late ordovician turinian chatfieldian carbon isotope excursions and their stratigraphic and paleoceanographic significance five positive carbon isotope excursions are reported from platteville decorah strata in the upper mississippi valley all occur in subtidal carbonate strata and are recognized in the mifflin grand detour quimbys mill spechts ferry and guttenberg intervals the positive carbon isotope excursions are developed in a platteville decorah succession in which background 13c values increase upward from about 2 at the base to about 0 vienna pee dee belemnite vpdb at the top a regional north south 13c gradient with lighter values to the north and heavier values to the south is also noted peak excursion 13c values of up to 2 75 are reported from the quimbys mill excursion and up to 2 6 from the guttenberg excursion although there are considerable local changes in the magnitudes of these events the quimbys mill spechts ferry and guttenberg carbon isotope excursions occur in units that are bounded by submarine disconformities and completely starve out in deeper more offshore areas closely spaced chemostratigraphic profiles of these sculpted pyrite impregnated hardground surfaces show that they are associated with very abrupt centimeter scale negative 13c shifts of up to several per mil possibly resulting from the local diagenetic effects of incursions of euxinic bottom waters during marine flooding events

distal orogenic effects on peripheral bulge sedimentation middle and upper ordovician of the nashville dome abstract a major switch in depositional style in the ordovician carbonates of the nashville dome corresponds closely with the onset of the late middle ordovician taconic orogeny this time marks a shift from tropical type to temperate type carbonates the initiation of widespread major phosphate deposition the introduction of large amounts of terrigenous silt and clay the occurrence of widespread seismically induced soft sediment deformation and a change from a low energy flat topped carbonate shelf to a high energy doubly dipping carbonate ramp soft sediment deformation and the introduction of siliciclastics are direct effects of the taconic orogeny the switch from tropical type to temperate type carbonates the initiation of phosphate deposition and the switch in carbonate ramp are lar ely oceanographic effects triggered by the orogeny in particular phosphate deposition and the switch to temperate type limestones appears to have been driven by upwelling along the eastern side of the nashville dome within the newly deepened taconic foreland basin a fourfold decrease in the rate of relative sea level rise occurred on the nashville dome nearly 3 m y following the onset of thrusting and foreland basin initiation subsidence rates were constant before and after this decrease and no evidence of a change in subsidence rates is seen to coincide with the onset of thrusting the slowing of subsidence may reflect viscoelastic uplift of the nashville dome but the abrupt change from one constant subsidence rate to another is not predicted by existing foreland basin models

global upper ordovician correlation by means of δ13c chemostratigraphy implications of the discovery of the guttenberg δ13c excursion gice in malaysia apart from a single study of the early katian 13 c chemostratigraphy in two regions in china no investigations of the sandbian and katian chemostratigraphy have been published from anywhere in asia a recent study of the conodont biostratigraphy of the classical ordovician succession on langkawi islands peninsular malaysia showed the presence there of strata coeval with those having the guttenberg carbon excursion gice on the yangtze platform in an effort to establish for the first time the presence of this widespread 13 c excursion in southern asia a series of samples from the upper part of the kaki bukit formation was isotopically analysed this resulted in the discovery of a conspicuous 13 c excursion with peak values of 2 above the baseline values the excursion is located just above the baltoniodus alobatus subzone and near the level of the first appearance of hamarodus europaeus hence the same stratigraphic position as the gice on the yangtze platform using the gice the malaysian study interval is closely correlated with the gice intervals at three localities representing an approximately 23 000 km long transect from malaysia across baltoscandia to central north america this shows the usefulness of 13 c chemostratigraphy to clarify previously obscure stratigraphic relationships between geographically very widely separated localities

