enhanced terrestrial weathering runoff and surface ocean carbonate production during the recovery stages of the paleocene eocene thermal maximum 1 the carbonate saturation profile of the oceans shoaled markedly during a transient global warming event known as the paleocene eocene thermal maximum petm circa 55 ma the rapid release of large quantities of carbon into the ocean atmosphere system is believed to have triggered this intense episode of dissolution along with a negative carbon isotope excursion cie the brevity 120 220 kyr of the petm reflects the rapid enhancement of negative feedback mechanisms within earth s exogenic carbon cycle that served the dual function of buffering ocean ph and reducing atmospheric greenhouse gas levels detailed study of the petm stratigraphy from ocean drilling program site 690 weddell sea reveals that the cie recovery period which postdates the cie onset by 80 kyr is represented by an expanded 2 5 m thick interval containing a unique planktic foraminiferal assemblage strongly diluted by coccolithophore carbonate collectively the micropaleontological and sedimentological changes preserved within the cie recovery interval reflect a transient state when ocean atmosphere chemistry fostered prolific coccolithophore blooms that suppressed the local lysocline to relatively deeper depths a prominent peak in the abundance of the clay mineral kaolinite is associated with the cie recovery interval indicating that continental weathering runoff intensified at this time as well robert and kennett 1994 such parallel stratigraphic changes are generally consonant with the hypothesis that enhanced continental weathering runoff and carbonate precipitation helped sequester carbon during the petm recovery period e g dickens et al 1997 zachos et al 2005

rapid inverse modeling of pressure interference tests using trajectory based traveltime and amplitude sensitivities 1 this paper presents an efficient trajectory based approach to integrate transient pressure data into high resolution reservoir and aquifer models the method involves alternating traveltime and peak amplitude matching of pressure response using inverse modeling and is particularly well suited for high resolution subsurface characterization using hydraulic tomography or pressure interference tests compared to traveltime inversion only our proposed approach results in a significantly improved match of the pressure response at the wells and also better estimates of subsurface properties this is accomplished with very little increase in computational cost utilizing the concept of a diffusive time of flight derived from an asymptotic solution of the diffusivity equation we develop analytical approaches to estimate the sensitivities for traveltime and peak amplitude of pressure response to subsurface properties the sensitivities are then used in an iterative least squares minimization to match the pressure data we illustrate our approach using synthetic and field examples in the field application at a fractured limestone formation the predominant fracture patterns emerging from the inversion are shown to be consistent with independent geophysical experiments and borehole data

impact of the paleocene eocene thermal maximum on deep ocean microbenthic community structure using rank abundance curves to quantify paleoecological response global climate change has often resulted in extinction events that can be quantitatively measured by taxonomic loss but are more diffi cult to assess in terms of ecological restructuring we use a commonly applied ecological tool rank abundance curves racs to evaluate the ecological response of benthic foraminiferal and ostracode communities to the paleoceneeocene thermal maximum which may be seen as an analog for current and future global warming racs are proxies for community structure and therefore changes in the shape of racs allow inferences to be drawn about and quantifi cation of ecological responses benthic foraminiferal communities became increasingly stressed during the paleocene eocene thermal maximum and community reorganization occurred before the taxonomically defi ned extinction horizon in contrast ostracode communities became less stressed during the same interval reinforcing the idea that different groups of organisms respond differently to extinction events and global warming the decoupling of ecologic impact from taxonomic impact during the paleocene eocene thermal maximum reaffi rms the fact that future climate change could have far reaching effects on taxa and ecosystems and proves the importance of examining both the taxonomic and ecologic responses of communities during extinction events

an inversion strategy for hydraulic tomography coupling travel time and amplitude inversion summary we present a hydraulic tomographic inversion strategy with an emphasis on the reduction of ambiguity of hydraulic travel time inversion results and the separation of the estimated diffusivity values into hydraulic conductivity and specific storage our tomographic inversion strategy is tested by simulated multilevel interference slug tests in which the positions of the sources injection ports and the receivers observation ports isolated with packers are varied simulations include the delaying effect of wellbore storage on travel times which are quantified and shown to be of increasing importance for shorter travel distances for the reduction of ambiguity of travel time inversion we use the full travel time data set as well as smaller data subsets of specified source receiver angles the inversion results of data subsets show different resolution characteristics and improve the reliability of the interpretation the travel time of a pressure pulse is a function of the diffusivity of the medium between the source and receiver thus it is difficult to directly derive values for hydraulic conductivity and specific storage by inverting travel times in order to overcome this limitation we exploit the great computational efficiency of hydraulic travel time tomography to define the aquifer structure which is then input into the underlying groundwater flow model modflow 96 finally we perform a model calibration amplitude inversion using the automatic parameter estimator pest enabling us to separate diffusivity into its two components hydraulic conductivity and specific storage

working in complex areas new restoration workflow based on quality control 2d and 3d restorations when working in complex areas the explorationist needs to construct 3d models and to check their coherency coherence can be analyzed on the current geometry but could also be quantified through restoration to achieve this restoration i e the search for an initial geometry with a realistic deformation pathway between the initial and the final geometries appropriate tools are necessary these include classical cross section balancing surface unfolding and volumetric restoration in this paper we will describe a workflow to do quantitative structural geology in complex areas this includes the construction and quality control of the surfacic model the line balancing the cross section surface and multi surface restoration and the volumic restoration in addition to the quality control of the geometries the restoration allows us to compute strain tensors this can be done in the three types of restoration and visualized through ellipses and ellipsoids resp 2d and 3d that represent the main strain or stress vectors we shall discuss the relationship between these strain tensors and the expected fracture network in density as in direction

dissociation of oceanic methane hydrate as a cause of the carbon isotope excursion at the end of the paleocene isotopic records across the latest paleocene thermal maximum lptm indicate that bottom water temperature increased by more than 4 c during a brief time interval 104 years of the latest paleocene 55 6 ma there also was a coeval 2 to 3 excursion in the 13c of the ocean atmosphere inorganic carbon reservoir given the large mass of this reservoir a rapid 13c shift of this magnitude is difficult to explain within the context of conventional hypotheses for changing the mean carbon isotope composition of the ocean and atmosphere however a direct consequence of warming bottom water temperature from 11 to 15 c over 104 years would be a significant change in sediment thermal gradients and dissociation of oceanic ch4 hydrate at locations with intermediate water depths in terms of the present day oceanic ch4 hydrate reservoir thermal dissociation of oceanic ch4 hydrate during the lptm could have released greater than 1 1 to 2 1 1018 g of carbon with a 13c of approximately 60 the release and subsequent oxidation of this amount of carbon is sufficient to explain a 2 to 3 excursion in 13c across the lptm fate of ch4 in oceanic hydrates must be considered in developing models of the climatic and paleoceanographic regimes that operated during the lptm

calcium isotope δ44 40ca variations of neogene planktonic foraminifera measurements of the calcium isotopic composition 44 40ca of planktonic foraminifera from the western equatorial pacific and the indian sector of the southern ocean show variations of about 0 6 over the past 24 myr the stacked 44 40ca record of globigerinoides trilobus and globigerina bulloides indicates a minimum in 44 40casw seawater calcium at 15 to 16 ma and a subsequent general increase toward the present interrupted by a second minimum at 3 to 5 ma applying a coupled calcium carbon cycle model we find two scenarios that can explain a large portion of the observed 44 40casw variations in both cases variations in the ca input flux to the ocean without proportional changes in the carbonate flux are invoked the first scenario increases the riverine calcium input to the ocean without a proportional increase of the carbonate flux the second scenario generates an additional calcium flux from the exchange of ca by mg during dolomitization in both cases the calcium flux variations lead to drastic changes in the seawater ca concentrations on million year timescales our 44 40casw record therefore indicates that the global calcium cycle may be much more dynamic than previously assumed

