relevant substrates environmental change associated with the end ordovician glaciation may have elevated the flux of organic material to marine sediments or caused an increase in physical reworking of sediments leading to increased microbial sulfate reduction rates and reduced epyr as such the hirnantian 34spyr excursion may be viewed as a dynamic biological response to global climate change highlighting the connections between the carbon and sulfur biogeochemical cycles

inclusion of the weathering of volcanic rocks in the geocarbsulf model the carbon cycle model geocarbsulf is extended by dividing the weathering of silicates into volcanic and non volcanic rocks the proportion of volcanic weathering is calculated as a function of time from the oceanic record of 87sr 86sr the volcanic proportion is then used to modify the equations for calculating atmospheric co2 by the addition of a new non dimensional volcanic weathering factor the effect of uplift and physical erosion on weathering is also modified by using only the distribution over time of the abundance of sandstones and shales and not sr isotopic data that had been used previously results indicate moderate change from geocarbsulf in the distribution of atmospheric co2 over phanerozoic time this includes an increased minimum in co2 during the late ordovician in agreement with the presence of a continental glaciation at that time and a shift of maximum mesozoic values from the jurassic to the early cretaceous

calibration of a conodont apatite based ordovician 87sr 86sr curve to biostratigraphy and geochronology implications for stratigraphic resolution the ordovician 87 sr 86 sr isotope seawater curve is well established and shows a decreasing trend until the mid katian however uncertainties in calibration of this curve to biostratigraphy and geochronology have made it diffi cult to determine how the rates of 87 sr 86 sr decrease may have varied which has implications for both the stratigraphic resolution possible using sr isotope stratigraphy and efforts to model the effects of ordovician geologic events we measured 87 sr 86 sr in conodont apatite in north american ordovician sections that are well studied for conodont biostratigraphy primarily in nevada oklahoma the appalachian region and ohio valley our results indicate that conodont apatite may provide an accurate medium for sr isotope stratigraphy and strengthen previous reports that point toward a signifi cant increase in the rate of fall in seawater 87 sr 86 sr during the middle ordovician darriwilian stage our 87 sr 86 sr results suggest that sr isotope stratigraphy will be most useful as a high resolution tool for global correlation in the mid darriwilian to mid sandbian when the maximum rate of fall in sr

oxygenation as a driver of the great ordovician biodiversification event the largest radiation of phanerozoic marine animal life quadrupled genus level diversity towards the end of the ordovician period about 450 million years ago a leading hypothesis for this great ordovician biodiversification event is that cooling of the ordovician climate lowered sea surface temperatures into the thermal tolerance window of many animal groups such as corals a complementary role for oxygenation of subsurface environments has been inferred based on the increasing abundance of skeletal carbonate but direct constraints on atmospheric o2 levels remain elusive here we use high resolution paired bulk carbonate and organic carbon isotope records to determine the changes in isotopic fractionation between these phases throughout the ordovician radiation these results can be used to reconstruct atmospheric o2 levels based on the o2 dependent fractionation of carbon isotopes by photosynthesis we find a strong temporal link between the great ordovician biodiversification event and rising o2 concentrations a pattern that is corroborated by o2 models that use traditional carbon sulfur mass balance we conclude that that oxygen levels probably played an important role in regulating early palaeozoic biodiversity levels even after the cambrian explosion an increase in biodiversity 450 million years ago coincided with a rise in atmospheric oxygen concentrations suggests a geochemical analysis oxygen availability may have thus helped spur the radiation alongside climatic cooling

reconstructing late ordovician carbon cycle variations abstract the role of carbon dioxide in regulating climate during the early paleozoic when severe glaciations occurred during a putative greenhouse world remains unclear here we present the first molecular carbon isotope proxy based estimates for late ordovician early katian pco2 levels and explore the limitations of applying this approach to the reconstruction of paleozoic pco2 carbon isotope profiles from three sites in laurentia iowa ontario and pennsylvania and one site in baltica estonia exhibit overall low isotope fractionation between organic and inorganic carbon during photosynthesis ep and these values declined during the early katian carbonate carbon isotope excursion or guttenberg carbon isotope excursion gice algal ep values are sensitive to changes in co2 concentrations algae cell morphologies and cell growth rates to constrain these factors we present molecular evidence that a decrease in the relative abundance of cyanobacteria and a change in the eukaryotic algae community co occurred with the gice regardless of local biotic or oceanographic influences a decline in ep values indicates photosynthesis was sensitive to carbon concentrations and via analogy with modern taxa constrains pco2 to below 8 pre industrial levels pil or about half of previous estimates in addition the global positive carbon isotope excursions expressed in a wide variety of sedimentary materials carbonate bulk organic matter n alkanes acyclic and cyclic isoprenoid hydrocarbons provide compelling evidence for perturbation of the global carbon cycle and this was likely associated with a decrease in pco2 approximately 10 million years prior to the hirnantian glaciations isotopic records from deeper water settings suggest a complex interplay of carbon sources and sinks with pco2 increasing prior to and during the early stages of the gice and then decreasing when organic carbon burial outpaced increased volcanic inputs