an alternative model for positive shifts in shallow marine carbonate 13c and 18o positive shifts in global seawater d 13 cdic are related to changes in the ratio of organic relative to inorganic carbon burial in oceanic basins whereas factors such as climatic cooling and the accumulation of polar ice are known to cause positive shifts in d 18 o here an alternative model is proposed for the formation of local positive isotope shifts in shallow marine settings the model involves geochemically altered platform top water masses and the effects of early meteoric diagenesis on carbonate isotopic composition both mechanisms are active on modern sub tropical carbonate platforms and result in low carbonate d 13 ca ndd 18 o relative to typical oceanic values during high amplitude transgressive events the impact of isotopically light meteoric fluids on the carbonate geochemistry is much reduced and 13 c depleted platform top water mixes with open oceanic water masses having higher isotope values both factors are recorded as a transient increase in carbonate 13 c and 18 o relative to low background values these processes must be taken into consideration when interpreting the geochemical record of ancient epeiric seas

ordovician k bentonites issues in interpreting and correlating ancient tephras abstract prominent upper ordovician k bentonites include the deicke and millbrig beds in the late ordovician of eastern north america and the kinnekulle k bentonite in the uppermost sandbian of baltoscandia these beds are thought to represent some of the largest ash fall deposits known in the phanerozoic record this report presents a comprehensive study of biotite compositions from the three beds covering a far more extensive geographic range than has previously been described these data show that the kinnekulle and millbrig are multiple event ash beds some parts of which are indistinguishable from one another tectonomagmatic discrimination diagrams combined with mg number data indicate that the deicke millbrig kinnekulle sequence represents the progressive transformation from calc alkaline to peraluminous magmatic sources consistent with a model of progressively evolving magmatism during the closure of the iapetus ocean it is concluded that the millbrig and kinnekulle beds are coeval and represent primarily simultaneous episodes of explosive volcanism although it cannot be excluded that some portions of both beds were produced by the same event

is mid late paleozoic ocean water chemistry coupled with epeiric seawater isotope records isotopes of epeiric sea carbonates are used to construct seawater records for modeling global changes in paleozoic ocean chemistry climate and for intercontinental correlation we present for the first time geochemical results of paleozoic brachiopods biogenic low mg calcite blmc from open ocean permian carboniferous seamounts of japan situated in the tropical mid panthalassic ocean strontium isotope values of blmc from the panthalassic and paleotethys oceans are coupled with those of coeval specimens from epeiric seas of north america europe and russia p 0 393 but not with those of epeiric sea whole rocks matrix aragonite calcite mac p 0 029 and conodonts biogenic apatite ba p 0 031 oxygen isotope values of blmc from the panthalassic and paleotethys exhibit mixed results with studies of counterparts from epeiric seas p 0 596 reflecting overprinting of local environmental conditions on global trends carbon isotope values of blmc and mac from the panthalassic and paleotethys oceans are generally dissimilar to those of coeval material from epeiric seas of north america europe and russia p 0 001 and 0 002 respectively factors such as water mass stratification evaporation dilution depth temperature carbon burial and or oxidation variations and syndepositional diagenesis within the local environment probably influenced the chemistry of the fauna and accumulating sediments this decoupling of carbon and oxygen isotope values from the open ocean with those from epeiric seas makes questionable the use of isotope results from epeiric seas for international correlation constructing global seawater records determining fluxes in the global carbon cycle and for modeling climate changes and subsequently atmospheric carbon dioxide levels

