shallow marine carbon and oxygen isotope and elemental records indicate icehouse greenhouse cycles during the early jurassic 1 for much of the mesozoic record there has been an inconclusive debate on the possible global significance of isotopic proxies for environmental change and of sequence stratigraphic depositional sequences we present a carbon and oxygen isotope and elemental record for part of the early jurassic based on marine benthic and nektobenthic molluscs and brachiopods from the shallow marine succession of the cleveland basin uk the invertebrate isotope record is supplemented with carbon isotope data from fossil wood which samples atmospheric carbon new data elucidate two major global carbon isotope events a negative excursion of 2 at the sinemurian pliensbachian boundary and a positive excursion of 2 in the late pliensbachian the sinemurian pliensbachian boundary event is similar to the slightly younger toarcian oceanic anoxic event and is characterized by deposition of relatively deepwater organic rich shale the late pliensbachian strata by contrast are characterized by shallow marine deposition oxygen isotope data imply cooling locally for both events however because deeper water conditions characterize the sinemurian pliensbachian boundary in the cleveland basin the temperature drop is likely of local significance in contrast a cool late pliensbachian shallow seafloor agrees with previous inference of partial icehouse conditions both the large scale long term and small scale short duration isotopic cycles occurred in concert with relative sea level changes documented previously from sequence stratigraphy isotope events and the sea level cycles are concluded to reflect processes of global significance supporting the idea of an early jurassic in which cyclic swings from icehouse to greenhouse and super greenhouse conditions occurred at timescales from 1 to 10 ma

heterogeneity cyclicity and diagenesis in a mississippian brachiopod shell of palaeoequatorial britain a shell of gigantoproductus okensis shows twenty growth lines with marked changes of fabric indicating periodical reduction of growth rates caused by environmental perturbations the number of growth lines suggests a lifespan of 20 years in agreement with the survival rates of extant brachiopods and with spiral deviation analysis geochemical analyses across the growth profile show a heterogeneous distribution of stable isotopes and trace elements it is possible to distinguish primary from altered carbonate and to interpret the isotopic data the oxygen isotope signal in the unaltered parts is periodical and annual with oscillation of 1 1 the higher values are at the growth lines winter and therefore most likely related to monsoon circulation during the visean the annual periodicity seems also present in the altered part of the shell suggesting that diagenesis could have reset the primary values but preserved their cyclicity

geochemistry of modern brachiopods applications and implications for oceanography and paleoceanography abstract modern rhynchonellida terebratulida thecideida and a few inarticulated brachiopods were collected live or soon after death at 30 locations from depths of 2 3940 m from the equator to high latitudes covering the atlantic pacific indian caribbean and mediterranean oceans seas well preserved fibers of the secondary layer combined with sr 450 1928 mg kg mn 1 199 mg kg and fe 1 610 mg kg contents confirm with few exceptions the excellent preservation of the modern brachiopod material evaluation of the stable isotope compositions was conducted on 276 specimens and on 374 published samples for a total database of 650 samples from 80 locations it revealed that oxygen isotope incorporation into shell calcite secondary layer of modern articulated brachiopods in most cases occurs in equilibrium with the ambient water and as such reflects surrounding environmental conditions thecideida as a group shallow water and low latitude incorporate oxygen isotopes 3 04 to 0 35 into shell calcite in equilibrium with their ambient water a large majority of genera and species of the terebratulida shallow water and low mid latitude also incorporate oxygen 2 30 to 3 48 into shell calcite in isotopic equilibrium with their surrounding water in contrast equilibrium incorporation of oxygen isotopes into shell calcite by the rhynchonellida is uncertain but a vital effect probably applies to the craniida the question of equilibrium disequilibrium incorporation of carbon isotopes into shell calcite of modern brachiopods remains unresolved at this time isotope compositions range up to 4 5 5 6 and 1 5 for 13 c and up to 5 5 5 9 and 0 3 for 18 o for shallow water low mid and high latitude brachiopods respectively strontium isotopes of modern brachiopods as expected show no significant variation with location latitude water depth temperature salinity and general water conditions once local habitat and ecological influences of fossil brachiopods from similar latitudes are considered their isotopic elemental values should be valuable diagenetic indicators and important oceanographic chemostratigraphic proxies

use of stable oxygen isotope determinations from brachiopod shells in palaeoenvironmental reconstruction abstract stable oxygen isotope analyses were obtained from fossil brachiopod shells from a shallow marine deposit of upper pleistocene age approximately 80 ka in new zealand as part of a palaeoenvironmental investigation bulk analyses of entire shells of calloria inconspicua yielded highly variable results a range of 2 30 rendering these data of limited use as palaeoenvironmental proxies attempts to obtain consistent oxygen isotope values by removing areas of the brachiopod shell thought to be prone to oxygen isotope disequilibrium effects vital effects revealed that the matching anterior portions of ventral and dorsal valves from the same individual which were secreted at the same time also yielded different oxygen isotope ratios the dorsal valve 18o values were higher and less variable than those obtained from the ventral valve of the same individual the investigation was then extended to living representatives of the same species from a similar shallow water habitat from the south island of new zealand the pattern of dorsal valves yielding higher and less variable oxygen isotope values than matching areas of the ventral valves was repeated in seven out of eight individuals investigated although there was considerable variation in the absolute values from specimen to specimen contrary to common practice therefore it seems that in this species it is the much thinner and lighter dorsal valve that provides a more consistent isotopic measurement if converted into absolute temperature estimates the dorsal valve measurements correspond to a temperature midway between the mean and maximum annual temperature experienced by this species in its present day habitat which may make it acceptable as a palaeoenvironmental indicator the high level of variation between individuals including an inferred temperature from one ventral valve above the mean maximum temperature experienced indicates that a range of individuals needs to be investigated in any palaeoenvironmental investigation to avoid misleading interpretations however intra and inter specimen variation in isotopic composition may provide valuable palaeobiological information on growth rates metabolism and possibly also pathological conditions in the past

