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

late ordovician global warming the boda event there is substantial evidence for mid ashgillian global warming before the latest ordovician hirnantian glaciation as shown by the movement of previously lower latitude benthic faunas such as trilobites and brachiopods to progressively higher latitudes and by an increase in endemic faunas at low latitudes this is shown by faunal dynamics on several paleocontinents and endorsed by published evidence of warmer water sediments from gondwana and elsewhere we term this global warming the boda event

neoproterozoic cap dolostone deposition in stratified glacial meltwater plume abstract neoproterozoic cap carbonates host distinctive geochemical and sedimentological features that reflect prevailing conditions in the aftermath of snowball earth interpretation of these features has remained contentious with hypotheses hinging upon timescale and synchronicity of deposition and whether or not geochemical signatures of cap carbonates represent those of a well mixed ocean here we present new high resolution sr and mg isotope results from basal ediacaran cap dolostones in south australia and mongolia least altered sr and mg isotope compositions of carbonates are identified through a novel incremental leaching technique that monitors the purity of a carbonate sample and the effects of diagenesis these data can be explained by the formation of these cap dolostones involving two chemically distinct solutions a glacial meltwater plume enriched in radiogenic sr and a saline ocean residue with relatively lower 87sr 86sr ratios model simulations suggest that these water bodies remained dynamically stratified during part of cap dolostone deposition most likely lasting for 8 thousand years our results can potentially reconcile previous conflicts between timescales estimated from physical mixing models and paleomagnetic constraints geochemical data from cap carbonates used to interpret the nature of snowball earth and its aftermath should be recast in terms of a chemically distinct meltwater plume

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

biogenic chert and the ordovician silica cycle abstract analysis of 161 nodular and bedded cherts shows that shallow water biosiliceous facies which were common in the lower ordovician had mostly retreated from peritidal lagoonal facies to deeper settings by the middle ordovician for decades this retreat was thought to have spanned the cambrian and ordovician periods our data suggest that the basinward shift may have taken approximately 2 14 m y in the late lower to early middle ordovician a likely cause for the departure of these often siliceous sponge cherts from shallow waters was depletion of shallow water dissolved silica dsi increased use of dsi by radiolarians may have commenced in the middle ordovician when radiolarians increased just as a pulse of radiolarite deposition began siliceous sponges may have been forced to relocate to deeper waters because radiolarians depleted shallow water dsi apparent low relative sea level in the middle ordovician may have hampered the formation and or preservation of shallow water cherts by reducing available shelf area to host such deposits however the resurgence of shelf chert in the upper ordovician while peritidal cherts remained virtually absent suggests that biology was critical to driving the basinward shift of cherty facies formation and preservation of abundant latest darriwilian through sandbian cherts may have been favored in deep water settings during a possible warming interval marked by sea level rise and extensive anoxia and euxinia that coincided with an ongoing decline in 87sr 86sr ratios and increased sea floor volcanic activity that probably enriched the dsi content of deep ocean waters ocean circulation associated with the onset of cooling in the katian may have optimized chert accumulation by stimulating surface water biosiliceous productivity before dsi rich chert preserving anoxic basins were ventilated as late ordovician glaciation intensified deep ocean ventilation by thermohaline sinking of oxygen rich waters probably decreased preservation potential of biosiliceous deposits while increasing oceanic recycling of silica

carbon and sulfur isotopic anomalies across the ordovician silurian boundary on the yangtze platform south china abstract abundance of organic matter carbon isotopic compositions of organic matter 13corg and sulfur isotopic compositions of iron sulfide 34ssulfide across the ordovician silurian o s boundary was analysed from two sections wangjiawan western hubei nanbazi northern guizhou on the yangtze platform south china the organic abundance across the o s boundary at these two sections is generally high except for the hirnantian interval at wangjiawan section in western hubei the 13corg values vary from about 30 8 vpdb in the mid ashgill to 27 6 in the upper hirnantian interval which abruptly return to the pre hirnantian values at nanbazi section in northern guizhou 13corg values vary from 30 5 to 26 6 from the mid ashgill to the upper hirnantian horizons which shift negatively to the low spike at 29 2 in the lowermost rhuddanian then increase slightly to relatively persistent values around 28 similar variation patterns of 34ssulfide values are unravelled at the two sections showing a positive excursion from the mid ashgill to the upper hirnantian then a sharp negative shift in the lowermost rhuddanian although with different background values of 34ssulfide from these two sections these data together with those from other areas demonstrate large climatic fluctuations from warming to cooling then to warming oceanic changes from and anoxic to oxygenated to anoxic water columns during the o s transition climatic fluctuations together with multiple oceanic anoxia and sea level fluctuations were likely responsible for the stepwise massive demise of the o s biotic crisis

the timing of late pleistocene mammalian extinctions in north america more than 375 14c dates from 150 fossil sites in north america have been analyzed to evaluate the question of extinction of late pleistocene megafauna when critically evaluated no 14c ages for any extinct pleistocene genera are younger than 10 000 yr b p