the ordovician sebree trough an oceanic passage to the midcontinent united states the sebree trough is a relatively narrow shale filled sedimentary feature extending for several hundred kilometers across the middle and late ordovician carbonate platform of the midcontinent united states the dark graptolitic shales within the trough stand in contrast to the coeval bryozoan brachiopod echinoderm rich limestones on the flanking platforms we infer from regional stratal patterns thickness and facies trends and temporal relations established by biostratigraphy and k bentonite stratigraphy that the sebree trough initially began to develop during late turinian to early chatfieldian time mohawkian series as a linear bathymetric depression situated over the failed late precambrian early cambrian reelfoot rift rising sea level and positioning of a subtropical convergence zone along the southern margin of laurentia caused the rift depression to descend into cool oxygen poor phosphate rich oceanic waters that entered the southern reaches of the rift from the iapetus ocean the trough apparently formed in a system of epicontinental estuarine circulation marked by a density stratified water column trough formation was accompanied by cessation of carbonate sedimentation deposition of graptolitic shales development of hardground omission surfaces substrate erosion and local phosphogenesis the carbonate platforms on either side of the trough are dominated by bryozoan brachiopod echinoderm grainstones and packstones that were deposited in zones of mixing where cool nutrient rich waters encountered warmer shelf waters concurrently lime mudstone and wackestone were deposited shoreward northern illinois wisconsin iowa minnesota michigan in warmer more tropical shallow seas coeval upward growth of the flanking carbonate platforms sustained and enhanced development of the trough shale facies five widespread diachronous late mohawkian and cincinnatian omission surfaces are present in the carbonate facies of the midcontinent these surfaces include sub deicke k bentonite ds1 top of black river limestone ds2 base and top of the guttenberg limestone member of the decorah formation ds3 and ds4 and top of the trenton limestone ds5 some of the surfaces correspond to previously described depositional sequence boundaries all five surfaces which embody deepening phases on top of highstand systems tracts converge in the sebree trough indicating that the trough was a long lived feature and was the source of eutrophic waters that episodically spread across the adjacent platforms terminating carbonate production late turinian and early chatfieldian incipient drowning episodes were followed by a final drowning event that began in the sebree trough during the late chatfieldian climacograptus spiniferus zone and reached southernmost minnesota and other regions far within the platform interior by richmondian time amorphognathus ordovicicus zone

post hunnebergian ordovician carbon isotope trend in baltoscandia its environmental implications and some similarities with that of nevada abstract carbon isotope changes during post hunnebergian ordovician time were investigated as the corresponding sequence of rocks is stratigraphically nearly complete in baltoscandia an attempt was made to use it to elaborate the general pattern of carbon isotope changes in most of the ordovician complications caused by several local hiatuses condensed sections and facies changes were mitigated by the study of overlapping sections a total of 326 new whole rock analyses and published data from 18 drill cores and 4 outcrops in estonia latvia and sweden were considered the following positive carbon isotope events were observed 1 the mid darriwilian excursion peak 13c value 1 9 in the aseri stage 2 the mid caradoc excursion 2 2 in the uppermost part of the keila stage 3 the first late caradoc excursion 2 3 in the lower part of the rakvere stage 4 the second late caradoc excursion 2 4 in the upper part of the nabala stage 5 the early ashgill excursion 2 5 in the lowermost part of the pirgu stage 6 the mid ashgill excursion 2 0 in the upper part of the pirgu stage 7 the widely known large hirnantian excursion in estonia the peak value reaches 6 7 in the porkuni stage the study interval comprises a long 19 ma period characterized by low magnitude carbon isotope changes and a following much briefer 12 ma interval with often medium scale shifts and a major event at the end the latter interval reflects onset in the mid caradoc of a period of variable climate alternation of arid and humid episodes which ended with a serious cooling and glaciation the baltoscandian and north american nevada 13c trends are in general lines very similar providing good prospects for global chemostratigraphical correlation and understanding of role of oceanic processes in carbon cycling

upper ordovician mohawkian carbon isotope δ13c stratigraphy in eastern and central north america regional expression of a perturbation of the global carbon cycle abstract the guttenberg carbon isotope excursion gice documented from eastern north america demonstrates the effects that regional geochemically distinct water masses upwelling and ocean circulation have on the carbon isotope record from carbonate platforms late turinian chatfieldian carbonates from oklahoma kentucky virginia and west virginia record a positive carbon isotope excursion 3 0 the gice excursion the gice excursion has relations to established biostratigraphy beginning in the north american midcontinent phragmodus undatus conodont zone and continuing through the plectodina tenuis zone sequence and event stratigraphy previously established models for positive carbon isotope shifts on carbonate platforms have been tested during the gice excursion where geochemically distinct water masses are defined for the upper ordovician a major eustatic sea level rise before the gice promoted a greater exchange of open ocean waters onto the carbonate platform of laurentia however restricted or sluggish circulation and exchange between water masses within the epeiric seas and the adjacent iapetus ocean were still apparent local variations documented in the gice excursion are directly related to upwelling of nutrient rich isotopically light waters increased primary productivity and the subsequent organic carbon production and burial