palaeoenvironmental significance of carbon and oxygen isotope stratigraphy of marine triassic jurassic boundary sections in sw britain abstract carbon isotope stratigraphy is a useful tool for stratigraphic correlation especially for strata deposited during major perturbations of the carbon cycle that affected the marine terrestrial and atmospheric reservoirs for the triassic jurassic boundary effectively defined by a first order mass extinction major fluctuations in carbon isotope values have been well documented but these datasets have generally been derived from bulk rock samples hence the extent to which features of the isotopic curve reflect diagenetic alteration or changing proportions of constituent materials is unconstrained here carbon and oxygen isotope data are presented from well preserved oyster shells liostrea comprising low magnesium calcite a mineral species relatively resistant to diagenetic alteration samples were obtained from lavernock point glamorgan wales a coastal section close to a candidate stratotype for the base of the jurassic at st audrie9s bay somerset england the carbon isotope signature from st audrie9s bay previously defined on the basis of analysis of bulk organic matter is confirmed by our new data major features are 1 the upper part of an initial9 negative isotope excursion in the lowest part of the section followed by 2 a pronounced positive excursion and 3 an extended main9 negative isotope excursion in the highest part of the section the data confirm that the carbon isotope stratigraphy previously documented from bulk organic matter in sw england records the chemical composition of the contemporaneous seawater bulk carbonates sampled over the same interval near lyme regis england show similar trends to those from oyster calcite in the lower part of the study section but there are more 13 c depleted values up section these lower values probably result from an admixture of primary and diagenetic carbonate palaeotemperatures calculated from oxygen isotope values from lavernock point oyster shells are relatively cool at the beginning of the positive carbon isotope excursion and increased by up to 10 c during the main negative carbon isotope excursion the new results are compatible with the view that positive carbon isotope excursions correspond to times of low atmospheric carbon dioxide content whereas negative carbon isotope excursions correspond to times of high atmospheric carbon dioxide content as is also found to be the case during the early jurassic toarcian oceanic anoxic event the mg ca and sr ca ratios and 18 o of investigated liostrea hisingeri show no correlation supporting data from modern bivalves that indicate that incorporation of mg and sr is controlled mainly by factors other than temperature

changing co2 conditions during the end triassic inferred from stomatal frequency analysis on lepidopteris ottonis goeppert schimper and ginkgoites taeniatus braun harris abstract end triassic fluctuations in atmospheric carbon dioxide co2 concentration were reconstructed by the use of stomatal frequency analysis on a single plant species the seedfern lepidopteris ottonis goeppert schimper stomatal index showed no distinct intra and interpinnule variation which makes it a suitable proxy for past relative co2 changes records of decreasing stomatal index and density from the bottom to the top of the rhaetian hettangian wustenwelsberg section bavaria germany indicate rising co2 levels during the triassic jurassic transition additionally stomatal frequency data of fossil ginkgoalean leaves ginkgoites taeniatus braun harris suggest a maximum palaeoatmospheric co2 concentration of 2750 ppmv for the latest triassic

criteria for the retention of original seawater 87sr86sr in ancient shelf limestones abstract a suite of 40 pennsylvanian and permian shelf limestones from kansas and oklahoma has been analyzed for major and trace elements and for c o and sr isotopes the chemistry and c and o isotope ratios were compared to the difference between the measured 87 sr 86 sr and original seawater ratio concentrations of mn sr and fe varied most systematically with the change in the seawater sr ratio all samples containing 700 ppm mn yielded altered ratios fe and sr contents were also found to have a less well defined correlation with the retention of the original sr ratio all limestones with 900 ppm sr and 20 of 22 samples with a sr mn 2 0 yielded correct ratios the geochemical guidelines were applied to the chemical and isotopic results from 76 shelf limestones mostly of pennsylvanian age from texas and oklahoma more than 92 of the samples that contain sr mn 2 0 yielded correct seawater ratios every sample with sr mn 2 0 retained the original seawater ratio

secular environmental precursors to early toarcian jurassic extreme climate changes the early toarcian oceanic anoxic event t oae about 183 myr ago was a global event of environmental and carbon cycle perturbations which deeply affected both marine biota and carbonate production nevertheless the long term environmental conditions prevailing prior to the main phase of marine extinction and carbonate production crisis remain poorly understood here we present a similar to 8 myr long record of early pliensbachian middle toarcian environmental changes from the lusitanian basin portugal in order to address the long term paleoclimatic evolution that ultimately led to carbonate production and biotic crises during the t oae paleotemperature estimates derived from the oxygen isotope compositions of well reserved brachiopod shells from two different sections reveal a pronounced similar to 5 degrees c cooling in the late pliensbachian margaritatus spinatum ammonite zones boundary this cooling event is followed by a marked similar to 7 10 degrees c seawater warming in the early toarcian that after a second cooling event in the mid polymorphum zone culminates during the t oae calcium carbonate caco3 contents the amount of nannofossil calcite and the mean size of the major pelagic carbonate producer schizosphaerella all largely covary with paleotemperatures indicating a coupling between climatic conditions and both pelagic and neritic caco3 production furthermore the cooling and warming episodes coincided with major marine regressions and transgressions respectively suggesting that the growth and decay of ice caps may have exerted a strong control on sea level fluctuations throughout the studied time interval this revised chronology of environmental changes shows important similarities with neogene and paleozoic episodes of deglacial black shale formation and thus prompts the reevaluation of ice sheet dynamics as a possible agent of mesozoic events of extinction and organic rich sedimentation c 2010 elsevier b v all rights reserved