rapid and sustained surface ocean acidification during the paleocene eocene thermal maximum the paleocene eocene thermal maximum petm has been associated with the release of several thousands of petagrams of carbon pg c as methane and or carbon dioxide into the ocean atmosphere system within 10 kyr on the basis of the co occurrence of a carbon isotope excursion cie widespread dissolution of deep sea carbonates and global warming in theory this rapid carbon release should have severely acidified the surface ocean though no geochemical evidence has yet been presented using boron based proxies for surface ocean carbonate chemistry we present the first observational evidence for a drop in the ph of surface and thermocline seawater during the petm planktic foraminifers from a drill site in the north pacific ocean drilling program site 1209 show a 0 8 decrease in boron isotopic composition 11b at the onset of the event along with a 30 40 reduction in shell b ca similar trends in 11b are present in two lower resolution records from the south atlantic and equatorial pacific these observations are consistent with significant global acidification of the surface ocean lasting at least 70 kyr and requiring sustained carbon release the anomalies in the b records are consistent with an initial surface ph drop of 0 3 units at the upper range of model based estimates of acidification

abrupt increase in seasonal extreme precipitation at the paleocene eocene boundary a prominent increase in atmospheric co at the paleocene eocene boundary ca 55 ma led to the warmest earth of the cenozoic for similar to 100 k y high resolution studies of continental flood plain sediment records across this boundary can provide crucial information on how the hydrological cycle responds to rapidly changing co2 here we show from continental records across the paleocene eocene boundary in the spanish pyrenees a subtropical paleosetting that during the early most intense phase of co2 rise normal semiarid coastal plains with few river channels of 10 200 m width were abruptly replaced by a vast conglomeratic braid plain covering at least 500 km 2 and most likely more than 2000 km 2 this braid plain is interpreted as the proximal parts of a megafan carbonate nodules in the megafan deposits attest to seasonally dry periods and together with megafan development imply a dramatic increase in seasonal rain and an increased intra annual humidity gradient the megafan formed over a few thousand years to similar to 10 k y directly after the paleocene eocene boundary only repeated severe floods and rainstorms could have contributed the water energy required to transport the enormous amounts of large boulders and gravel of the megafan during this short time span the findings represent evidence for considerable changes in regional hydrological cycles following greenhouse gas emissions less

global carbon cycle perturbation across the eocene oligocene climate transition the eocene oligocene transition eot 34 ma marks a tipping point in the long term cenozoic greenhouse to icehouse climate transition paleorecords reveal stepwise rapid cooling and ice growth across the eot tightly coupled to a transient benthic 13c excursion and a major and permanent deepening of the carbonate compensation depth ccd based on biogeochemical box modeling merico et al 2008 suggested that a combination of 1 glacioeustatic sea level fall induced shelf basin carbonate burial fractionation and 2 shelf carbonate weathering can account for the carbon cycle perturbation but this finding has been questioned alternative proposed mechanisms include increased ocean ventilation decreased carbonate burial increased organic carbon burial increased silicate weathering and increased ocean calcium concentration here we use an improved version of the biogeochemical box model of merico et al 2008 to reevaluate these competing hypotheses and an additional mechanism the expansion of carbon capacitors such as permafrost and peatlands we find that changes in calcium concentration silicate weathering and carbonate or organic carbon burial each yield a response that is fundamentally at odds with the form and or sign of the paleorecords shelf basin carbonate burial fractionation ccd change plus shelf carbonate weathering sequestration of 12c enriched carbon into carbon capacitors and possibly increased ocean ventilation 13c excursion offers the best fit to the paleorecords further work is needed to understand why the eot carbon cycle perturbation is so unique when the forcing mechanisms hypothesized to be responsible cooling and ice growth are not peculiar to this event

neodymium isotopic reconstruction of late paleocene early eocene thermohaline circulation abstract high resolution fish tooth nd isotopic records for eight deep sea drilling project and ocean drilling program sites were used to reconstruct the nature of late paleocene early eocene deep water circulation the goal of this reconstruction was to test the hypothesis that a change in thermohaline circulation patterns caused the abrupt 4 5 c warming of deep and bottom waters at the paleocene eocene boundary the paleocene eocene thermal maximum petm event the combined set of records indicates a deep water mass common to the north and south atlantic southern and indian oceans characterized by mean nd values of 8 7 and different water masses found in the central pacific ocean nd 4 3 and caribbean sea nd 1 2 the geographic pattern of nd isotopic values before and during the petm suggests a southern ocean deep water formation site for deep and bottom waters in the atlantic and indian ocean basins the nd data do not contain evidence for a change in the composition of deep waters prior to the onset of the petm this finding is consistent with the pattern of warming established by recently published stable isotope records suggesting that deep and bottom water warming during the petm was gradual and the consequence of surface water warming in regions of downwelling

abrupt deep sea warming palaeoceanographic changes and benthic extinctions at the end of the palaeocene a remarkable oxygen and carbon isotope excursion occurred in antarctic waters near the end of the palaeocene 57 33 myr ago indicating rapid global warming and oceanographic changes that caused one of the largest deep sea benthic extinctions of the past 90 million years in contrast the oceanic plankton were largely unaffected implying a decoupling of the deep and shallow ecosystems the data suggest that for a few thousand years ocean circulation underwent fundamental changes producing a transient state that although brief had long term effects on environmental and biotic evolution

towards an understanding of the ca isotopic signal related to ocean acidification and alkalinity overshoots in the rock record abstract in this contribution we explore the idea that the ca isotope proxy has utility as an indicator of carbonate authigenesis i e post depositional precipitation of caco3 within the sedimentary package given the strong contrast in isotopic fractionation factor between the formational and diagenetic environments ca isotopes have the potential to fingerprint carbonate authigenesis when it occurs close to the seawater sediment interface we demonstrate that ca isotopes are particularly applicable to exploring ocean acidification events and potentially ocean anoxic events and focus our attention on ocean acidification related to the paleocene eocene thermal maximum petm we present three scenarios that vary in the magnitude and duration of the carbon fluxes that are simulated using an earth system model of intermediate complexity cgenie and we use the cgenie output to constrain the upper boundary conditions of 1 d reactive transport models of authigenesis and recrystallization in the sedimentary section along with simple mixing calculations the models inform our exploration of the hypothesis that authigenic carbonate induced by a saturation state overshoot during the petm explains recently published ca isotope records and perhaps bulk carbonate records over ocean anoxic event oae 2 our simulations suggest that fractionation factor variability does not explain the petm 44ca records and we propose a 44ca caco3 space framework to assist with the elucidation of authigenic additions over time scales that are short relative to the residence time of ca in the ocean 1 ma ultimately we find that the authigenic zone generated in the sedimentary column may be influenced by alkalinity overshoots or redox state the caco3 produced in this zone can overprint temporal signals with depth dependent signals that reflect lithology and sedimentation rate and need not be spatially uniform even when driven by a global event ultimately we demonstrate the utility of ca isotopes for exploring short time scale climatic events and a quantitative framework to guide interpretations