carbon oxygen and strontium isotopes in paleozoic carbonate components an evaluation of original seawater chemistry proxies abstract brachiopods trilobites cements and whole rock matrix material were evaluated for their reliability as proxies of original seawater carbon oxygen and strontium isotope chemistry in this process coeval material was evaluated from individual horizons of formations spanning the permian to cambrian unaltered shells of low mg calcite articulated brachiopods retain original seawater oxygen carbon and strontium isotope compositions as old as late ordovician assessments of older specimens are hampered by a lack of suitable material coeval brachiopod whole rock sets a definitive assessment of cement marine chemistry is difficult due to the paucity of material but despite this caveat cements hold some promise for retaining original carbon and possibly strontium isotope seawater values in contrast the potential of whole rock material as a proxy of original seawater chemistry is quite complex in some but not all instances the carbon isotopic composition of whole rock after detailed scrutiny and evaluation appears to represent an original seawater chemistry signal in a few instances their oxygen isotope compositions reflect original seawater values unlike the stable isotope compositions the strontium isotopes of all studied whole rock material permian to upper cambrian appear not to reflect original seawater chemistry values thus the potential for retaining original seawater isotope chemistry and serving as specific proxies in order of decreasing reliability are 1 unaltered low mg calcite brachiopods c o and sr isotopes 2 pristine marine cements c and sr isotopes and 3 whole rock material c isotopes carbon oxygen and strontium isotope compositions of ordovician trilobites mirror those of coeval unaltered brachiopods cambrian trilobites hold significant promise as an important proxy of original seawater isotope chemistry but further studies are needed to ascertain their full potential the survey of isotopes in some ordovician and cambrian intermediate low mg calcite trilobites demonstrates their potential as an important proxy of original seawater chemistry

comparative sequence stratigraphy of two classic upper ordovician successions trenton shelf new york ontario and lexington platform kentucky ohio implications for eustasy and local tectonism in eastern laurentia abstract comparison of the classic upper ordovician mohawkian to lower cincinnatian caradoc to lower ashgill black river and trenton groups in new york state southern ontario with the tyrone lexington formations exposed in the jessamine dome southern cincinnati arch in north central kentucky and southern ohio reveals striking similarities previous emphasis on complex local facies mosaic has obscured widespread regional patterns biostratigraphy and k bentonites provide broad constraints on inter regional correlations however an allostratigraphic approach permits higher resolution correlations and a partial test of eustatic vs strictly local tectonic models to explain stratigraphic patterns upper mohawkian to lower cincinnatian 455 449 ma depositional sequences previously recognized for the jessamine dome and nashville dome areas are correlated between the two main study areas and further refined chatfieldian rocklandian to shermanian or cobourgian of traditional terminology sequences m5 and m6 of previous workers are interpreted to be composite sequences and are each subdivided into three smaller scale sequences which also have counterparts in the new york ontario strata in turn these correlations indicate at least partial allocyclic control on sedimentary cycles complex lateral variations within depositional sequences especially in the late shermanian to edenian indicate that tectonically controlled patterns of basinal subsidence and uplift of crustal blocks perhaps reflecting forebulge migration exerted a strong influence on the local facies and motif of depositional sequences these tectonic features however did not obliterate the underlying allocyclic pattern indeed high resolution sequence stratigraphy enables detailed resolution of shifting patterns of minor uplift and subsidence

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

late middle ordovician environmental change and extinction harbinger of the late ordovician or continuation of cambrian patterns positive excursions in carbon isotope compositions of carbonate 3 and organic carbon 4 6 from the late middle ordovician middle caradocian of the midcontinent and the eastern united states indicate widespread increases in productivity and rates of organic carbon burial that may have drawn down atmospheric p co 2 precipitating global cooling although not necessarily ice sheet formation these climatic changes were associated with regional orogenic uplift a relative rise in sea level changes in epeiric sea circulation patterns and carbonate platform destruction that led to regional extinction of marine benthos the combination of sea level rise changing ocean circulation and extinction in the middle caradocian is similar to the suite of environmental changes described for cambrian biomere boundaries suggesting shared causes for these events in contrast middle caradocian environmental changes are markedly different from the environmental patterns associated with the late ordovician mass extinction despite the evidence for long term cooling from the middle to the late ordovician