geochemical and climatic effects of increased marine organic carbon burial at the cenomanian turonian boundary perhaps the most significant event in the cretaceous record of the carbon isotope composition of carbonate1 2 other than the 1 2 5 negative shift in the carbon isotope composition of calcareous plankton at the cretaceous tertiary boundary3 is the rapid global positive excursion of 2 13c enrichment which took place between 91 5 myr and 90 3 myr late cenomanian to earliest turonian c t boundary event 1 4 5 this excursion has been attributed to a change in the isotope composition of the marine total dissolved carbon tdc reservoir resulting from an increase in rate of burial of 13c depleted organic carbon which coincided with a major global rise in sea level5 during the so called c t oceanic anoxic event oae 6 here we present new data from nine localities which demonstrate that a positive excursion in the carbon isotope composition of organic carbon at or near the c t boundary7 8 is nearly synchronous with that for carbonate and is widespread throughout the tethys and atlantic basins fig 1 as well as in more high latitude epicontinental seas the postulated increase in the rate of burial of organic carbon may have had a significant effect on co2 and o2 concentrations in the oceans and atmosphere and consequent effects on global climate and sedimentary facies

an isotopic study of biogeochemical relationships between carbonates and organic carbon in the greenhorn formation carbon isotopic compositions of total carbonate inoceramid carbonate micritic carbonate secondary cements total organic carbon and geoporphyrins have been measured in 76 different beds within a 17 m interval of a core through the greenhorn formation an interbedded limestone and calcareous shale unit of cretaceous age cenomanian turonian from the western interior seaway of north america results are considered in terms of variations in the processes of primary production which led to the biosynthesis of the molecular precursors of the geoporphyrins and in secondary processes those mediating the transformation of primary organic material into sedimentary total organic carbon it is shown that the porphyrin isotopic record reflects primary isotopic variations more closely than the toc isotopic record and that in these sediments toc is enriched in 13c relative to its primary precursor by 0 6 to 2 8 this enrichment is attributed to isotope effects within the consumer foodweb and is associated with respiratory heterotrophy variations in this secondary enrichment are correlated with variations in the isotopic composition of marine carbonate this correlation is attributed to effects of environmental changes on the marine foodweb these may have included increased atmospheric oxygen associated with the cenomanian turonian oceanic anoxic event the isotopic fractionation associated with fixation of carbon by primary producers is observed to have varied by 1 5 during the interval of deposition it is suggested that this change is due to a variation in the makeup of the community of primary producers and or to a decrease in the atmospheric abundance of co2 during the oceanic anoxic event

δ13c and δ18o values of triassic brachiopods and carbonate rocks as proxies for coeval seawater and palaeotemperature abstract a dataset of 160 isotope 13c and 18o values from anisian ladinian carnian and rhaetian articulate brachiopod shells complemented by 158 carbon and oxygen isotope values from whole rock carbonates define the first continuous stable isotope baseline trends for the triassic seawater the carbon isotope data suggest the existence of several short term high amplitude excursions in the early triassic followed by a predominance of values around 0 5 1 during the middle triassic a rise to 3 5 during the carnian plateau at this level during the late carnian to early norian and a 1 5 decline in the middle norian to values around 2 during the late norian rhaetian interval the causation scenarios for these rapid oscillations are at present equivocal but may in part reflect a biological instability of the carbon cycle following the recovery from the end permian extinction event and or an input of mantle derived co2 from enhanced volcanic activity the 18o values from well preserved brachiopods from the tethyan realm range from 3 9 to 0 6 v pdb these values require open marine triassic seawater 18o values close to 0 v smow for the calculated temperatures to be within the range of tolerance of the coexisting reef building corals a 2 18o increase within the uppermost cordevolian and early julian suggests either a distinct temperature decline in the southern alps during that time interval an increase in seawater salinity or their combination oxygen isotope values for the muschelkalk brachiopods range between 6 2 and 2 0 and likely reflect a strong influx of meteoric waters into the germanic basin that shifted the oxygen isotopes to more negative values

δ18o and δ13c of permian brachiopods a record of seawater evolution and continental glaciation abstract two hundred sixty four 18 o and 13 c values of permian articulate brachiopod shells were analyzed and 81 of these values were characterized as well preserved and biostratigraphically well defined these were then utilized for construction of baseline oxygen and carbon isotope curves for the permian interval in addition 21 13 c whole rock values are reported for the wordian and capitanian the early permian asselian to artinskian times are characterized by 2 5 decrease in oxygen isotope values from 0 7 to 3 3 v pdb this is attributed to a 4 7 c increase in temperature in the southern urals concomitant with the retreat of the permo carboniferous ice sheets and return of the 18 o depleted melt water into the oceans the late permian samples from iran jolfa at kuh e ali bashi and china meishan yield 18 o values and presumably temperatures similar to those that followed the termination of the large scale glaciation in the lower permian in between the upper kungurian to capitanian samples from the delaware basin guadalupe mountains are enriched in 18 o at 1 5 to 3 we have no definitive explanation for these data but tentatively suggest that the anomaly can potentially be a result of evaporative enrichment of seawater in 18 o due to intracratonic arid setting of the basin the 18 o enriched nature of the zechstein samples 1 2 to 2 5 on the other hand is in all probability a reflection of the high evaporation rates in the zechstein sea the permian interval is characterized by a relatively constant 13 c at about 4 the exceptions are again the brachiopods from the delaware basin guadalupe mountains which show 1 6 increase in the guadalupian to values of up to 5 9 in the wordian a tentative explanation as in the case of oxygen is based on the proposition that the semi enclosed delaware basin was likely stratified with sequestration of the 13 c depleted carbon to the deeper water layers and a complementary 13 c enrichment in the upper oxygenated layer the coeval open ocean water dic may have been similar to that of the remainder of the permian interval at 4 as indicated by whole rock carbonate samples from oman sicily and iran in the latest permian the trend mimics the well known 13 c drop at the permian triassic boundary