dynamics of fossil fuel co2 neutralization by marine caco3 a detailed model of the ocean circulation and carbon cycle was coupled to a mechanistic model of caco3 diagenesis in deep sea sediments to simulate the millennium scale response of the oceans to future fossil fuel co2 emissions to the atmosphere and deep sea simulations of deep sea injection of co2 show that caco3 dissolution is sensitive to passage of high co2 waters through the atlantic ocean but caco3 dissolution has a negligible impact on atmospheric pco2 or the atmospheric stabilization co2 emission in the coming centuries the ultimate fate of the fossil fuel co2 will be to react with caco3 on the seafloor and on land an initial caco3 dissolution spike reverses the net sedimentation rate in the ocean until it is attenuated by an enhanced vertical gradient of alkalinity after about 1000 years the magnitude of the initial spike is sensitive to assumptions about the kinetics for caco3 dissolution but subsequent behavior appears to be less model dependent neutralization by seafloor caco3 occurs on a timescale of 5 6 kyr and is limited to at most 60 70 of the fossil fuel release even if the fossil fuel release is smaller than the seafloor erodible inventory of caco3 additional neutralization by terrestrial caco3 restores a balance between caco3 weathering and seafloor accumulation on a timescale of 8 5 kyr while the deficit of seafloor caco3 the lysocline is replenished with an e folding timescale of approximately 18 kyr the final equilibrium with caco3 leaves 7 8 of the fossil fuel co2 remaining in the atmosphere to be neutralized by the silicate rock cycle on a time frame of hundreds of thousands of years

the calcium riverine and hydrothermal isotopic fluxes and the oceanic calcium mass balance calcium isotope ratios relative to seawater were studied in natural waters in order to constrain the ca isotopic flux to the oceans and to discuss the oceanic ca budget this study includes the analysis of 1 ca isotopes in continental waters at the regional scale of the upper rhine valley and 2 the determination of the 44ca values of some major rivers and hydrothermal vents the data indicate that the global 44ca variability of the studied waters with a maximal range of 1 is limited and must be linked to mass fractionation processes at the scale of a small watershed aubure vosges france the 44ca river flux changes due to the variation of the proportion of waters resulting from chemical alteration of rocks and biologically fractionated soil solutions ca isotopes could therefore be an important tool to quantify the impact of the plants and the biosphere on the river water chemistry at the regional scale of the rhine valley as well as at the global scale of world rivers the 44ca variability of river samples ranges from 0 5 to 1 without any relationship with the lithology of the watershed or the climate similarly the 44ca value of hydrothermal vents is also uniform and close to the mean value of river waters consequently the 44ca flux to the ocean should remain rather constant through time with a mean of 1 1 0 2 this value confirms that the ca budget of the present day seawater is in steady state this was not necessarily the case in the past non steady state periods should have been due to intensity variations of incoming and outcoming ca fluxes rather than to the variations in their isotopic signatures

persistent environmental change after the paleocene eocene thermal maximum in the eastern north atlantic the paleocene eocene thermal maximum petm 56 ma is associated with abrupt climate change carbon cycle perturbation ocean acidification as well as biogeographic shifts in marine and terrestrial biota that were largely reversed as the climatic transient waned we report a clear exception to the behavior of the petm as a reversing climatic transient in the eastern north atlantic deep sea drilling project site 401 bay of biscay where the petm initiates a greatly prolonged environmental change compared to other places on earth where records exist the observed environmental perturbation extended well past the 13 c recovery phase and up to 650 kyr after the petm onset according to our extraterrestrial 3he based age model we observe a strong decoupling of planktic foraminiferal 18 o and mg ca values during the petm 13 c recovery phase which in combination with results from helium isotopes and clay mineralogy suggests that the petm triggered a hydrologic change in western europe that increased freshwater flux and the delivery of weathering products to the eastern north atlantic this state change persisted long after the carbon cycle perturbation had stopped we hypothesize that either long lived continental drainage patterns were altered by enhanced hydrological cycling induced by the petm or alternatively that the climate system in the hinterland area of site 401 was forced into a new climate state that was not easily reversed in the aftermath of the petm

global perturbation of the marine calcium cycle during the permian triassic transition a negative shift in the calcium isotopic composition of marine carbonate rocks spanning the end permian extinction horizon in south china has been used to argue for an ocean acidification event coincident with mass extinction this interpretation has proven controversial both because the excursion has not been demonstrated across multiple widely separated localities and because modeling results of coupled carbon and calcium isotope records illustrate that calcium cycle imbalances alone cannot account for the full magnitude of the isotope excursion here we further test potential controls on the permian triassic calcium isotope record by measuring calcium isotope ratios from shallow marine carbonate successions spanning the permian triassic boundary in turkey italy and oman all measured sections display negative shifts in 44 40ca of up to 0 6 consistency in the direction magnitude and timing of the calcium isotope excursion across these widely separated localities implies a primary and global 44 40ca signature based on the results of a coupled box model of the geological carbon and calcium cycles we interpret the excursion to reflect a series of consequences arising from volcanic co2 release including a temporary decrease in seawater 44 40ca due to short lived ocean acidification and a more protracted increase in calcium isotope fractionation associated with a shift toward more primary aragonite in the sediment and potentially subsequently elevated carbonate saturation states caused by the persistence of elevated co2 delivery from volcanism locally changing balances between aragonite and calcite production are sufficient to account for the calcium isotope excursions but this effect alone does not explain the globally observed negative excursion in the 13c values of carbonate sediments and organic matter as well only a carbon release event and related geochemical consequences are consistent both with calcium and carbon isotope data the carbon release scenario can also account for oxygen isotope evidence for dramatic and protracted global warming as well as paleontological evidence for the preferential extinction of marine animals most susceptible to acidification warming and anoxia

the role of the global carbonate cycle in the regulation and evolution of the earth system we review one of the most ancient of all the global biogeochemical cycles and one which reflects the profound geochemical and biological changes that have occurred as the earth system has evolved through time that of calcium carbonate caco3 in particular we highlight a mid mesozoic revolution in the nature and location of carbonate deposition in the marine environment driven by the ecological success of calcareous plankton this drove the creation of a responsive deep sea sedimentary sink of caco3 the result is that biologically driven carbonate deposition provides a significant buffering of ocean chemistry and of atmospheric co2 in the modern system however the same calcifying organisms that under pin the deep sea carbonate sink are now threatened by the continued atmospheric release of fossil fuel co2 and increasing acidity of the surface ocean we are not yet in a position to predict what the impact on caco3 production will be or how the uptake of fossil fuel co2 by the ocean will be affected this uncertainty in the future trajectory of atmospheric co2 that comes from incomplete understanding of the marine carbonate cycle is cause for concern

correlation between isotope records in marine and continental carbon reservoirs near the palaeocene eocene boundary changes in the isotope content of the large marine carbon reservoir can force shifts in that of the smaller carbon pools in the atmosphere and on land the carbon isotope compositions of marine carbonate sediments from the late palaeocene vary considerably exhibiting a sudden decrease close to the palaeocene eocene boundary which coincides with deep sea benthic extinctions1 and with changes in ocean circulation here we report that these fluctuations in the marine carbon isotope record are closely tracked by the terrestrial records provided by palaeosol carbonates and mammalian tooth enamel in using palaeosol carbonates to reconstruct the co2 content of the ancient atmosphere2 isotope shifts of this sort will have to be taken into account the sharp decrease in 13c 12c ratios in the late palaeocene provides a datum for precise correlation of marine and continental records and suggests that abrupt climate warming at this time may have played an important role in the evolution of land mammals