sea level forcing of carbon isotope excursions in epeiric seas implications for chemostratigraphy five new 13c excursions are reported from the upper ordovician galena group of iowa the 13ccarb and 13corg trends are compared to sea level trends based on conventional sedimentological and novel chemostratigraphic end methods it is found that rising 13c values occur during rising sea level peak magnitude 13c values are coincident with inferred peak flooding and declining 13c values occur with declining sea levels the relationship to sea level is explained by a simple model of episodic flooding of the galena platform by cool oxygen depleted nutrient rich bottom waters originating from the sebree trough which was itself connected to the nearby iapetus ocean flooding of the inner galena shelf during sea level transgressions caused local changes in the carbon isotope balance of inner shelf waters due to 1 locally increased primary productivity and organic carbon burial 2 locally increased exchange of 13c enriched dissolved inorganic carbon dic with surrounding epeiric sea water masse

depletion of 13c in seawater σc02 on modern carbonate platforms significance for the carbon isotopic record of carbonates seawater co2 from modern carbonate platforms bahama banks and florida is depleted in 13c by as much as 4 relative to open ocean water depletion in 13c is caused by isotopically light co2 input from respiration of marine and terrestrial organic matter during water mass residence on the bank as such depletion in 13c is related to changes in water chemistry driven by evaporation freshwater discharge and caco3 withdrawal deviation of modern platform seawater 13c values away from those of surface seawater suggests that 13c values of ancient cratonic carbonate must be cautiously interpreted initial depositional environment as well as alteration during diagenesis must be considered in extracting valid secular trends for oceanic 13c variation

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

the importance of ocean temperature to global biogeochemistry variations in the mean temperature of the ocean on time scales from millennial to millions of years in the past and projected for the future are large enough to impact the geochemistry of the carbon oxygen and methane geochemical systems in each system the time scale of the temperature perturbation is key on time frames of 1 100 ky atmospheric co2 is controlled by the ocean co2 temperature dependent solubility and greenhouse forcing combine to create an amplifying feedback with ocean temperature the caco3 cycle increases this effect somewhat on time scales longer than f5 10 ky the co2 t feedback can be seen in the climate record from vostok and a model including the temperature feedback predicts that 10 of the fossil fuel co2 will reside in the atmosphere for longer than 100 ky timing is important for oxygen as well the atmosphere controls the ocean on short time scales but ocean anoxia controls atmospheric po2 on million year time scales and longer warming the ocean to cretaceous temperatures might eventually increase po2 by approximately 25 in the absence of other perturbations the response of methane clathrate to climate change in the coming century will probably be small but on longer time scales of 1 10 ky there may be a positive feedback with ocean temperature amplifying the long term climate impact of anthropogenic co2 release d 2004 elsevier b v all rights reserved

anatomy of an embayment in an ordovician epeiric sea upper mississippi valley usa the integration of stratigraphic geochemical and biostratigraphic data from middle ordovician carbonates and shales indicates that the north american epeiric sea was partitioned into shelf areas with distinct characteristics the upper mississippi valley part of the epeiric sea was appraised by using regionally traceable and geochemically fingerprinted k bentonites as well as detailed lithologic correlation in the midcontinent the decorah formation records a time of high clastic sediment influx and abundant freshwater runoff from the transcontinental arch that created a salinity stratified water column and led to episodic dysoxia later relative flooding of the clastic source areas greatly reduced both the clastic sediment and freshwater runoff as a result the salinity stratification broke down oxygenating the seafloor and permitting carbonates to form associated with this change clarity of the water improved and the photic zone expanded allowing seasonal blooms of gloeocapsomorpha prisca to occur resulting in increased burial of organic matter the increase in g prisca and total organic carbon coincided with but lagged behind a regional 13 c excursion in addition the timing of the initiation of the isotopic anomaly is different across the studied area suggesting that local environmental conditions influenced the isotopic record data presented in this study support the partitioning of distinct areas within epeiric seas and the importance of this setting in storing inorganic and organic carbon and recording environmental and biological changes