stability of atmospheric co2 levels across the triassic jurassic boundary the triassic jurassic boundary 208 million years ago is associated with widespread extinctions in both the marine and terrestrial biota the cause of these extinctions has been widely attributed to the eruption of flood basalts of the central atlantic magmatic province this volcanic event is thought to have released significant amounts of co2 into the atmosphere which could have led to catastrophic greenhouse warming but the evidence for co2 induced extinction remains equivocal here we present the carbon isotope compositions of pedogenic calcite from palaeosol formations spanning a 20 myr period across the triassic jurassic boundary using a standard diffusion model we interpret these isotopic data to represent a rise in atmospheric co2 concentrations of about 250 p p m across the boundary as compared with previous estimates of a 2 000 4 000 p p m increase the relative stability of atmospheric co2 across this boundary suggests that environmental degradation and extinctions during the early jurassic were not caused by volcanic outgassing of co2 other volcanic effects such as the release of atmospheric aerosols or tectonically driven sea level change may have been responsible for this event

deciphering kinetic metabolic and environmental controls on stable isotope fractionations between seawater and the shell of terebratalia transversa brachiopoda this study presents carbon and oxygen stable isotope data obtained from high resolution sampling 500 m of the brachiopod terebratalia transversa from the san juan islands washington state usa the aim of this study is to unravel the respective effects of physiological and environmental controls on the stable isotopic composition of brachiopod shell calcite based on an sem study of the shell a three dimensional sampling was performed in order to investigate carbon and oxygen isotope variations along isochrons and ontogenetic transects the primary as well as the outer part of the secondary shell layer display large and variable isotopic offsets as high as 7 for 13c and 6 for 18o relative to expected equilibrium values the significant positive correlations between 18o and 13c values indicate that the isotopic compositions of these shell domains are mainly controlled by kinetic isotope fractionation effects the ontogenetic 13c and 18o variations can be used to establish a growth curve of the studied specimen whose age is estimated close to 8 years the extent of apparent o 18 disequilibrium observed in this study is about as large as any yet measured in any organism which makes this brachiopod an interesting and important case the carbon and oxygen isotope compositions increase from the outer towards the inner part of the secondary layer where they reach values of 0 0 8 and 0 8 to 0 2 respectively corresponding calculated temperatures are between 12 and 13 8 c and fall in the range of seawater temperatures recorded off the san juan islands 7 13 c these results suggest that the calcite fibres were secreted more and more slowly during the thickening of the shell throughout the animal s life finally approximating isotopic equilibrium this study illustrates that the stable isotopic composition of the modern brachiopod t transversa is predominantly influenced by kinetic fractionation and to a minor degree by metabolic effects except for the innermost part of the shell the measured isotope ratios do not reflect environmental conditions during shell precipitation it remains to be tested by comparable studies whether other modern brachiopod species or even fossil brachiopods reflect comparable fractionation effects these results point out the need for re examination of paleozoic oceanographic conditions

glacial interglacial surface water variations in the caribbean sea during the last 300 ky based on calcareous nannofossil analysis abstract quantitative and qualitative analyses of nannofossil assemblages from odp site 999 in the caribbean sea were performed to reveal changes in upper seawater structures and implications for climatic changes during the last 300 000 years overall there is an inverse relationship in stratigraphic fluctuations between the absolute abundance aa of a lower photic taxon florisphaera profunda and 18 o this fluctuation pattern is considered to represent climatic changes in the subtropical under water suw in the caribbean cross spectral analysis demonstrates that the suw was characterized by nutrient rich water during interglacials changes in orbitally driven gyre circulation system strongly affected fluctuations in the suw in the caribbean conversely the surface water was enriched in nutrients during glacials as the result of increased terrigenous materials and shallowing of the thermocline based on changes of the n ratio abundance of reticulofenestrids relative to f profunda and results of cross spectral analysis between them and 18 o the relationship between the thermocline variation and the ice volume fluctuation suggests that changes in the subtropical gyre circulation system in the north atlantic have had stronger influences on the caribbean thermocline variations and there may be a little contribution of climatic fluctuations that originated in the southern ocean to the caribbean sea a large floral turnover in nannofossil assemblages between oxygen isotope stages 6 and 5 was observed in hole 999a which corresponds to termination ii on the basis of floral compositions photosynthetic primary productions had been more active than today before termination ii