sedimentary response to paleocene eocene thermal maximum carbon release a model data comparison possible sources of carbon that may have caused global warming at the paleocene eocene boundary are constrained using an intermediate complexity earth system model confi gured with early eocene paleogeography we fi that 6800 pg c 13 c of 22 is the smallest pulse modeled here to reasonably reproduce observations of the extent of seafl oor caco 3 dis solution this pulse could not have been solely the result of methane hydrate destabilization suggesting that additional sources of co 2 such as volcanic co 2 the oxidation of sedimentary organic carbon or thermogenic methane must also have contributed observed contrasts in dissolution intensity between atlantic and pacifi c sites are reproduced in the model by reduc ing bioturbation in the atlantic during the event simulating a potential consequence of the spread of low oxygen bottom waters

core top calibration of mg ca in tropical foraminifera refining paleotemperature estimation 1 optimal use of mg ca as a paleotemperature proxy requires establishing calibrations for different species of foraminifera and quantifying the influence of dissolution to achieve this goal we have measured mg ca and 18o in a series of tropical and subtropical core tops including four depth transects the ceara rise the sierra leone rise and the rio grande plateau in the atlantic and the ontong java plateau in the pacific focusing on spinose mixed layer dwelling species globigerinoides ruber and globigerinoides sacculifer and nonspinose thermocline dwelling neogloboquadrina dutertrei shell mg ca in g sacculifer is 5 15 lower than in g ruber while n dutertrei mg ca is 49 55 lower than in g ruber this statistically significant offset has allowed us to establish different calibrations for each species multilinear regression analysis was used to develop calibration equations that include a correction term for the dissolution effect on mg ca in foraminiferal calcite presented in this paper are two sets of calibrations one set using core depth as a dissolution correction and another using co32 as a dissolution parameter the calibrations suggest that g ruber is the most accurate recorder of surface temperature while g sacculifer records temperatures below the surface at 20 30 m the depth habitat of n dutertrei is more uncertain owing to the wide range in habitat depths depending on hydrographic conditions but on average mg ca and 18o data suggest it is at 50 m of the three species n dutertrei is the most sensitive to dissolution up to 23 decrease in shell mg ca per km while g sacculifer is the most resistant

a continental shelf perspective of ocean acidification and temperature evolution during the paleocene eocene thermal maximum a rapid and large injection of isotopically light carbon into the ocean atmosphere reservoirs is signaled by a negative carbon isotope excursion cie at the paleocene eocene boundary 56 m y ago to better understand the extent of ocean warming and acidification associated with the carbon injection we generated elemental and isotopic records of surface and thermocline planktonic foraminifera across the paleocene eocene boundary from an expanded section along the mid atlantic coastal plain new jersey usa ocean temperatures derived from magnesium calcium paleothermometer document a lag in thermocline warming relative to surface waters implying a progressive deepening of the mixed layer in addition to global warming a similar magnitude of acidification as recorded by boron calcium b ca on the shelf compared with open ocean sites confirms widespread acidification of the surface ocean an increase in seawater alkalinity after the cie as recorded by b ca in planktonic foraminifera likely played an important role in neutralizing the added carbon possibly minimizing benthic extinction along the shelf

reversed deep sea carbonate ion basin gradient during paleocene eocene thermal maximum 1 the paleocene eocene thermal maximum petm 55 ma ago was marked by widespread caco3 dissolution in deep sea sediments a process that has been attributed to massive release of carbon into the ocean atmosphere system the pattern of carbonate dissolution is key to reconstructing changes in deep sea carbonate chemistry and ultimately the rate magnitude and location of carbon input here we show that during the petm the deep sea undersaturation was not homogeneous among the different ocean basins application of a sediment model to a suite of data records from different sites and ocean basins shows that a globally uniform decrease in deep sea carbonate ion concentration co32 is inconsistent with the data rather we demonstrate that deep sea co32 increased from the atlantic through the southern ocean into the pacific our results show that the petm deep sea co32 basin gradient during dissolution was reversed relative to the modern

regulation of atmospheric co2 by deep sea sediments in an earth system model 1 we have extended the genie 1 earth system model to include a representation of sedimentary stratigraphy and the preservation of biogenic carbonates delivered to the ocean floor this has enabled us to take a novel approach in diagnosing modern marine carbon cycling assimilating observation of the calcium carbonate caco3 content of deep sea sediments with an ensemble kalman filter the resulting calibrated model predicts a mean surface sediment content 32 5 wt close to the observed value 34 8 wt and a global burial rate of caco3 in deep sea sediments of 0 121 pgc yr 1 in line with recent budget estimates of 0 10 0 14 pgc yr 1 we employ the genie 1 model in quantifying the multimillennial scale fate of fossil fuel co2 emitted to the atmosphere in the absence of any interaction between ocean and sediments an equilibrium partitioning of co2 is reached within 1000 years of emissions ceasing with 34 645 ppm remaining in the atmosphere out of a total fossil fuel burn of 4173 pgc an additional 12 of co2 emissions 223 ppm are sequestered as bicarbonate ions hco3 by reaction with deep sea carbonates seafloor caco3 neutralization on a timescale of 1 7 ka excess of carbonate weathering on land over deep sea burial results in a further net transformation of 14 of co2 emissions 261 ppm into hco3 terrestrial caco3 neutralization on a timescale of 8 3 ka we have also assessed the importance of a changing climate in modulating the stabilization of atmospheric co2 through ocean sediment interaction increased ocean stratification suppresses particulate organic carbon export which in turn enhances seafloor caco3 preservation the resulting reduction in the sequestration of fossil fuel co2 represents a new positive feedback on millennial scale climate change

oceanic calcium changes from enhanced weathering during the paleocene eocene thermal maximum no effect on calcium based proxies 1 during the paleocene eocene thermal maximum petm 55 myr ago prominent climatic and biogeochemical changes took place in the atmosphere ocean and on land for example deep sea temperatures rose by 5 c to 6 c while sea surface temperatures at high latitudes increased by up to 9 c in the sedimentary record the onset of the petm is marked by widespread dissolution of calcium carbonate on the seafloor in addition there is evidence for globally higher humidity precipitation and increased weathering during the petm both calcium carbonate dissolution and enhanced weathering probably affected the seawater calcium concentration here we investigate implications that possible changes in the ocean s calcium inventory may have had on boron calcium b ca and magnesium calcium mg ca ratios which are used as proxies for deep water carbonate chemistry and temperature respectively we also examine effects on 44ca of seawater which is used as an indicator for variations in the marine calcium cycle we focus on the magnitude of change in the ocean s calcium ion concentration as a result of the carbon perturbation which resulted in increased weathering fluxes and the dissolution of calcite on the ocean floor during the petm different ranges of carbon input scenarios and their effect on ocean chemistry were examined using the long term ocean atmosphere sediment carbon cycle reservoir loscar model we found that under the most plausible scenario the calcium ion concentration change ca2 was less than 0 7 and around 2 in the most extreme scenario our results show that b ca and mg ca proxies were not affected within analytical precision by changes in oceanic calcium due to weathering and carbonate dissolution during the petm the most extreme scenario ca2 2 would result in 4 mol kg 1 uncertainty in reconstruction of co32 the same scenario affects the temperature reconstruction by 0 2 c the effect on the ocean s calcium isotope budget was insignificant as well resulting in 44casw of less than 0 05