discovery of the ordovician millbrig k bentonite bed in the trenton group of new york state implications for regional correlation and sequence stratigraphy in eastern north america the ordovician chatfieldian millbrig k bentonite bed is a key stratigraphic marker horizon that is regionally synchronous over much of eastern and central north america this prominent marker is an independent source of correlation among the major chronostratigraphic and sequence stratigraphic units in this region the general stratigraphic position of the millbrig k bentonite has suggested to some authors that it is identical with the hounsfield k bentonite at dexter new york the traditional type area of the middle ordovician or mohawkian series in north america but previously available geochemical and biostratigraphical evidence has been insufficient to confirm this correlation analyses of apatites and melt inclusions in quartz phenocrysts from the millbrig k bentonite at eight localities in kentucky missouri virginia and pennsylvania and the hounsfield k bentonite at its type locality at dexter new york using high precision electron microprobe analysis techniques shows that the millbrig and the hounsfield have identical apatite and melt inclusion chemistry indicating a geochemical correlation this correlation is supported by conodont biostratigraphy and 13c isotope chemostratigraphy the new data demonstrate that the millbrig k bentonite and therefore the base of the chatfieldian stage of the north american mohawkian series by definition lies very close to the base of the traditional rocklandian stage of new york furthermore the millbrig k bentonite bed lies in close proximity to the base of the taconic supersequence over much of the midcontinent region and in particular lies just below the m5 sequence boundary recognized in kentucky and tennessee our results permit extension of the chatfieldian sequences into new york state and southern ontario and contributes to the resolution of the long standing uncertainty about the position of the base of the trenton group in ontario furthermore viewed in a broad context of regional stratigraphic relations we conclude that our results suggest that the persistent correlation difficulties reflect diachronous effects of widespread changes in oceanographic circulation patterns that emerged during taconic orogeny finally regional differences in the timing and character of sequence bounding surfaces and facies similarities summarized here suggest that the causes of relative sea level change during the chatfieldian may have been primarily tectonoeustatic mechanisms

nature and regional significance of unconformities associated with the middle ordovician hagan k bentonite complex in the north american midcontinent stratal patterns of the middle ordovician hagan k bentonite complex and associated rocks show that the black river trenton unconformity in the north american midcontinent formed through the complex interplay of eustasy sediment accumulation rates siliciclastic influx bathymetry seawater chemistry and perhaps local tectonic uplift the unconformity is diachronous and is an amalgamated surface that resulted from local late turinian lowstand exposure followed by regional early chatfieldian transgressive drowning and sediment starvation the duration of the unconformity is greatest in southern wisconsin northern illinois and northern indiana where the deicke and millbrig k bentonite beds converge at the unconformity on the basis of published isotopic ages for the deicke and millbrig beds it is possible that in these regions erosion and nondeposition spanned a period of as much as 3 2 m y two broad coeval depositional settings are recognized within the north american midcontinent during early chatfieldian time 1 an inner shelf subtidal facies of fossiliferous shale spechts ferry shale member and ion shale member of the decorah formation and argillaceous lime mudstone and skeletal wackestone guttenberg and kings lake limestone members extended from the canadian shield and transcontinental arch southeastward through minnesota wisconsin iowa and missouri 2 a seaward relatively deep subtidal sediment starved middle shelf extended eastward from the mississippi valley region to the taconian foreland basins in the central and southern appalachians and southward through the pericratonic arkoma and black warrior basins in the inner shelf region the black river trenton unconformity is a composite of at least two prominent hardground omission surfaces one at the top of the castlewood and carimona limestone members and the other at the top of the guttenberg and kings lake limestone members both merging to a single surface in the middle shelf region the inner and middle shelves redeveloped later in approximately the same regions during devonian and mississippian time