the gisp2 δ18o climate record of the past 16 500 years and the role of the sun ocean and volcanoes measured 18o 16o ratios from the greenland ice sheet project 2 gisp2 ice core extending back to 16 500 cal yr b p provide a continuous record of climate change since the last glaciation high resolution annual 18o 16o results were obtained for most of the current millennium a d 818 1985 and record the medieval warm period the little ice age and a distinct 11 yr 18o 16o cycle volcanic aerosols depress central greenland annual temperature 1 5 c maximally and annual 18o 16o for about 4 yr after each major eruptive event on a bidecadal to millennial time scale the contribution of solar variability to holocene greenlandic temperature change is 0 4 c the role of thermohaline circulation change on climate problematic during the holocene is more distinct for the 16 500 10 000 cal yr b p interval analogous to 14c age calibration terminology we express time in calibrated cal yr b p a d 1950 0 cal yr b p the oldest dryas bolling older dryas allerod younger dryas sequence appears in great detail bidecadal variance in 18o 16o but not necessarily in temperature is enhanced during the last phase of lateglacial time and the younger dryas interval suggesting switches of air mass transport between jet stream branches the branched system is nearly instantaneously replaced at the beginning of the bolling and holocene at 14 670 and 11 650 cal yr b p respectively by an atmospheric circulation system in which 18o 16o and annual accumulation initially track each other closely thermodynamic considerations of the accumulation rate temperature relationship can be used to evaluate the 18 o 16o temperature relationship the gisp2 ice layer count years of major gisp2 climate transitions also support the use of coral 14c ages for age calibration

the sporormiella proxy and end pleistocene megafaunal extinction a perspective counts of dispersed spores of the pyrenomycete dung fungus sporormiella have recently gained prominence as a technique to examine the end pleistocene mass extinction early investigations were able to identify sporormiella occurrence on the dung of extinct species including squirrel and mammoth these early studies also noted an important trend in sporormiella abundance over time in north america such that spore abundances were high during the late pleistocene low for most of the holocene and again prominent with the introduction of large grazing animals by early explorers in more recent studies changes in the abundance of spores of this fungus in sediments have been used as a proxy to define megafaunal population presence decline and extinction during the late pleistocene and a number of sites in the northeastern usa show a similar pattern of sporormiella abundance over time it is our opinion that some critical taxonomic and taphonomic investigations have not been completed for sporormiella and because of this there are complications in interpreting the sporormiella spore abundance data we constructively evaluate this analytical technique and propose supporting studies that could enhance its potential as an indicator of megaherbivore extinction and its use as a proxy for the end pleistocene extinction

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

the magnitudes of millennial and orbital scale climatic change in eastern north america during the late quaternary abstract temporal differences among fossil pollen samples from eastern north america provide a measure of the amount of climatic change that occurred on a broad spatial scale since the last glacial maximum 21 000 cal yr bp square chord distances scds quantify the difference between pollen samples and thus represent the potential magnitude of climatic change underlying the pollen record the magnitude varied significantly among time scales with small changes common at centennial to millennial scales and large changes common at multi millennial i e orbital scales scds measured across 3000 yr intervals averaged 0 20 and often exceeded the maximum difference expected from samples collected within the same biome 0 15 scds across individual millennia were smaller and averaged 0 08 scds across the millennia at the beginning 13 000 12 000 cal yr bp and end 12 000 11 000 cal yr bp of the younger dryas chronozone 12 900 11 600 cal yr bp however averaged 0 20 and 0 18 respectively these rapid step changes large at sub millennial scales equal about 5 25 of the total glacial interglacial transition large magnitude progressive changes in insolation ice sheet extent and atmospheric composition parallel the dominant trends in the scd data which show that progressive change comprises the first order climatic pattern of the holocene rather than stable or oscillatory patterns

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

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

patterns of faunal extinction and paleoclimatic change from mid holocene mammoth and polar bear remains pribilof islands alaska abstract qagnax cave a lava tube cave on st paul island in the pribilofs has recently produced a mid holocene vertebrate faunal assemblage including woolly mammoth polar bear caribou and arctic fox several dates on the mammoth remains converge on 5700 14c yr bp these dates 2300 yr younger than mammoth dates previously published from the pribilof islands make these the youngest remains of proboscideans and of non extinct quaternary megafauna recovered from north america persistence of mammoths on the pribilofs is most parsimoniously explained by the isolation of the pribilofs and the lack of human presence in pre russian contact times but an additional factor may have been the local existence of high quality forage in the form of grasses enriched by nutrients derived from local holocene tephras this interpretation is reinforced by stable carbon and nitrogen isotope values obtained from the mammoth remains the endpoint of mammoth survival in the pribilofs is unknown but maybe coterminous with the arrival of polar bears whose remains in the cave date to the neoglacial cold period of 4500 to 3500 14c yr bp the polar bear record corroborates a widespread cooling of the bering sea region at that time