oxygen isotopic composition of alkaline anorogenic granites as a clue to their origin the problem of crustal oxygen abstract the primary isotopic characteristics of alkaline granites are often obscured by secondary processes enhanced by their unusual chemical compositions this is true for radiogenic as well as for stable isotopes for example the 87 sr 86 sr ratios can vary drastically in closed systems because of very high rb sr ratios and can also be easily modified by direct or indirect interaction with continental crust because of low sr concentrations moreover the frequent occurrence of the granitic massifs as hypovolcanic complexes increases the probability of interaction with meteoric waters which is a common source of important isotopic variability the investigation of oxygen isotope systematics in alkaline acidic rocks from various environments shows the 18 o content of their quartz to be highly invariable and the 18 o values to be close to the mantle range of values this is due to the resistance of quartz to isotopic exchange which makes it a good tracer of primary isotopic composition if we eliminate the quartz 18 o values for which interaction with meteoric water is well documented five samples the total range of variation seventeen samples is from 6 0 to 7 3 relative to smow the values can easily be accounted for by and correspond to equilibrium with mantle type material in a temperature range of 1200 800 c if we consider possible effects of fractional crystallization this temperature range can probably be reduced to its lower limit which is much more likely for rocks of acidic composition the present oxygen isotope study strongly supports an origin for alkaline anorogenic granites from mantle dominated sources

massive dissociation of gas hydrate during a jurassic oceanic anoxic event in the jurassic period the early toarcian oceanic anoxic event about 183 million years ago is associated with exceptionally high rates of organic carbon burial high palaeotemperatures and significant mass extinction heavy carbon isotope compositions in rocks and fossils of this age have been linked to the global burial of organic carbon which is isotopically light in contrast examples of light carbon isotope values from marine organic matter of early toarcian age have been explained principally in terms of localized upwelling of bottom water enriched in 12c versus 13c refs 1 2 5 6 here however we report carbon isotope analyses of fossil wood which demonstrate that isotopically light carbon dominated all the upper oceanic biospheric and atmospheric carbon reservoirs and that this occurred despite the enhanced burial of organic carbon we propose that as has been suggested for the late palaeocene thermal maximum some 55 million years ago the observed patterns were produced by voluminous and extremely rapid release of methane from gas hydrate contained in marine continental margin sediments

triassic jurassic organic carbon isotope stratigraphy of key sections in the western tethys realm austria the late triassic period is recognized as one of the five major mass extinctions in the fossil record all these important intervals in earth history are associated with excursions in c isotope records thought to have been caused by perturbations in the global carbon cycle the nature and causes of c isotopic events across the triassic jurassic t j transition however are poorly understood we present several new high resolution organic c isotope records from the eiberg basin austria including the proposed global boundary stratotype section and point gssp for the base of the jurassic the triassic jurassic boundary interval in these records is characterized by the initial and main negative organic carbon isotope excursions cie of up to 8 the initial and main cies are biostratigraphically constrained by first and last occurrences of boundary defining macro and microfossils e g ammonites high resolution c isotope records appear to be an excellent correlation proxy for this period in the eiberg basin pyrolysis analysis demonstrates increased hydrogen index hi values for organic matter coinciding with the initial cie terrestrial organic matter influx and mass occurrences of green algae remains may have influenced the c isotope composition of the sedimentary organic matter this may have contributed to the extreme amplitude of the initial cie in the eiberg basin

an accretionary distally steepened ramp at an intrashelf basin margin an alternative explanation for the upper triassic steinplatte reef northern calcareous alps austria abstract the upper triassic massive limestone the oberrhdtkalk at the steinplatte austria formed along the edge of an intrashelf basin that was situated within a shallow marine to supratidal shelf approximately 40 km wide this transition from shelf to intrashelf basin is marked by a distinct slope break that has been widely cited as an example of a reef rimmed shelf it is instead a distally steepened ramp the oberrhdtkalk consists of the ramp sediments lying between the dachsteinkalk of the shelf and the kossen formation of the intrashelf basin the ramp interpretation is based on the geometry and lateral facies progression in the profile from the shallow marine to peritidal shelf across the ramp and into the basin and on the absence of reef or grainstone deposits at the slope break typical of a rimmed shelf the oberrhdtkalk at the steinplatte is an important example of shelf margin deposition because 1 1 it formed in a protected and low energy intrashelf basin setting thus expanding the range of distally steepened ramps that have been used to develop a general model 2 2 it differs from previously described examples of distally steepened ramps largely from open ocean shelf margin settings in that a it evolved constructionally from a homoclinal ramp rather than forming at a drowned shelf edge or an antecedent tectonic structure b the sediments of the distal slope are largely autochthonous c slumping and breccia deposits on the distal slope are of minor importance turbidites on the basin floor are absent and d skeletal packstone and grainstone characterize the outer ramp and slope rather than mudstone and wackestone 3 3 it provides an alternative ramp model for other upper triassic shelf and platform margins in the northern calcareous alps which have commonly been interpreted as reef or sediment rimmed

oxygen isotope fluctuations in a modern north sea oyster crassostrea gigas compared with annual variations in seawater temperature implications for palaeoclimate studies abstract a total of 181 oxygen isotope values from sequential samples of the left shell of a modern pacific oyster crassostrea gigas that lived on a sub tidal oyster bank in the list basin north sea germany shows periodically varying values between 1 3 and 2 5 in order to test whether these 18 o fluctuations reflect seawater temperature changes the isotope values of the shell were compared to actual seawater temperature variations from the region c gigas serves as an excellent proxy for temperature of palaeoseawater and the results show that the examined oyster precipitated its shell in 18 o equilibrium with the ambient seawater a cessation of the oyster shell calcification starts at water temperatures below 6 c at lower temperatures than previously thought for crassostrea for palaeoclimate investigations the termination of shell production is important because the lowest temperatures might not be represented in the shell higher water temperatures are therefore potentially over represented in time spans when the shell grows faster and mean oxygen isotope values may potentially bias the mean seawater temperatures of annual variations towards higher temperatures