subaerial exposure and deposition of shallowing upward sequences evidence from stable isotopes of purbeckian peritidal carbonates basal cretaceous swiss and french jura mountains purbeckian lowermost cretaceous peritidal carbonates are characterized by open marine lagoonal intertidal and lacustrine facies arranged in milankovitch type shallowing upward sequences shallowing upward sequences typically consist of 2 6 individual beds the sequences may be i complete ii incomplete or ii pedogenetically overprinted reflecting the duration of subaerial exposure and or the extent of erosion and pedogenetic modification at the cycle tops the stable isotopic composition of the peritidal micrites reveals homogenous 6 o values attributed to diagenetic stabilization in a meteoric water buffered system carbon isotopes show three distinctly different carbon isotope patterns dependent on the completeness of the shallowing upward sequences complete shallowing upward sequences consist of l6 individual carbonate beds the carbon isotope values show a facies dependent pattern open marine carbonate muds record enriched 6i3c values of 0 28 while lagoonal 0 82 intertidal 2 46 10 and lacustrine micrites 2 96 are increasingly depleted this distinct pattern is explained by carbonate mud deposition in environments of differing salinity and marine influence incomplete sequences 2 5 carbonate beds are characterized by depleted 6 c values below subaerial exposure surfaces that become progressively enriched in c with increasing depth pedogenetically overprinted sequences 1 3 carbonate beds show strong i3c depletion throughout the sequence with little variation in the carbon isotopic composition the depleted values 4 51 10 of the pedogenetically altered micrites suggest that modification during subaerial exposure was associated with equilibration with meteoric solutions enriched in isotopically light soil gas coz the duration of subaerial exposure is the most crucial factor determining the extent of pedogenetic alterations the completeness of the shallowing upward sequences and the carbon isotope pattern the recorded patterns clearly illustrate that micrites have a good potential for the preservation of their primary carbon isotopic composition if the duration of subaerial exposure is rather brief otherwise the recorded carbon isotope patterns may support sequence stratigraphic analysis by providing a refinement of the time stratigraphic interpretation

sr c and o isotope geochemistry of ordovician brachiopods a major isotopic event around the middle late ordovician transition here we present sr c and o isotope curves for ordovician marine calcite based on analyses of 206 calcitic brachiopods from 10 localities worldwide these are the first ordovician wide isotope curves that can be placed within the newly emerging global biostratigraphic framework a total of 182 brachiopods were selected for c and o isotope analysis and 122 were selected for sr isotope analysis seawater 87sr 86sr decreased from 0 7090 to 0 7078 during the ordovician with a major quite rapid fall around the middle late ordovician transition most probably caused by a combination of low continental erosion rates and increased submarine hydrothermal exchange rates mean 18o values increase from 10 to 3 through the ordovician with an additional short lived increase of 2 to 3 during the latest ordovician due to glaciation although diagenetic alteration may have lowered 18o in some samples particularly those from the lower ordovician maximum 18o values which are less likely to be altered increase by more than 3 through the ordovician in both our data and literature data we consider that this long term rise in calcite 18o records the effect of decreasing tropical seawater temperatures across the middle late ordovician transition superimposed on seawater 18o that was steadily increasing from 3 standard mean ocean water smow by contrast 13c variation seems to have been relatively modest during most of the ordovician with the exception of the globally documented but short lived latest ordovician 13c excursion up to 7 nevertheless an underlying trend in mean 13c can be discerned changing from moderately negative values in the early ordovician to moderately positive values by the latest ordovician these new isotopic data confirm a major reorganization of ocean chemistry and the surface environment around 465 to 455 ma the juxtaposition of the greatest recorded swings in phanerozoic seawater 87sr 86sr and 18o at the same time as one of the largest marine transgressions in phanerozoic earth history suggests a causal link between tectonic and climatic change and emphasizes an endogenic control on the o isotope budget during the early paleozoic better isotopic and biostratigraphic constraints are still required if we are to understand the true significance of these changes we recommend that future work on ordovician isotope stratigraphy focus on this outstanding middle late ordovician event