proboscideans and paleoenvironments of the pleistocene great lakes landscape vegetation and stable isotopes abstract in this study we review the history of proboscideans in the great lakes region ontario and western new york in the context of local glacial and vegetational histories further we investigate mammoth mammuthus and mastodon mammut environmental niche partitioning using stable isotope analysis of bone and dentin collagen 13 c col 15 n col and structural carbonate in tooth enamel bioapatite 13 c sc 18 o sc and demonstrate that stable isotopes can be used to identify non locals among museum specimens with no contextual records new radiocarbon dates suggest that ontario mastodons lived in tundra like environments as well as their more common spruce forest habitat local ontario new york mammoths and mastodons consumed 100 c 3 plant diets and drank low 18 o waters consistent with colder than modern climates and proximity to glacial meltwater sources mammoths and mastodons occupied distinct environmental niches characterized by different oxygen and nitrogen isotope compositions and geographical locations this suggests that direct competition for resources was not a major factor in their local extinction we suggest that both mammoths and mastodons obtained water from sources formed primarily from precipitation rather than glacial meltwater we describe how high 15 n values in mammoths could have been caused by a combination of preferences for dry environments consumption of low nutrient forage particularly stems and stalks coprophagy geophagy and dung fertilization we argue that low 15 n values in mastodons could have been caused by consumption of trees and shrubs including nitrogen fixing taxa and a preference for recently deglaciated landscapes and or spruce environments finally we raise the possibility that mastodons contributed to the spruce pine transition by browsing directly on spruce trees

changes in marine productivity and redox conditions during the late ordovician hirnantian glaciation abstract changes in marine productivity and redox conditions during the end ordovician hirnantian glaciation and ordovician silurian transition were investigated through mo isotope and major and trace element analyses of the wangjiawan hubei province and nanbazi guizhou province sections from the yangtze platform of south china katian shales of the wufeng formation which yield the graptolites dicellograptus complanatus dicellograptus complexus and paraorthograptus pacificus were deposited under euxinic conditions at both localities as shown by high mo ef u ef and 98 mo values a major sea level regression during the hirnantian glaciation resulted in shallowing and a shift toward better oxygenated conditions within the yangtze sea as well as deposition of thin bedded siliceous sediments calcirudite debris flows and limestone turbidites of the kuanyinchiao formation the base of which correlates with the first phase of the end ordovician mass extinction the termination of the hirnantian glaciation at the top of the kuanyinchiao formation was associated with a major sea level transgression a rapid expansion of euxinia in the yangtze sea as documented by a return of high mo ef u ef and 98 mo values and the second phase of the mass extinction during which the cool adapted hirnantian fauna went extinct the long term cooling trend of the middle and late ordovician which culminated in the hirnantian glaciation was driven by enhanced burial of organic carbon as documented by 13 c carb 13 c org and 34 s py records increased organic carbon burial was linked to high rates of marine productivity as shown by high toc and biogenic ba concentrations especially at the deeper less restricted wangjiawan locale producing the hice hirnantian isotopic curve excursion 13 c carb excursion the locus of organic carbon burial during the hirnantian crisis shifted to deeper water environments that were located outside the study region the relatively rapid onset and termination of the hirnantian glaciation were probably due to crossing of tipping points in the late ordovician climatic oceanic system

extinctions in north america s late glacial landscapes human caused extinctions of terrestrial mammals in large parts of the world such as north america may have been side effects of rapid long distance dispersals biogeographic range change by homo sapiens moving outward from the old world the extinctions help explain how modern humans briskly explored and populated large empty and increasingly unfamiliar landmasses infrequent opportunistic human hunting along with the climate caused fragmentation of megafaunal populations may have led to nonrandom human dispersals through megafaunal source areas which effectively were continental stepping stones resulting in temporally clustered extinctions the process in north america was three step and mostly occurred before the younger dryas cold interval first was a foreshock when late glacial climatic changes and a trickle of first foragers fragmented continental megafaunal populations second was a severe additional shock when human foragers targeted the pockets of fragmented subpopulations and preferentially hunted them and third was an extended aftershock of sustained hunting inbreeding damage and acute competition for contracting resources during which megafaunal taxa dwindled and became extinct some taxa may have managed to survive into the younger dryas or beyond if there were pre clovis people in the continent the second shock phase may have preceded clovis perhaps by up to a millennium but by the time of the third aftershock phase the clovis dispersal was rapidly underway

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

the anatomy of a climatic oscillation vegetation change in eastern north america during the younger dryas chronozone century scale climate changes reshaped circulation patterns over the north atlantic and adjacent regions during the last glacialto interglacial transition here we show that vegetation across eastern north america shifted dramatically at the beginning and end of the younger dryas chronozone ydc 12 900 11 600 cal yr b p when changes in ocean circulation rapidly cooled and then warmed the north atlantic sea surface on both the site specific scale and the continental scale vegetation changed only gradually during the millennia before 15 000 13 000 cal yr b p and after 11 000 9000 cal yr b p the ydc but climate changes ca 12 900 and 11 600 cal yr b p altered the vegetation on both spatial scales within centuries plant associations changed and some taxa rapidly migrated hundreds of kilometers 300 km within b100 yr in limited regions near the north atlantic coast abrupt cooling ca 12 900 cal yr b p resulted in a return to earlier vegetation types elsewhere however the vegetation patterns during the ydc were distinct from those of both earlier and later intervals they indicate abrupt non reversing seasonal temperature changes that were probably related to atmospheric circulation changes during the ydc rather than to the direct influence of north atlantic sea surface temperatures atmospheric circulation patterns during the ydc were unique within the last 21 000 yr because of a unique combination of climate controls insolation ice sheet extent and atmospheric composition were significantly different from their full glacial states even when the north atlantic returned to near full glacial conditions the ydc vegetation patterns demonstrate 1 rapid ecological responsiveness to abrupt climate change and 2 spatially varied patterns of ydc climate change r 2002 elsevier science ltd all rights reserved