an osmium isotope excursion associated with the late paleocene thermal maximum evidence of intensified chemical weathering in the latest paleocene an abrupt shift to more negative 13c values has been documented at numerous marine and terrestrial sites bralower et al 1997 cramer et al 1999 kaiho et al 1996 kennett and stott 1991 koch et al 1992 stott et al 1996 thomas and shackleton 1996 zachos et al 1993 this carbon isotope event cie is coincident with oxygen isotope data that indicate warming of surface waters at high latitudes of nearly 4 6 c kennett and stott 1991 and more moderate warming in the subtropics thomas et al 1999 here we report 187os 188os isotope records from the north atlantic and indian oceans which demonstrate a 10 increase in the 187os 188os ratio of seawater coincident with the late paleocene cie this excursion to higher 187os 188os ratios is consistent with a global increase in weathering rates the inference of increased chemical weathering during this interval of unusual warmth is significant because it provides empirical evidence supporting the operation of a feedback between chemical weathering rates and warm global climate which acts to stabilize earth s climate walker et al 1981 estimates of the duration of late paleocene cie bains et al 1999 bralower et al 1997 norris and rohl 1999 rohl et al 2000 in conjunction with the os isotope data imply that intensified chemical weathering in response to warm humid climates can occur on timescales of 104 105 years this interpretation requires that the late paleocene thermal maximum os isotope excursion be produced mainly by increased os flux to the ocean rather than a transient excursion to higher 187os 188os ratios in river runoff although we argue that the former is more likely than the latter we cannot rule out significant changes in the 187os 188os ratio of rivers

b ca in planktonic foraminifera as a proxy for surface seawater ph boron isotope systematics indicate that boron incorporation into foraminiferal caco3 is determined by the partition coefficient k d frac left rm b rm ca right rm caco3 left rm b left rm oh right 4 rm hco 3 right rm seawater and b oh 4 hco3 seawater providing in principle a method to estimate seawater ph and pco2 we have measured b ca ratios in globigerina bulloides and globorotalia inflata for a series of core tops from the north atlantic and the southern ocean and in globigerinoides ruber white from ocean drilling program odp site 668b on the sierra leone rise in the eastern equatorial atlantic b ca ratios in these species of planktonic foraminifera seem unaffected by dissolution on the seafloor k d shows a strong species specific dependence on calcification temperature which can be corrected for using the mg ca temperature proxy a preliminary study of g inflata from southern ocean sediment core chat 16k suggests that temperature corrected b ca was 30 higher during the last glacial correspondingly ph was 0 15 units higher and aqueous pco2 was 95 atm lower at this site at the last glacial maximum the covariation between reconstructed pco2 and the atmospheric pco2 from the vostok ice core demonstrates the feasibility of using b ca in planktonic foraminifera for reconstructing past variations in ph and pco2

carbon addition and removal during the late palaeocene thermal maximum basic theory with a preliminary treatment of the isotope record at odp site 1051 blake nose the late palaeocene thermal maximum lptm was a brief interval at c 55 ma characterized by a 2 5 to 3 per thousand shift in the 13c of global carbon reservoirs the geochemical perturbation probably represents a massive input of 12c rich carbon to the exogenic carbon cycle largely unresolved issues concerning this carbon injection during the lptm are the rates of carbon input and removal simple expressions are developed here to describe a 13c excursion in the exogenic carbon cycle after carbon input a change in global 13c d ex dt can be explained to a first approximation by a set of parameters the initial mass and isotopic composition of the global carbon cycle mex o ex o and the fluxes and isotopic compositions of external carbon inputs outputs and injected carbon fin in fout out fadd add in general for a given exogenic carbon cycle a large fadd or low add results in a larger 13c excursion likewise for a given negative 13c excursion a large mex or low ex requires a greater input of 12c differences in fin in fout and out cause changes in the response of ex over time for a negative 13c excursion of given magnitude a greater fin requires a greater input of 12c and lessens the time for ex to return to initial conditions a decrease in out caused by an increase in the relative output of organic matter and carbonate has a similar effect variable dmadd dt produces transients in ex that are related to the source function but modified by carbon removal in theory a well dated and representative global 13c excursion could be used to derive the carbon inputs and ouputs ocean drilling program odp site 1051 has an expanded early palaeogene section and recent work at this location has provided a well dated 13c record across the lptm this 13c record contains transient variations of apparently global nature these observed transients are best explained by a pulsed injection of ch4 into an exogenic carbon cycle with a greater carbon throughput or enhanced burial of organic matter after carbon addition

climate impact of late quaternary equatorial pacific sea surface temperature variations magnesium calcium data from planktonic foraminifera in equatorial pacific sediment cores demonstrate that tropical pacific sea surface temperatures ssts were 2 8 0 7 c colder than the present at the last glacial maximum glacial interglacial temperature differences as great as 5 c are observed over the last 450 thousand years changes in sst coincide with changes in antarctic air temperature and precede changes in continental ice volume by about 3 thousand years suggesting that tropical cooling played a major role in driving ice age climate comparison of sst estimates from eastern and western sites indicates that the equatorial pacific zonal sst gradient was similar or somewhat larger during glacial episodes extraction of a salinity proxy from the magnesium calcium and oxygen isotope data indicates that transport of water vapor into the western pacific was enhanced during glacial episodes

variations in the marine ca cycle over the past 20 million years a 20 million year marine ca isotope record is constructed based on measurements of 36 nannofossil ooze samples from dsdp site 590 the ca isotopic composition d 44 ca relative to our bbulk earthq average of carbonate ooze samples varies between 0 2 and 0 9 and the inferred d 44 ca of seawater calcium varies between 1 1 and 0 4 modern seawater value is 0 95 on our scale fluctuations in the seawater ca isotope ratio occur in 2 to 4 million year intervals and indicate that the supply and removal of ca from the oceans are seldom in balance the ca isotope record is used to reconstruct past weathering fluxes and marine calcium concentrations the inferred marine concentration of ca fluctuates by about f20 on 2 4 million year time scales and by about f50 over the 20 million year record these variations are presumably superimposed on the previously inferred 100 million year variations the seawater ca concentration was about 0 5 times present at 20 ma and generally increased until 6 ma 1 7 times present local maxima in seawater calcium concentrations occur at 6 4 and 4 ma preceding periods of enhanced marine productivity and high mass accumulation rates at site 590 while the calculated calcium concentrations are sensitive to the assumed d 44 ca value for the weathering flux the 2 4 million year features of the derived

multivariate analysis of cross hole georadar velocity and attenuation tomograms for aquifer zonation 1 we have investigated the potential of combining cross hole georadar velocity and attenuation tomography as a method for characterizing heterogeneous alluvial aquifers a multivariate statistical technique known as k means cluster analysis is used to correlate and integrate information contained in velocity and attenuation tomograms cluster analysis allows us to identify objectively the major common trends in the tomographic data and thus to reduce the information to a limited number of characteristic parameter combinations the application of this procedure to two synthetic data sets indicates that it is a powerful tool for converting the complex relationships between the tomographically derived velocity and attenuation structures into a lithologically and hydrologically meaningful zonation of the probed region in addition these synthetic examples allow us to evaluate the reliability of further petrophysical parameter estimates we find that although absolute values of the tomographically inferred petrophysical parameters often differ significantly from the actual parameters the clustering approach enables us to reliably identify the major trends in the petrophysical properties finally we have applied the approach to a cross hole georadar data set collected in a well studied alluvial aquifer a comparison of the clustered tomographic section with well log data demonstrates that our approach delineates the hydrostratigraphic zonation