brachiopods as indicators of original isotopic compositions in some paleozoic limestones the original stable isotopic composition of paleozoic marine carbonate rocks is important to establish a baseline for evaluating diagenetic alteration and providing a reliable data base for modeling exogenic geochemical cycles of the elements we have compared the 18 o and 13 c values in the nonluminescent portions of brachiopods with similar published data of whole brachiopods other whole fossils and estimates of original isotopic composition of marine cements the oxygen and carbon isotopic records for each of these paleozoic components show generally good internal consistency significant discrepancies however were noted between results on the different components isotopic and trace element data presented in this study suggest that permo carboniferous whole brachiopods are little altered chemically nonetheless a more reliable but not fool proof approach for obtaining pristine isotopic values is microsampling of least altered regions based on cathodoluminescence in conjunction with staining techniques and elemental analyses the carbon and oxygen isotopic compositions of all components decrease in 18 o and 13 c in geologically older material neither temporal trend is monotonic however oxygen isotopic results suggest an important positive shift in 18 o of about 2 during the early carboniferous whereas the carbon isotope trend shows a major positive shift 2 3 during the mid carboniferous

geochemistry of brachiopods oxygen and carbon isotopic records of paleozoic oceans abstract combined trace element and isotope studies of 319 brachiopods covering the ordovician to permian time span show that 13c and 18o in well preserved specimens varied during the paleozoic the overall 13c secular trend is in accord with the previously published observations but its details are obscured by vital isotopic fractionation effects at generic level nonetheless the results suggest that the negative correlation between marine 13ccarbonate and 34ssulphate deteriorates at time scales of 106 years due to the long residence time and thus slow response of so42 in the ocean for oxygen isotopes all devonian and older specimens have 18o of 4 while the well preserved permian samples have near present day 18o of about 1 pdb this isotopic dichotomy is probably not due to post depositional phenomena salinity or biogenic fractionation effects this leaves open the perennial arguments for a change in 18 o 16 o of sea water versus warmer ancient oceans the present data are difficult to explain solely by the temperature alternative the coincidence of the proposed shift in 18o with the large late paleozoic changes in marine 87 sr 86 sr 13 c 12 c 34 s 32 s and sea level stands argues for a tectonic cause and for a change in 18 o 16 o of sea water although such explanation is difficult to reconcile with global balance considerations and with isotopic patterns observed in alteration products of ancient basalts and ophiolites whatever the precise cause or combination of causes the implications for tectonism and or paleoclimatology are of first order significance

oxygen isotope values from high latitudes clues for permian sea surface temperature gradients and late palaeozoic deglaciation abstract the permian was a period of waning large scale continental glaciations in the southern hemisphere the waning of these ice sheets during the early permian led to discharge of 18o depleted ice melt water into the oceans this coupled with rising seawater temperatures resulted in a concomitant decline of about 2 5 in the 18o of seawater as recorded by brachiopod shells from low latitude

brachiopod δ18o values do reflect ambient oceanography lacepede shelf southern australia although commonly used as proxies for attributes of ancient ocean waters the 18 o values of brachiopods from modern seas are little studied to evaluate the utility of brachiopods as recorders of regional oceanography modern shells from the lacepede shelf 25 000 km 2 of southern australia were analyzed for 18 o and the results were compared to the values of ambient seawater southern ocean waters cover this area of extensive cool water carbonate deposition but there are distinct sectors of seasonal upwelling and lesser fluvial outflow 18 o values of brachiopods across the environmental spectrum from 40 to 300 m water depth are in general isotopic equilibrium with surrounding seawater nevertheless 18 o values from individual sample sites vary as much as 0 60 the area of cold water upwelling in particular is clearly delimited by a group of high 18 o values the range of values across this one shelf on the order of 2 5 is similar to the range of values postulated on the basis of similar results for secular changes in many ancient oceans

carbon and oxygen isotopic composition of silurian brachiopods gotland sweden palaeoceanographic implications abstract one hundred and seventy two non luminescent brachiopod shells from the silurian sequence of gotland were investigated for their carbon and oxygen isotopic composition diagenetic alteration of the shell calcite was excluded by means of petrographic trace element and cathodoluminescence analysis oxygen and carbon isotopic signals vary considerably within the uppermost llandovery to the ludlow average 18o and 13c values of well defined stratigraphic units range from 2 4 to 5 9 and 1 to 8 respectively we observed parallel trends in the carbon and oxygen isotope curves with the most prominent shifts occurring in the lower wenlock upper wenlock and middle ludlow average 18o values 2 4 to 2 9 recorded in the middle ludlow are among the highest 18o values reported for the early palaeozoic the recorded 18o variations cannot solely be explained by changes in sea surface temperature and salinity the variations in the isotopic signals correlate negatively with changes in sea level heavy carbon and oxygen signals coincide with sea level lowstands whereas light signals are recorded during sea level highstands sea level highstands were probably characterized by the formation of warm saline waters on subtropical epicontinental shelves inducing oxygen deficiency in the basins alumshale facies the low 18o values are attributed to 18o depletion in surface waters owing to the storage of 18o enriched saline waters in the basins low 13c values are explained by a low surface water productivity since nutrients were not supplied to the photic zone but rather stored in the deeper ocean during sea level lowstands colder waters that formed in higher latitudes may have represented the main intermediate water source a better ventilation of the basins is documented by the deposition of well aerated sediments whereas the high 18o values are explained by the change in oceanic circulation the high 13c values are attributed to an enhanced primary productivity and possibly to an enhanced burial of corg the model discussed here may provide an attractive scenario for accounting for the recorded short term variations in the isotopic signals without the necessity of introducing an isotopic correction factor for silurian sea water