comprehensive analysis of nanodiamond evidence relating to the younger dryas impact hypothesis during the end of the last glacial period in the northern hemisphere near 12 9k cal a bp deglacial warming of the bolling allerod interstadial ceased abruptly and the climate returned to glacial conditions for an interval of about 1300 years known as the younger dryas stadial the younger dryas impact hypothesis proposes that the onset of the younger dryas climate reversal pleistocene megafaunal extinctions and disappearance of the clovis paleoindian lithic technology were coeval and caused by continent wide catastrophic effects of impact bolide events in north america while there are no known impact structures dated to the younger dryas onset physical evidence of the impact bolide events is argued to be present in sediments spanning several continents at stratigraphic levels inferred to date to the bolling allerod younger dryas boundary ydb reports of nanometer to submicron sized diamonds in ydb sediments in particular the rare 2h hexagonal polytype of diamond lonsdaleite have been presented as strong evidence for shock processing of crustal materials we review the available data on diamonds in sediments and provide new data we find no evidence for lonsdaleite in ydb sediments and find no evidence of a spike in nanodiamond concentration at the ydb layer to support the impact hypothesis

organic matter accumulation of late ordovician sediments in north guizhou province china sulfur isotope and trace element evidences abstract the organic rich upper ordovician sediments wufeng and guanyinqiao formations on the yangtze platform are considered to be one of the main source rocks here we present geochemical proxies including redox indicator s c ratios and sulfur isotopes and productivity indices toc mo and ba contents from nanbazi section in north guizhou province south china in order to investigate the mechanism of organic matter accumulation the geochemical data suggest a stagnant and anoxic environment predominated the yangtze sea during the wufeng period whereas ventilated and oxygenated marine conditions pervaded the yangtze sea during the guanyinqiao period variations in the concentration of toc mo and ba indicate that higher organic carbon export in the wufeng intervals than those in the guanyinqiao intervals these variations in redox and productivity during the late ordovician were associated with different mechanisms and forcing processes the abrupt change from anoxic to oxygenated condition at the beginning of the guanyinqiao was concomitant with the global glacial period likely resulted from the glacio eustatic sea level fall and subsequent circulation of cold dense oxygenated waters upon the shelf seabed the productivity variations were related to the change of nutrient supply which is consistent with volcanic activities and runoff to the yangtze sea redox changes together with primary productivity fluctuations could have played a significant role on the variation of organic matter accumulation during the late ordovician in south china

large perturbations of the carbon and sulfur cycle associated with the late ordovician mass extinction in south china high resolution 13 c data of organic carbon from a continuous section of the late ordovician early silurian reveal two positive 13 c excursions that are associated with the mass extinction in south china the fi rst stratigraphic 34 s measurements on pyrite tied to well established biostratigraphy indicate a large perturbation of the sulfur cycle consistent with major sea level changes related to the glaciation the elevated 34 s values of pyrites and a large short lived negative 34 s excursion of 20 associated with the decay of the glaciation suggest deep water anoxia during the hirnantian stage in contrast to the conventional view that the global oceans were oxygenated we suggest that deep water anoxia may have contributed to the late ordovician mass extinction in south china and possibly elsewhere

spatial variation of carbon isotopic compositions of carbonate and organic matter from the late ordovician sedimentary succession in the yangtze platform south china implications for sea level eustacy and shoaling of marine chemocline abstract spatial correlation of isotopic chemostratigraphy across ancient epeiric basins is of particular interest in the field of geology this study examines the carbon isotopic compositions of carbonate and organic matter from the late ordovician sedimentary succession in the yangtze platform including the linxiang lx formation deposited in the bottom and the tiezufeike tzfk daduhe ddh wufeng wf formations in the top paired 13ccarb and 13corg analyses of the upper ordovician strata on the yangtze platform were recorded and the results show that the rocks in the lx formation have high 13ccarb and 13corg values relative to those in the ddf tzfk wf formations additionally a variation of 2 was found between shallow and deep water settings during the late ordovician heavier 13ccarb and 13corg values are observed at the wukemuchang wkmc and wanhe wh sections representing the shallow regions of the yangtze platform relative to the tianjiawan tjw and tianba tb sections representing the deeper margin of the yangtze platform we suggest that the variations of 13c in carbonate and organic matter are related to the sea level eustacy and shoaling of marine chemocline 1 sea level rise driven decrease in local scale carbonate weathering 2 decreased decomposition of organic matter under anoxic conditions and 3 incorporation of non photosynthetic chemoautorophic bacteria living in deeper waters the 13c 13c 13ccarb 13corg values in both the wh and wkmc sections display an increasing trend upward from the lx formation to the overlying strata varying from 27 8 to 31 2 and from 28 1 to 31 1 respectively these increased 13c values are related to the enhanced nutrients and correspondingly high primary productivity and thus that the anoxic water conditions and high primary productivity may be the significant factors in the deposition of late ordovician black shales