history of carbonate ion concentration over the last 100 million years abstract instead of having been more or less constant as once assumed it is now apparent that the major ion chemistry of the oceans has varied substantially over time for instance independent lines of evidence suggest that calcium concentration ca2 has approximately halved and magnesium concentration mg2 approximately doubled over the last 100 million years on the other hand the calcite compensation depth and hence the caco3 saturation has varied little over the last 100 my as documented in deep sea sediments we combine these pieces of evidence to develop a proxy for seawater carbonate ion concentration co32 over this period of time from the calcite saturation state which is proportional to the product of ca2 times co32 but also affected by mg2 we can calculate seawater co32 our results show that co32 has nearly quadrupled since the cretaceous furthermore by combining our co32 proxy with other carbonate system proxies we provide calculations of the entire seawater carbonate system and atmospheric co2 based on this reconstructed atmospheric co2 is relatively low in the miocene but high in the eocene finally we make a strong case that seawater ph has increased over the last 100 my

a transient rise in tropical sea surface temperature during the paleocene eocene thermal maximum the paleocene eocene thermal maximum petm has been attributed to a rapid rise in greenhouse gas levels if so warming should have occurred at all latitudes although amplified toward the poles existing records reveal an increase in high latitude sea surface temperatures ssts 8 to 10 c and in bottom water temperatures 4 to 5 c to date however the character of the tropical sst response during this event remains unconstrained here we address this deficiency by using paired oxygen isotope and minor element magnesium calcium ratios of planktonic foraminifera from a tropical pacific core to estimate changes in sst using mixed layer foraminifera we found that the combined proxies imply a 4 to 5 c rise in pacific sst during the petm these results would necessitate a rise in atmospheric pco 2 to levels three to four times as high as those estimated for the late paleocene

calibration of mg ca thermometry in planktonic foraminifera from a sediment trap time series 1 paired mg ca and 18o measurements on planktonic foraminiferal species g ruber white g ruber pink g sacculifer g conglobatus g aequilateralis o universa n dutertrei p obliquiloculata g inflata g truncatulinoides g hirsuta and g crassaformis from a 6 year sediment trap time series in the sargasso sea were used to define the sensitivity of foraminiferal mg ca to calcification temperature habitat depths and calcification temperatures were estimated from comparison of 18o of foraminifera with equilibrium calcite based on historical temperature and salinity data when considered together mg ca mmol mol of all species except two show a significant r 0 93 relationship with temperature t c of the form mg ca 0 38 0 02 exp 0 090 0 003 t equivalent to a 9 0 0 3 change in mg ca for a 1 c change in temperature small differences exist in calibrations between species and between different size fractions of the same species o universa and g aequilateralis have higher mg ca than other species and in general data can be best described with the same temperature sensitivity for all species and pre exponential constants in the sequence o universa g aequilateralis g bulloides g ruber g sacculifer other species this approach gives an accuracy of 1 2 c in the estimation of calcification temperature the 9 sensitivity to temperature is similar to published studies from culture and core top calibrations but differences exist from some literature values of pre exponential constants different cleaning methodologies and artefacts of core top dissolution are probably implicated and perhaps environmental factors yet understood planktonic foraminiferal mg ca temperature estimates can be used for reconstructing surface temperatures and mixed and thermocline temperatures using g ruber pink g ruber white g sacculifer n dutertrei p obliquiloculata etc the existence of a single mg thermometry equation is valuable for extinct species although use of species specific equations will where statistically significant provide more accurate evaluation of mg ca paleotemperature

a travel time based hydraulic tomographic approach 1 hydraulic tomography is a method to identify the three dimensional spatial distribution of hydraulic properties in the subsurface we propose a tomographic approach providing the inversion of travel times of hydraulic or pneumatic tests conducted in a tomographic array the inversion is based on the relation between the peak time of a recorded transient pressure curve and the diffusivity of the investigated system the development of a transformation factor enables the inversion of further travel times besides the peak time of a transient curve as the early travel times of the curve are mainly related to preferential flow features while the inversion based on late travel times are reflecting an integral behavior it can be assumed that the different inversion results reflect the properties of the overall system by comparing the different reconstructions the system interpretation therefore becomes more comprehensive and reliable furthermore the similarity of the proposed hydraulic tomographic approach to seismic travel time tomography allows us to apply the inversion algorithms which are used for seismic tomography we therefore apply the method of staggered grids which enables to refine the grid resulting in a higher nominal resolution to data from a set of interference tests arranged in a tomographic array the tests were conducted in an unsaturated fractured sandstone cylinder in the laboratory the three dimensional reconstructions of the diffusivity distribution are found to be highly reliable and robust in particular the mapped fracture of the sandstone cylinder coincides with our reconstructed diffusivity distribution

additive effects of acidification and mineralogy on calcium isotopes in triassic jurassic boundary limestones the end triassic mass extinction coincided with a negative 13c excursion consistent with release of 13c depleted co2 from the central atlantic magmatic province however the amount of carbon released and its effects on ocean chemistry are poorly constrained the coupled nature of the carbon and calcium cycles allows calcium isotopes to be used for constraining carbon cycle dynamics and vice versa we present a high resolution calcium isotope 44 40ca record from 100 m of marine limestone spanning the triassic jurassic boundary in two stratigraphic sections from northern italy immediately above the extinction horizon and the associated negative excursion in 13c 44 40ca decreases by 0 8 in 20 m of section and then recovers to preexcursion values coupled numerical models of the geological carbon and calcium cycles demonstrate that this 44 40ca excursion is too large to be explained by changes to seawater 44 40ca alone regardless of co2 injection volume and duration less than 20 of the 44 40ca excursion can be attributed to acidification the remaining 80 likely reflects a higher proportion of aragonite in the original sediment based largely on high concentrations of sr in the samples our study demonstrates that coupled models of the carbon and calcium cycles have the potential to help distinguish contributions of primary seawater isotopic changes from local or diagenetic effects on the 44 40ca of carbonate sediments differentiating between these effects is critical for constraining the impact of ocean acidification during the end triassic mass extinction as well as for interpreting other environmental events in the geologic past