isotope signatures associated with early meteoric diagenesis the environments in which carbonate diagenesis proceeds have been documented in previous studies of holocene and late pleistocene sediments and limestones on barbados west indies variations in the carbon and oxygen isotopic composition of limestones produced during early freshwater diagenesis have been observed in this study to occur in specific patterns six potentially useful patterns emerge when one views stable isotope data within a stratigraphic framework 1 the subaerial exposure surface is characterized by strongly 12c enriched limestones 13c compositions of underlying limestones grow progressively heavier with increasing depth 2 the subaerial exposure surface may also be marked by slight 18o enrichment 3 an abrupt shift in 18o values may differentiate sediments above the exposure surface from those below 4 sediments altered in the marine meteoric mixing zone may be characterized by positive covariance between their 18o and 13c compositions 5 the vadose phreatic boundary may be marked by a sharp increase in 13c values in the seaward portions of a fresh groundwater system and 6 samples contemporaneously altered in a single fresh groundwater system within an areally restricted region should display a narrow range of 18o and a wide range of 13c compositions analysis of samples from five palaeozoic and mesozoic formations which contained petrographic evidence of early freshwater diagenesis showed that isotope patterns similar to those observed in barbados limestones have been preserved in rocks as old as mississippian these isotope patterns could prove to be useful for identifying diagenetically induced porosity trends in carbonate rocks they might be used to identify limestones diagenetically altered in meteoric environments to identify mixing zone cements and dolomites and to trace the regional and vertical distributions of early meteoric groundwater systems in ancient carbonate formations

chemical correlation of k bentonite beds in the middle ordovician decorah subgroup upper mississippi valley strata of the champlainian middle ordovician decorah subgroup in the upper mississippi valley region have been correlated on the basis of the chemical composition of k bentonite beds in widely distributed outcrops and cores the four principal k bentonite beds in the decorah the deicke millbrig elkport and dickeyville can be differentiated by their unique chemical fingerprints which were established using a linear discriminant function analysis the elements that served as the best discriminators of differences between beds were in order of atomic number na sc ti zr sm eu tb dy yb lu hf ta and th although no one element serves to delineate a k bentonite bed completely from others a combination of elements can do so the chemical signatures of the deicke and millbrig k bentonite beds the two thickest and most widespread k bentonites in the mississippi valley were recognized in outcrop and subsurface from southern minnesota to southeastern missouri a distance of about 900 km the elkport and the dickeyville k bentonites were chemically identified in a limited area in northern illinois southwestern wisconsin and northern iowa the decorah consists of widespread lithologic units that are approximately parallel to k bentonite beds in some areas but in other areas lateral gradation of lithologies as shown by k bentonite correlations indicates contemporaneity of decorah lithofacies

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

archean cherts derived from chemical biogenic and clastic sedimentation in a shallow restricted basin examples from the gorge creek group in the pilbara block the 3ae0 ga chert sequence of the gorge creek group is exposed at ord ranges about 50 km east of port hedland in the pilbara block the chert sequence examined in this study is 15 m thick and consists of oxide rich laminated chert grey chert silicified clastic rock carbonaceous black chert and carbonate rich laminated chert although the cherts have undergone postdepositional silica enrichment such as cementation and metasomatic silicification primary precipitation of silica at the site of deposition is indicated by abundant microstructures mosaic and spherulitic structures other primary to early diagenetic components were carbonates sulphates gypsum and anhydrite and organic matter although these mineral associations on the whole correspond to those of modern marine evaporites they are different from modern equivalents with respect to abundant precipitation of amorphous silica and presumed primary precipitation of iron carbonate siderite this feature is a possible manifestation of peculiar physicochemical conditions in the water mass from which the chemical sediments were precipitated compared with modern ocean waters the concentrations of fe and si were significantly higher and the ph value might have been lower these conditions could be obtained by contributions of fe and si enriched hydrothermal solutions and continental run off to the site of deposition grey cherts contain detrital quartz and altered fe ti oxides and were formed in a period of input of terrigenous detrital materials they are characterized by higher concentrations of tio2 a l 2 o 3 cr ni zn rb and zr compared with the other types of chert and by very low 4 al2o3 tio2 values these features are attributed to the supply of terrigenous detrital materials that contain abundant fe ti oxides ilmenite and titanomagnetite and fine tio2 particles such detrital materials might have been formed by extensive chemical alteration of source rocks and residual enrichment of ti relative to al