on the uncertainty of sea ice isostasy during late winter 2007 coincident measurements of sea ice were collected using various sensors at an ice camp in the beaufort sea canadian arctic analysis of the archived data provides new insight into sea ice isostasy and its related r factor through case studies at three scales using different combinations of snow and ice thickness components at the smallest scale 1m point scale isostasy is not expected so we calculate a residual and define this as zjey to describe vertical displacement due to deformation from 1 to 10m length scales we explore traditional isostasy and identify a specific sequence of thickness calculations which minimize freeboard and elevation uncertainty an effective solution exists when the r factor is allowed to vary ranging from 2 to 12 with mean of 5 17 mode of 5 88 and skewed distribution at regional scales underwater airborne and spaceborne platforms are always missing thickness variables from either above or below sea level for such situations realistic agreement is found by applying small scale skewed ranges for the r factor these findings encourage a broader isostasy solution as a function of potential energy and length scale overall results add insight to data collection strategies and metadata characteristics of different thickness products

perturbation of the marine nitrogen cycle during the late ordovician glaciation and mass extinction abstract the late ordovician was a critical interval in geologic history during which both the biosphere and marine environments underwent severe perturbations including one of the big five phanerozoic mass extinctions and the massive but short term 0 5 myr hirnantian glaciation the onset and termination of the hirnantian glaciation have been widely accepted as the triggers for the two extinction pulses that comprise the late ordovician biocrisis but the mechanisms that caused the hirnantian glaciation itself remain poorly known here we analyze the nitrogen isotope composition 15 n of two sections in south china wangjiawan and nanbazi in order to better understand nitrogen cycle perturbations in the late ordovician ocean and their relationship to contemporaneous climatic and biogeochemical changes low 15 n 1 in the upper katian and lower rhuddanian of both sections suggests intensive i e near quantitative denitrification and thus nitrogen fixation as the main source of biologically available nitrogen for primary producers a positive 15 n excursion in both sections during the hirnantian indicates weaker i e non quantitative denitrification possibly as a result of more vigorous thermohaline circulation and improved ocean ventilation weaker denitrification would have reduced the flux of n 2 o an intermediate product of denitrification to the atmosphere n 2 o is a potent greenhouse gas and a major decline in its production would have led to cooler climatic conditions and ultimately the hirnantian glaciation a global survey of published nitrogen isotope records suggests that similar processes operated broadly within the late ordovician global ocean

first plants cooled the ordovician the late ordovician period ending 444 million years ago was marked by the onset of glaciations the expansion of non vascular land plants accelerated chemical weathering and may have drawn down enough atmospheric carbon dioxide to trigger the growth of ice sheets

post clovis survival of american mastodon in the southern great lakes region of north america abstract the end of the pleistocene in north america was marked by a wave of extinctions of large mammals with the last known appearances of many species falling between ca 11 000 10 000 14c yr bp temporally this period overlaps with the clovis paleoindian cultural complex 11 190 10 530 14c yr bp and with sudden climatic changes that define the beginning of the younger dryas chronozone ca 11 000 10 000 14c yr bp both of which have been considered as potential proximal causes of this extinction event radiocarbon dating of enamel and filtered bone collagen from an extinct american mastodon mammut americanum from northern indiana usa by accelerator mass spectrometer yielded direct dates of 10 055 40 14c yr bp and 10 032 40 14c yr bp indicating that the animal survived beyond the clovis time period and into the late younger dryas although the late survival of this species in mid continental north america does not remove either humans or climatic change as contributing causes for the late pleistocene extinctions neither clovis hunters nor the climatic perturbations initiating the younger dryas chronozone were immediately responsible for driving mastodons to extinction

facies patterns and geography of the yangtze region south china through the ordovician and silurian transition abstract lithofacies and biofacies changes through the ordovician and silurian transition on the yangtze platform are coincident with stepwise mass extinctions recovery events global sea level changes and regional palaeogeographic configurations facies patterns through three intervals the late mid ashgill hirnantian and early rhuddanian indicate that black shale occupied most of the yangtze platform region during the late mid ashgill and early rhuddanian while the hirnantian possesses more diverse facies types the black shale was replaced by carbonate facies during the hirnantian coincident with a global sea level low stand biofacies changes from the late mid ashgill graptolitic to the hirnantian shelly facies were apparently signalled by gradual and diachronous existence of a mixed facies the manosia facies in the yangtze region however the biofacies change was abrupt from the hirnantian to the early rhuddanian when graptolitic facies occupied most areas on the yangtze platform leaving only a very narrow limited belt of shelly facies along the southern margin of the platform in northern guizhou the early rhuddanian unified biofacies pattern is a result of a global sea level rise which may be synchronized with a recovery bioevent of graptolites after hirnantian mass extinction

younger dryas black mats and the rancholabrean termination in north america of the 97 geoarchaeological sites of this study that bridge the pleistocene holocene transition last deglaciation approximately two thirds have a black organic rich layer or black mat in the form of mollic paleosols aquolls diatomites or algal mats with radiocarbon ages suggesting they are stratigraphic manifestations of the younger dryas cooling episode 10 900 b p to 9 800 b p radiocarbon years this layer or mat covers the clovis age landscape or surface on which the last remnants of the terminal pleistocene megafauna are recorded stratigraphically and chronologically the extinction appears to have been catastrophic seemingly too sudden and extensive for either human predation or climate change to have been the primary cause this sudden rancholabrean termination at 10 900 50 b p appears to have coincided with the sudden climatic switch from allerod warming to younger dryas cooling recent evidence for extraterrestrial impact although not yet compelling needs further testing because a remarkable major perturbation occurred at 10 900 b p that needs to be explained