within shell variations in carbon and oxygen isotope compositions of two modern brachiopods from a subtropical shelf environment off amami o shima southwestern japan 1 this study examines the fidelity of carbon 13c and oxygen 18o isotope compositions of two modern brachiopod species kikaithyris hanzawai and basiliola lucida to use as proxies of 13c values of total dissolved inorganic carbon and temperature and or 18o values of seawater respectively well preserved shells of k hanzawai and living individuals of b lucida were collected from a subtropical shelf environment off amami o shima southwestern japan some portions of the shells are in isotopic equilibrium with the ambient seawater while other portions are not the degree of disequilibrium differs between the two species and between different portions of each shell statistically significant positive correlations are recognized between the 13c and 18o values of these samples which can be ascribed to a kinetic fractionation effect far from the posterior shell edge and along the axis of shell growth the 18o values of the secondary shell layer of k hanzawai mostly fall within the expected range of equilibrium calcite the 13c values from the inner surface of the secondary shell layer in both species are relatively constant and are equivalent to or very close to equilibrium calcite therefore these portions of the shells are most suitable for collecting reliable environmental proxy data although the 13c and 18o values of modern brachiopod shells are predominantly controlled by a kinetic fractionation effect the appropriate selection of species and shell portions that reflect the isotopic composition of ambient seawater can facilitate the reconstruction of secular variations in oceanic 13c or 18o values

palaeoenvironmental changes in the late triassic rhaetian of the northern calcareous alps clues from stable isotopes and microfossils abstract the triassic kossen formation rhaetian in the northern calcareous alps has been studied with respect to oxygen and carbon isotope ratios of brachiopod shells and whole rocks together with the stratigraphic range and ecology of ostracod assemblages in order to detect palaeotemperature changes in the kossen formation and determine their significance for environmental and climatic conditions in the rhaetian sea of the eiberg basin northern calcareous alps for this purpose 60 18 o measurements on 43 articulate brachiopods samples from 8 different horizons were carried out the results indicate a progressive decrease of 2 5 c in seawater bottom temperature in the middle late rhaetian the carbonate microfacies as well as macro and microfossil assemblages indicate a gradual increase of water depth in the eiberg basin and thereby explain the observed bottom water cooling the oxygen isotope data further suggest that the palaeobathymetric temperature gradient in the eiberg basin was rather low indicating that almost no deep water exchange with tethys existed at that time carbon isotopes from brachiopod shells and from bulk carbonates show a trend to heavier values from the hochalm member up to the lowest unit 3 of the eiberg member that parallels oxygen isotopes this positive 13 c trend is interrupted by a sudden 1 5 negative excursion in the late rhaetian late rhaetian event a time span when the oxygen isotopes remain heavy

atmospheric pco2 perturbations associated with the central atlantic magmatic province the effects of a large igneous province on the concentration of atmospheric carbon dioxide pco2 are mostly unknown in this study we estimate pco2 from stable isotopic values of pedogenic carbonates interbedded with volcanics of the central atlantic magmatic province camp in the newark basin eastern north america we find pre camp pco2 values of 2000 parts per million ppm increasing to 4400 ppm immediately after the first volcanic unit followed by a steady decrease toward pre eruptive levels over the subsequent 300 thousand years a pattern that is repeated after the second and third flow units we interpret each pco2 increase as a direct response to magmatic activity primary outgassing or contact metamorphism the systematic decreases in pco2 after each magmatic episode probably reflect consumption of atmospheric co2 by weathering of silicates stimulated by fresh camp volcanics

shell structure patterns and trends of oxygen and carbon stable isotopes in modern brachiopod shells this study investigates 13c and 18o variations in the shells of modern brachiopods representing all extant groups of calcite precipitating brachiopods collected live from 8 locations sem examinations determined the ultrastructural characteristics of each species prior to isotope analyses 13c and 18o analyses of shell carbonate were carried out with samples representing disparate morphological features and ultrastructural shell layers of both ventral and dorsal valves generally 18o values from the fibrous secondary or prismatic tertiary shell layers of the articulated terebratulida and rhynchonellida species were in oxygen isotopic equilibrium with ambient seawater isotopic temperatures extrapolated from these values are close to measured annual mean seawater temperatures 18o values were relatively unaffected by shell specialisation the only exception was antarctic species liothyrella uva which did not have a complete tertiary shell layer typical of this genus and had 18o values of the innermost layer strongly correlated with 13c and mostly not in oxygen isotopic equilibrium with ambient seawater with the exception of the rhynchonellid notosaria nigricans the outer primary layer material was depleted in 13c and 18o and highly variable inclusion of this material even as part of a whole shell sample could lead to misinterpretation of seawater temperature therefore only fossil secondary layer material should be used the anomalous articulated thecideidine brachiopod thecidellina barretti is composed of mainly primary shell material and was not in oxygen isotope equilibrium 18o values from the laminar secondary layer material of the inarticulated craniida are highly variable therefore these species are not recommended for use as palaeoenvironmental proxies this study suggests caution when employing fossil brachiopod shells with similar ultrastructures to modern craniid and thecideidine brachiopods the carbon isotope composition is highly variable in all of the brachiopods studied analysis of samples from specialised regions of the secondary shell layer show a pattern of depletion in 13c relative to non specialised secondary material the carbon isotope variability is independent of 18o and is repeated in most of the articulated species regardless of geographical location this is possibly a vital effect produced by metabolic prioritisation