understanding the causes and consequences of past marine carbon cycling variability through models abstract on geological time scales the production and degree of recycling of biogenic carbon in the marine realm and ultimately its removal to sediments exerts a dominant control on atmospheric co 2 and hence variability in climate this is a highly complex system involving a myriad of inter connected biological chemical and physical processes for this reason alone linking observations often highly abstracted in the form of proxies to the primary processes involved and ultimately to explanatory hypotheses for specific geological events and transitions is challenging the past few decades have seen a progressive improvement in theoretical and process based understanding of the various components that make up the marine carbon cycle and hand in hand with this the development of numerical model representations of the complete system models have also been designed and or adapted with paleoclimate questions in mind and applied to quantitatively explore the role of the marine carbon cycle in both perturbations and long term geologic evolutionary trends in global climate and possible feedbacks between them however we must ask whether paleoclimate models incorporate sufficiently appropriate representations of the dynamics and sensitivities of the marine carbon cycle and indeed whether in the geological context we really know what these dynamics are here we provide a comprehensive overview of how marine carbon cycling and the biological carbon pump is treated in available paleoclimate models with the aim of critically evaluating their ability to help interpret past marine carbon cycle and climate dynamics to this end we first provide an overview of commonly used paleoclimate models and some of their associated paleo applications drawing from a wide range of global carbon cycle box models and earth system models of intermediate complexity emics secondly we review and evaluate the three dominant processes involved in the cycling of organic and inorganic carbon in the marine system and how they are represented in models namely biological productivity at the ocean surface remineralisation dissolution of particulate carbon within the water column and the benthic pelagic coupling at the seafloor we generate and employ illustrative examples using the model genie to show how different parameterisations of water column and sediment processes can lead to significantly different model projections our compilation reveals the prevalence of static parameterisations of marine carbon cycling among existing paleoclimate models which are commonly empirically derived from present day observations although such approaches tend to represent carbon transfer in the modern ocean well they are potentially compromised in their ability to reflect the true degree of freedom and strength of feedbacks with respect to past climate events particularly those characterised by environmental boundary conditions that differ fundamentally from today finally we discuss the importance of using models of different complexities and how questions of model uncertainty may start to be addressed

benthic foraminiferal b ca ratios reflect deep water carbonate saturation state boron calcium ratios were measured in four benthic foraminiferal species three calcitic cibicidoides wuellerstorfi cibicidoides mundulus and uvigerina spp and one aragonitic hoeglundina elegans from 108 core top samples located globally comparison of coexisting species shows b ca of c wuellerstorfi c mundulus h elegans uvigerina spp suggestive of strong vital effects on benthic foraminiferal b ca a dissolution effect on benthic b ca is not observed core top data show large intra species variations 50 130 mol mol in b ca within a single species benthic foraminiferal b ca show a simple linear correlation with deep water co32 providing a proxy for past deep water co32 reconstructions empirical sensitivities of co32 on b ca have been established to be 1 14 0 048 and 0 69 0 072 mol mol per mol kg for c wuellerstorfi and c mundulus respectively the uncertainties associated with reconstructing bottom water co32 using b ca in c wuellerstorfi and c mundulus are about 10 mol kg a preliminary application shows that the last glacial maximum lgm b ca ratios were increased by 12 at 1 2 km and decreased by 12 at 3 5 4 0 km relative to holocene values in the north atlantic ocean this implies that the lgm co32 was higher by not vert similar 25 30 mol kg at intermediate depths and lower by not vert similar 20 mol kg in deeper waters consistent with glacial water mass reorganization in the north atlantic ocean inferred from other paleochemical proxies

effects of ocean acidification on the marine calcium isotope record at the paleocene eocene thermal maximum highlights 44ca was measured in bulk carbonate and barite at two sites over the petm diagenetic effects on 44ca are observed associated with ocean acidification multiple sites and proxy archives necessary to reconstruct the past accurately abstract carbonates are used extensively to reconstruct paleoclimate and paleoceanographic conditions over geologic time scales however these archives are susceptible to diagenetic alteration via dissolution recrystallization and secondary precipitation particularly during ocean acidification events when intense dissolution can occur despite the possible effects of diagenesis on proxy fidelity the impacts of diagenesis on the calcium isotopic composition 44ca of carbonates are unclear to shed light on this issue bulk carbonate 44ca was measured at high resolution in two pacific deep sea sediment cores odp sites 1212 and 1221 with considerably different dissolution histories over the paleocene eocene thermal maximum petm 55 ma 55 ma the 44ca of marine barite was also measured at the deeper site 1221 which experienced severe carbonate dissolution during the petm large variations 0 8 0 8 in bulk carbonate 44ca occur in the deeper of the two sites at depths corresponding to the peak carbon isotope excursion which correlate with a large drop in carbonate weight percent such an effect is not observed in either the 1221 barite record or the bulk carbonate record at the shallower site 1212 which is also less affected by dissolution we contend that ocean chemical changes associated with abrupt and massive carbon release into the ocean atmosphere system and subsequent ocean acidification at the petm affected the bulk carbonate 44ca record via diagenesis in the sedimentary column such effects are considerable and need to be taken into account when interpreting ca isotope data and potentially other geochemical proxies over extreme climatic events that drive sediment dissolution

temperature control on the incorporation of magnesium strontium fluorine and cadmium into benthic foraminiferal shells from little bahama bank prospects for thermocline paleoceanography surface sediments from little bahama bank lbb intersecting the subtropical thermocline were used to assess the influence of temperature on the incorporation of mg sr f and cd into shells of benthic foraminifera samples were obtained from twelve cores along the southern slope of lbb covering a temperature range of 18 4 5 c between 301 and 1585 m we studied the composition of ten calcitic and one aragonitic species which are often used in paleochemical reconstructions mg ca ratios decrease with increasing water depth in all benthic species both with calcitic and aragonitic mineralogy showing a strong correlation with water temperature similar decrease is seen in sr ca but with no correlation with temperature none of the benthic species studied here exhibits a depth or temperature related change in f ca similar trends are observed when using an ocean wide dataset which includes shallow and deep core tops 300 5000 m we suggest that temperature is the primary control on the mg content of benthic foraminifera based on inorganic precipitation experiments and thermodynamic considerations presented here a 30 40 decrease in the mg distribution coefficient in calcite may be expected as a result of a temperature change from 25 c to 5 c which is about half the observed change in lbb a calibration curve applied to c pachyderma data from core tops along the slope of little bahama bank suggests that water temperature may be inferred from mg ca ratios with an uncertainty of about 0 8 c therefore the mg content of benthic foraminifera may provide a new independent temperature proxy for studying shallow waters paleoceanography the linear decrease in sr ca with increasing depth is not correlated with temperature the trend is constant from the ocean surface down to 5 km suggesting that pressure related effects on the calcification process are a more likely explanation than post depositional dissolution mg ca ratios in aragonitic shells of h elegans covary with temperature in accord with recent observations from corals in contrast the sr and f chemistry of h elegans is very different than that of corals and inorganically precipitated aragonites the disparities between the elemental composition of biogenic and inorganic phases and the large intergeneric and interspecific differences observed both in planktonic and benthic foraminifera implicate temperature related physiological processes in regulating the coprecipitation of elements in foraminiferal shells our work demonstrates that cd ca ratios of shallow calcitic species reflect the vertical distribution of nutrients no significant influence of temperature on the partitioning of cd into the shells was found our data extend the previous deep water calibration boyle 1992 thereby allowing for the reconstruction of the nutrient chemistry of shallow thermocline waters

a simple model for the caco3 saturation state of the ocean the strangelove the neritan and the cretan ocean 1 a simple model of the caco3 saturation state of the ocean is presented it can be solved analytically and is intended to identify the fundamental controls on ocean carbonate ion concentration it should also attract researchers unfamiliar with complex biogeochemical models despite its limitations the model calculated caco3 saturation state of today s ocean agrees well with observations in general the model reveals three distinctly different modes of operation the strangelove ocean of high supersaturation which is dominated by inorganic caco3 precipitation 2 the neritan ocean of indefinite saturation dominated by biogenic shallow water caco3 precipitation and 3 the cretan ocean of low saturation dominated by biogenic pelagic caco3 precipitation in the latter mode the deep ocean co32 is remarkably stable provided that the biogenic production of caco3 exceeds the riverine flux of ca2 and co32 this explains the overall constancy of the saturation state of the ocean documented over the last 100 ma the model is then used to address diverse questions one important result is that the recovery of the oceanic carbonate chemistry from fossil fuel neutralization in the future will be accelerated due to expected reduced biogenic calcification