the geochemistry of carbonate diagenesis the past present and future stable carbon and oxygen isotopes 18o and 13c values and trace elements have been applied to the study of diagenesis of carbonate rocks for over 50 years as valuable as these insights have been many problems regarding the interpretation of geochemical signals within mature rocks remain for example while the 18o values of carbonate rocks are dependent both upon the temperature and the 18o value of the fluid and additional information including trace element composition aids in interpreting such signals direct evidence of either the temperature or the composition of the fluids is required such information can be obtained by analysing the 18o value of any fluid inclusions or by measuring the temperature using a method such as the clumped isotope technique such data speak directly to a large number of problems in interpreting the oxygen isotope record including the well known tendency for 18o values of carbonate rocks to decrease with increasing age unlike the 18o 13c values of carbonates are considered to be less influenced by diagenesis and more a reflection of primary changes in the global carbon cycle through time however many studies have not sufficiently emphasized the effects of diagenesis and other post depositional influences on the eventual carbon isotopic composition of the rock with the classic paradigm that the present is the key to the past being frequently ignored finally many additional proxies are poised to contribute to the interpretation of carbonate diagenesis although the study of carbonate diagenesis is at an exciting point with an explosion of new proxies and methods care should be taken to understand both old and new proxies before applying them to the ancient record

tracking the hirnantian glaciation using os isotopes article i nfo article history here we present initial 187 os 188 os osi values integrated with 13 corg for the first paleozoic section the ordovician silurian boundary gssp at dob s linn scotland our 187 os 188 os data tracks major changes in climate that occurred during the late ordovician hirnantian glaciation which coincides with the second largest known mass extinction during the complanatus and early anceps biozones osi values increase from 0 28 1 08 this provides evidence for a period of increased silicate weathering of radiogenic continental crust likely from the caledonian orogen this increase in weathering was likely the driving mechanism for the drawdown in atmospheric co2 and global cooling that resulted in the onset of the hirnantian glaciation a decrease to less radiogenic osi occurs at the base hirnantian extraordinarius biozone and coincides with the trend to more positive 13 corg values that mark the onset of the hirnantian glaciation the trend in osi during this interval is ascribed to hirnantian ice cover and reduced chemical weathering rates cutting the supply of radiogenic material to the iapetus ocean the reduction in silicate weathering enabled atmospheric co2 to return back to greenhouse levels causing rapid deglaciation during the mid persculptus biozone this period is marked by an abrupt increase in osi values from 0 6 to 1 08 over 19 cm of stratigraphy and coincides with the deglacial limb of the 13 corg profile we interpret the osi data to reflect the leaching of exposed

local and global perspectives on carbon and nitrogen cycling during the hirnantian glaciation abstract the impact of climate and ocean circulation changes on marine carbon and nitrogen cycling was investigated for a period covering the late ordovician hirnantian glaciation three sections were studied two from nevada one proximal and one distal and one from the yukon the opportunity to compare 13 c carb 13 c org and 13 c grap profiles between ocean and epeiric platform settings enabled a more thorough assessment of environmental and diagenetic factors influencing the preservation of seawater 13 c values at each stratigraphic section using the best preserved sedimentary components from the two nevada sections a lowstand sedimentary gradient of 4 was found between platform and ocean settings during the hirnantian glaciation gradients of similar magnitude have been reported from hirnantian platforms in the canadian arctic and baltic basins taking the outboard sections as the most representative of the ocean carbon pool a mean positive 13 c shift of just 2 7 0 4 is calculated which is significantly smaller than the 5 7 positive shifts recorded in epeiric platform settings the discrepancy is attributed to the effects of local carbon cycling in tropical and subtropical epeiric seas it is hypothesized that increased carbonate weathering caused 13 c values of local carbon weathering fluxes to increase which in turn caused seawater 13 c values to increase in basin proximal settings in addition nutrient dust fluxes may have contributed to increased levels of photosynthetic activity in proximal settings driving sedimentary 13 c values even higher much higher than sediment deposited in outboard settings where carbon exchanges with the surface ocean were less restrictive a 15 n profile reconstructed from deposits of the distal vinini creek section records a 1 5 positive shift through the hirnantian glacial interval interpreted as a major late ordovician upwelling zone high organic carbon 1 wt and high hydrogen indices 400 600 make the vinini creek section a suitable candidate for the preservation of original sedimentary 15 n records to explain the results a conceptual model of ocean nitrogen cycling under greenhouse climate conditions is presented that highlights the role of cyanobacteria as both primary producers and nitrogen fixers it is hypothesized that in greenhouse climates the fixed nitrogen inventory of the abyssal ocean was low due to efficient denitrification in the ocean s expansive oxygen minimum zones this caused algal productivity to become strongly dependent on continuous supplies of fixed nitrogen from cyanobacteria in the photic zone yielding sedimentary 15 n values between 0 and 2 by contrast the cooler icehouse climate of the hirnantian led to increased ocean ventilation greater partitioning of atmospheric oxygen into downwelling surface waters and oxygen minimum zone shrinkage as a result fixed nitrogen levels climbed in the ocean s abyssal depths due to the lower denitrification rates this in turn allowed nitrogen with high 15 n values to recycle back into the photic zone driving sedimentary 15 n values higher during the hirnantian glaciation