polyphase tectonics at the southern tip of the manila trench mindoro tablas islands philippines abstract the southern termination of the manila trench within the south china sea continental margin in mindoro is marked by a complex polyphase tectonic fabric in the arc trench gap area onshore southern mindoro the active deformation front of the manila trench is marked by parallel folds and thrusts grading southward to n50 w trending left lateral strike slip faults this transpressive tectonic regime active at least since the late pliocene has overprinted the collision of an early miocene volcanic arc with the south china sea continental margin san jose platform the collision is postdated by deposition of the late miocene early pliocene elastics of the east mindoro basin the tectonic and geological framework of this arc which overlies a metamorphic basement and eocene elastics suggests that it was built on a drifted block of the south china sea continental margin

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

δ18o and δ13c values of modern brachiopod shells abstract researchers have not rigorously tested the hypothesis that calcite from modern brachiopod shells is precipitated in oxygen isotope equilibrium with ambient seawater isotopic variability at the intraspecimen and intertaxon levels has not been examined without such data for modern brachiopods similar data from ancient brachiopods cannot be accurately interpreted in this study a survey is made of 18 o and 13 c values of terebratulid rhynchonellid thecideidine and craniacean brachiopods from antarctica the bay of fundy curacao japan new zealand norway puget sound palau sicily and south africa this suite of samples provides a wide range of taxonomic levels temperatures salinities and depositional environments for evaluating the degree of isotopic equilibrium attained during precipitation of brachiopod calcite new data indicate that modem brachiopod calcite is not always precipitated in oxygen and carbon isotope equilibrium with ambient seawater calcite from the primary layer and specialized shell structures hinge brachidium foramen interarea muscle scars are depleted in both 18 o and 13 c a characteristic of biological fractionation or vital effects often found in other calcerous marine organisms our findings suggest that these portions of the brachiopod shell should be avoided during sampling of ancient brachiopods secondary layer calcite the material most often analyzed in ancient brachiopods has higher 18 o and 13 c values which approach and sometimes correspond with predicted equilibrium values therefore secondary layer calcite is the most suitable portion of the brachiopod shell for use as an ancient seawater proxy although near equilibrium precipitation in secondary layer calcite is encouraging to those studying the isotopic composition of ancient oceans these data come with caveats large intraspecimen variability in the 18 o values of secondary layer calcite 1 in some samples limits the use of brachiopods as precise indicators of the 18 o value or temperature of ancient seawater the 18 o and 13 c values of secondary layer calcite deviate from predicted equilibrium values toward the lower values of the primary layer and specialized shell structures indicating a measurable vital effect in most cases measured 18 o values are lower than the calculated equilibrium values dictated by seasonal variations in the 18 o value and temperature of seawater ontogenetic variations in the 13 c values of secondary layer calcite have also been measured and must be assessed when interpreting ancient data modern brachiopods occur in a wide range of seawater salinities and temperatures therefore the relation between salinity and the 18 o value of seawater must be known to correctly calculate the temperature of calcite precipitation from secondary layer 18 o values errors of up to 15 c are found if ambient seawater is assumed to have a constant 18 o value e g 0 smow and the 18 o values of secondary layer calcite are used to calculate temperature coupled with vital effects and intraspecimen variability these errors can obscure the resolution of secular variations in the rock record

strontium isotope evolution of late permian and triassic seawater the 87sr 86sr values based on brachiopods and conodonts define a nearly continuous record for the late permian and triassic intervals minor gaps in measurements exist only for the uppermost brahmanian lower part of the upper olenekian and middle norian and only sparse data are available for the late permian these 219 measurements include 67 brachiopods and 114 conodont samples from the tethyan realm as well as 37 brachiopods and one conodont sample from the mid european middle triassic muschelkalk sea the late permian lower triassic interval is characterized by a steep 1 3 10 3 rise from 0 7070 at the base of the dzhulfian to 0 7082 in the late olenekian a rate of change comparable to that in the cenozoic in the mid triassic anisian and ladinian the isotope values fall to 0 7075 followed again by a rise to 0 7081 in the middle late norian the 87sr 86sr values decline again in the late norian sevatian and rhaetian to 0 7076 the sharp rise in the 87sr 86sr values during the late permian early triassic was coincident with widespread clastic sedimentation because of the paucity of tectonic uplifts the enhanced erosion may have been due to intermittent humid phases during mainly an arid interval coupled with the absence of a dense protective land plant cover following the mass extinction during the latest permian the apex of the 87sr 86sr curve at the olenekian anisian boundary coincides with cessation of the large scale clastic sedimentation and also marks the final recovery of land vegetation as indicated by the renewed onset of coal formation in the middle triassic the rising 87sr 86sr values from the middle carnian to the late norian coincide with the uplift and erosion of the cimmeride indosinian orogens marking the closure of the palaeotethys the subsequent rhaetian decline that continues into jurassic pliensbachian toarcian boundary on the other hand coincides with the opening of the vardar ocean and its eastern continuation in the izmir ankara ophiolitic belt samples from the upper muschelkalk are more radiogenic than the global trend this may reflect separation of the basin from the open ocean due to strong meteoric influx from a large land mass in the north the germanic basin became increasing brackish up section in the north and east but because of the high evaporation rates the salt content was not much reduced in the southern and central basin where a rich but increasingly endemic marine fauna survived