evaluating the ca isotope proxy the use of ca isotopes as a proxy for mass flux imbalances in the ca cycle is evaluated critically a compiled ca isotope record for the last 45 ma derived from bulk nannofossil ooze and with a temporal resolution of 0 5 ma and an interpretation of the record are presented in the context of the global ca cycle this analysis which assumes that nannofossil ooze records isotopic variations in seawater indicates a dynamic ca cycle in the cenozoic such dynamic behavior has serious implications for the c cycle and suggests feedbacks between the ca and c cycles to stabilize or buffer the oceanic carbon reservoir alternative applications of the ca isotope proxy are investigated using numerical models to determine the extent to which ca isotopes are sensitive to other aspects of the ca cycle the results of the simulations are applied to specific cases in the cenozoic the simulations illustrate how variations in the global fractionation factor between calcium carbonate and seawater can produce trends similar to those observed when comparing previously published ca isotopic compositions of marine barite to the nannofossil ooze record the large drop in the 44 ca value of bulk nannofossil ooze near the eocene oligocene boundary can be reconciled in two ways either as a substantial increase in weathering relative to sedimentation or as an indicator of changing depositional mode within the ocean though the preferred interpretation is not clear at present it is evident that ca isotopes stand to be a unique proxy for ca cycling once the isotope systematics are elucidated

paleocene and eocene kaolinite distribution in the south atlantic and southern ocean antarctic climatic and paleoceanographic implications abstract clay mineral associations of paleocene and eocene age have been examined in six drilled sequences from the southern south atlantic and southern ocean these sites are located to provide three depth transects across intermediate water masses widespread abundance of pedogenic smectite at all locations suggests globally warm climates and alternating wet and dry seasons on the adjacent continental margins including antarctica as was the case during the late cretaceous remarkably kaolinite is observed only in paleocene eocene sediments at the highest latitudes of these sites and must have originated from antarctica the restriction of kaolinite to the antarctic region is inferred to have resulted from especially higher rainfall there during the paleocene eocene relative to the lower latitude areas examined this inferred high rainfall is considered to have resulted from globally warm temperatures that increased poleward latent heat transport compensating for a strong heat deficit in the antarctic region relative to the tropics kaolinite was not observed in the latest cretaceous maastrichtian sediments of maud rise antarctica kaolinite first appears in the clay mineralogical assemblages in the earliest paleocene 64 to 64 5 ma at a time of relatively cool intermediate waters and before a warming trend of surface waters currents at intermediate water depths transported fine terrigenous sediments from the antarctica during the latest paleocene and early eocene 59 to 52 ma at a time when the oxygen isotopic strongly in east antarctica during the latest paleocene and early eocene 59 to 59 ma at a time when the oxygen isotopic data indicate maximum warmth of surface and intermediate waters of the southern ocean these are interpreted to reflect a paleocene maximum of antarctic rainfall this development peaked at 57 3 m close to the paleocene eocene boundary a time of maximum warmth based on oxygen isotopic data increased illite content and associated chlorite and random mixed layer clays at the end of the middle eocene 41 ma suggest local development of poorly weathered soils on antarctica favored by a cooling of the southern ocean coeval extension of kaolinite into shallower water depths and similar clay mineral associations in shallower and deeper sites indicate the development of cooler conditions led to an increasing influence of antarctic environments upon intermediate water masses at high latitudes

calcium and calcium isotope changes during carbon cycle perturbations at the end permian negative carbon and calcium isotope excursions as well as climate shifts took place during the most severe mass extinction event in earth s history the end permian 252 ma investigating the connection between carbon and calcium cycles during transient carbon cycle perturbation events such as the end permian may help resolve the intricacies between the coupled calcium carbon cycles as well as provide a tool for constraining the causes of mass extinction here we identify the deficiencies of a simplified calcium model employed in several previous studies and we demonstrate the importance of a fully coupled carbon cycle model when investigating the dynamics of carbon and calcium cycling simulations with a modified version of the long term ocean atmosphere sediment carbon cycle reservoir model which includes a fully coupled carbon calcium cycle indicate that increased weathering rates and ocean acidification potentially caused by siberian trap volcanism are not capable of producing trends observed in the record as previously claimed our model results suggest that combined effects of carbon input via siberian trap volcanism 12 000 pg c the cessation of biological carbon export and variable calcium isotope fractionation due to a change in the seawater carbonate ion concentration represents a more plausible scenario this scenario successfully reconciles 13c and 44ca trends observed in the sediment record as well as the proposed warming of 6 c

calibration of the b ca proxy in the planktic foraminifer orbulina universa to paleocene seawater conditions the b ca ratio of planktic foraminiferal calcite a proxy for the surface ocean carbonate system displays large negative excursions during the paleocene eocene thermal maximum petm 55 9 ma consistent with rapid ocean acidification at that time however the b ca excursion measured at the petm exceeds a magnitude that modern ph calibrations can explain numerous other controls on the proxy have been suggested including foraminiferal growth rate and the total concentration of dissolved inorganic carbon dic here we present new calibrations for b ca versus the combined effects of ph and dic in the symbiont bearing planktic foraminifer orbulina universa grown in culture solutions with simulated paleocene seawater elemental composition high ca low mg and low total boron concentration b t we also investigate the isolated effects of low seawater b t high ca reduced symbiont photosynthetic activity and average shell growth rate on o universa b ca in order to further understand the proxy systematics and to determine other possible influences on the petm records we find that average shell growth rate does not appear to determine b ca in high calcite saturation experiments in addition our paleocene calibration shows higher sensitivity than the modern calibration at low b oh 4 dic given a large dic pulse at the petm this amplification of the b ca response can more fully explain the petm b ca excursion however further calibrations with other foraminifer species are needed to determine the range of foraminifer species specific proxy sensitivities under these conditions for quantitative reconstruction of large carbon cycle perturbations

could changing ocean circulation have destabilized methane hydrate at the paleocene eocene boundary 1 during the paleocene eocene thermal maximum petm 55 ma marine and terrestrial carbon isotope values exhibit a negative shift of at least 2 5 indicative of massive destabilization of marine methane hydrates releasing 2000 gigatons of methane carbon the cause of the hydrate destabilization is unknown but has been speculated to be warming due to a change from high latitude to low latitude deepwater formation here we present results from a numerical ocean model indicating that a sudden switch of deepwater formation from southern to northern high latitudes caused middepth and deep ocean warming of 3 5 c the switch is caused by a slow increase in the intensity of the atmospheric hydrologic cycle as expected under increasing temperatures and consistent with petm sedimentary evidence deepened subtropical subduction prior to the thermohaline circulation switch causes warming of 1 4 c in limited areas at thermocline through upper intermediate depths which could destabilize methane hydrates gradually and at progressively greater depths warming accompanying a south to north switch in deepwater formation would produce sufficient warming to destabilize seafloor gas hydrates over most of the world ocean to a water depth of at least 1900 m

a palaeogene perspective on climate sensitivity and methane hydrate instability the palaeoceneeocene thermal maximum petm a rapid global warming event and carbon cycle perturbation of the early palaeogene provides a unique test of climate and carbon cycle models as well as