large scale climatic fluctuations in the latest ordovician on the yangtze block south china likely under warm and humid conditions low cia values however indicate the near absence of chemical weathering thereby refl ecting cool and or arid conditions in this paper the paleo climatic changes during the ordovician silurian transition were reconstructed in the light of cia values derived from the chemical composition of fi ne grained siliciclastic rocks in the mid upper yangtze river region china the infl u ences of paleoclimatic changes on biota are also discussed abstract the ordovician silurian transition was a critical interval in earth s history marked by dramatic climatic oceanic and biological turnovers here we present the chemical index of alteration cia as a proxy of changes in intensity of chemical weathering and its varia tions across the ordovician silurian boundaries wufeng through guanyinqiao to longmaxi formations from wangjiawan and nanbazi on the yangtze block south china in order to explore the climatic changes our data show that the cia values of sediments commonly range from 75 to 90 in the wufeng and longmaxi formations indicating a high degree of chemical weathering and thus a hot and humid climate during deposition in contrast a sharp drop in cia values most 60 70 in the guanyinqiao formation or hirnantian suggests an overall cold and arid climate interrupted by several intervals of warm climate when deposited the temporal coincidence of two phases of massive biotic extinctions with the beginning and end of the cold climate epoch respectively suggests that the large climatic changes could be one of the main controls on the mass extinctions although other factors may also have played a role

accelerator radiocarbon dating at the molecular level molecular level 14c dating is the isolation of specific classes of molecules for their 14c dating by accelerator mass spectrometry ams complex matrices such as fossil bone are difficult to date due to their extreme chemical heterogeneity by isolating individual amino acids contaminants humates are removed and crystalline amino acids result bones with 0 1 0 2 n and collagenous compositions can be dated accurately because structural collagen is present contaminants are removable with xad resin bones with 0 1 n and non collagenous compositions yield dates hundreds to thousands of years too young because most of the preserved organic matter is exogenous accelerator 14c dates on collagenous and non collagenous bones are not comparable due to intrinsic dating inaccuracies ams 14c dating of amino acids demonstrated that 1 post 10 800 year ages for north american megafauna are due to sample contamination not holocene ages on extinct fauna 2 a clovis age 10 900 years was established for a human fossil from the anzick site montana 3 holocene ages cannot be established absolutely for many north american human fossils because the bones were non collagenous 4 accurate ages are attainable on vertebrate fossils as small as passerine birds from pacific island localities 5 well preserved bones are datable without their destruction by extracting protein with water at high temperatures and 6 stratigraphic anomalies to 45 000 years in european upper paleolithic rock shelters are recognizable by dating bone directly

a sulfidic driver for the end ordovician mass extinction the end ordovician extinction consisted of two discrete pulses both linked in various ways to glaciation at the south pole the first phase starting just below the normalograptus extraordinarius zone particularly affected nektonic and planktonic species while the second pulse associated with the normalograptus persculptus zone was less selective glacially induced cooling and oxygenation are two of many suggested kill mechanisms for the end ordovician extinction but a general consensus is lacking we have used geochemical redox indicators such as iron speciation molybdenum concentrations pyrite framboid size distribution and sulfur isotopes to analyze the geochemistry in three key hirnantian sections these indicators reveal that reducing conditions were occasionally present at all three sites before the first pulse of the end ordovician extinction and that these conditions expanded towards the second pulse even though the n extraordinarius zone appears to have been a time of oxygenated deposition pyrite is significantly enriched in 34s in our sections as well as in sections reported from south china this suggests a widespread reduction in marine sulfate concentrations which we attribute to an increase in pyrite burial during the early hirnantian the s isotope excursion coincides with a major positive carbon isotope excursion indicating elevated rates of organic carbon burial as well we argue that euxinic conditions prevailed and intensified in the early hirnantian oceans and that a concomitant global sea level lowering pushed the chemocline deeper than the depositional setting of our sites in the n persculptus zone an interval associated with a major sea level rise our redox indicators suggests that euxinic conditions and ferruginous in some places encroached onto the continental shelves in our model the expansion of euxinic conditions during the n extraordinarius zone was generated by a reorganization of nutrient cycling during sea level fall and we argue overall that these dynamics in ocean chemistry played an important role for the end ordovician mass extinction during the first pulse of the extinction euxinia and a steepened oxygen gradient in the water column caused habitat loss for deep water benthic and nektonic organisms during the second pulse the transgression of anoxic water onto the continental shelves caused extinction in shallower habitats

predominance of stratified anoxic yangtze sea interrupted by short term oxygenation during the ordo silurian transition abstract the ordo silurian transition was a critical interval in geological history during which profound biotic climatic and oceanic changes occurred in order to explore the oceanic palaeoredox changes multiple geochemical proxies including ratios of s c fehr fet fep fehr and dop values are presented here from three sections wangjiawan western hubei sanjiaguan northern hunan and nanbazi northern guizhou across the ordo silurian boundary on the yangtze platform these palaeoredox data indicate a predominance of stratified anoxic ferruginous ocean on the yangtze block during this transition which was interrupted by a brief episode of oceanic oxygenation in the early hirnantian this oxygenation temporally coinciding with the end ordovician glaciation and global glacio eustatic sea level fall likely resulted from enhanced circulation of polar cold dense oxygen rich water onto the low latitude shelf the prior and subsequent longer term episodes of anoxic ocean particularly the later one which started in the late hirnantian occurred in parallel with the rapid climatic warming and sea level rise which could have slowed down oceanic circulation thereby enhancing oceanic stratification anoxia and organic preservation oceanic redox changes together with rapid climatic and sea level fluctuations were likely responsible for the stepwise massive demise of the ordo silurian biotic crisis

comparison of organic and inorganic carbon isotope patterns across the frasnian famennian boundary abstract the carbon isotopic composition of organic matter is reported for two frasnian famennian boundary sections from the rheinische schiefergebirge germany during the late frasnian 13 c org values commonly range from 27 5 to 26 highest 13 c org values around 24 are encountered immediately above and below the kellwasser horizons all samples from the kellwasser horizons are depleted in 13 c org by 2 5 to 4 7 this depletion is explained by a higher proportion of biomass derived from isotopically depleted chemoautotrophic bacteria a comparison of the positive 13 c excursions shows that the 13 c org shifts precede the 13 c carb shifts by some 10 5 years consequently 13 c values document a shift towards lower values below the upper kellwasser horizon a contribution of terrestrial organic matter as well as a thermal alteration of the 13 c org signals do not provide compelling explanations for the earlier 13 c org shift increases in primary productivity or carbon burial rate will change the co 2 aq content of surface waters affect the carbon isotope fractionation during photosynthetic carbon uptake and thus enrich organic carbon in 13 c however both processes cannot account for the earlier onset of the 13 c org shift because the 13 c carb record should document the resulting 13 c enrichment in surface waters as well a reduction in the calcium carbonate precipitation rate due to the global extinction of the reef ecosystem may have played an important role in reducing the co 2 aq content of surface waters without changing the isotopic composition of surface waters whether this process or other factors such as a rise in sea surface temperature or a change in the phytoplankton association account for the earlier onset of the positive shift in the 13 c org curve must be determined by further studies that may be able to confirm the global significance of the reported 13 c org pattern in frasnian famennian boundary sections from other parts of the globe

response of late ordovician paleoceanography to changes in sea level continental drift and atmospheric pco2 potential causes for long term cooling and glaciation abstract we performed sensitivity experiments using an ocean general circulation model at two stages of the late ordovician caradoc 454 ma ashgill 446 ma under a range of atmospheric pco2 values 8 18 pal pre industrial atmospheric level at high and low sea level the model results indicate that the long term cooling trend during the late ordovician can be explained by progressive cooling of the global ocean in response to falling levels of atmospheric pco2 sea level change and paleogeographic change these results also explain the occurrence of low latitude cool water carbonates in north america in all simulations a drop in sea level led to a reduction in poleward ocean heat transport this indicates a possible positive feedback that could have enhanced global cooling in response to sea level drop during the late ordovician alterations in poleward ocean heat transport linked to changes of atmospheric pco2 also indicate that there is a threshold of 10 pal above which ocean current change cannot be responsible for glaciation in the late ordovician continental drift could explain the observed global cooling trend in the late ordovician through a combined poleward ocean heat transport feedback and increased ice albedo effect if atmospheric pco2 was low during the entire late ordovician the model results further indicate that the response of meridional overturning to changes in paleogeography atmospheric pco2 and sea level is stronger than the response of surface circulation to these perturbations because the overturning circulation is so strong meridional overturning was the dominant mechanism for described changes in heat transport in the late ordovician

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

american mastodon extirpation in the arctic and subarctic predates human colonization and terminal pleistocene climate change existing radiocarbon 14c dates on american mastodon mammut americanum fossils from eastern beringia alaska and yukon have been interpreted as evidence they inhabited the arctic and subarctic during pleistocene full glacial times 18 000 14c years b p however this chronology is inconsistent with inferred habitat preferences of mastodons and correlative paleoecological evidence to establish a last appearance date lad for m americanum regionally we obtained 53 new 14c dates on 36 fossils including specimens with previously published dates using collagen ultrafiltration and single amino acid hydroxyproline methods these specimens consistently date to beyond or near the 50 000 y b p limit of 14c dating some erroneously young 14c dates are due to contamination by exogenous carbon from natural sources and conservation treatments used in museums we suggest mastodons inhabited the high latitudes only during warm intervals particularly the last interglacial marine isotope stage mis 5 when boreal forests existed regionally our 14c dataset suggests that mastodons were extirpated from eastern beringia during the mis 4 glacial interval 75 000 y ago following the ecological shift from boreal forest to steppe tundra mastodons thereafter became restricted to areas south of the continental ice sheets where they suffered complete extinction 10 000 14c years b p mastodons were already absent from eastern beringia several tens of millennia before the first humans crossed the bering isthmus or the onset of climate changes during the terminal pleistocene local extirpations of mastodons and other megafaunal populations in eastern beringia were asynchrononous and independent of their final extinction south of the continental ice sheets