dissolution kinetics of calcium carbonate in equatorial pacific sediments benthic chambers were deployed in the equatorial eastern pacific ocean on a transect along the equator between 103 w and 140 w and on a transect across the equator at 140 w in order to establish the rate of calcium carbonate dissolution on the seafloor dissolution was determined from the rate of alkalinity increase within an incubation chamber measured over an 80 120 hour incubation period dissolution rates were lowest at eastern pacific sites 0 2 0 4 mmol caco3 m2 d and highest at the equatorial 140 w sites 0 5 0 7 mmol m2 d both oxygen consumption rates and the degree of bottom water saturation govern dissolution rates measured dissolution and oxygen consumption rates are used with a numerical model to constrain the value of the dissolution rate constant k formulated according to the equation developed by keir 1980 dissolution rate k 1 n the observed dissolution fluxes are predicted by the model when k 5 to 100 d and n 4 5 this range of k values has important implications regarding the type of carbonate dissolving and its location within the sediment column at low values of k organic carbon rain rates to the seafloor become the dominant driving force of carbonate dissolution at higher values of k the degree of bottom water undersaturation becomes more important dissolution of carbonate within equatorial pacific sediments can be adequately described with k 20 10 d a rate constant much lower than some previously used values dissolution rates do not vary significantly over chamber boundary layer thicknesses between 200 and 800 m indicating that dissolution is not controlled by hydrodynamic conditions chambers acidified with hcl yield very large dissolution rates but for a given degree of acidification the dissolution rate was constant for sites ranging from water depths of 3300 4400 m this implies that there are not more and less easily dissolved forms of caco3 arriving on the seafloor between these depths a budget for alkalinity in the deep pacific predicted by the dissolution model and based on the assumption that all carbonate dissolution takes place in the sediments is within 85 of the input required by a published box model alkalinity budget based on the distribution of nutrients and the water mass transport rates

the role of caco3 compensation in the glacial to interglacial atmospheric co2 change the only viable explanations put forth to date for the glacial to interglacial change in atmospheric co2 content suggested from measurements of the co2 content of gas extracted from ice cores involve changes in the ocean s nutrient cycles any nutrient change capable of creating the 80 atm changes in atmosphere co2 pressure suggested by the ice core results also creates significant change in the deep ocean s co3 content evidence from deep sea sediments suggests that these co3 changes are compensated on the time scale of a few thousand years by reductions or increases in amount of caco3 accumulating in deep sea sediments this compensation process has two important consequences first it significantly increases the magnitude of the co2 change per unit of nutrient forcing second it causes a delay in the response of the atmospheric co2 change while the first of these consequences is a boon to those seeking to explain the co2 change the second may prove to be a curse the ice core co2 record shows no evidence of a significant lag between the co2 response and the polar warming in any case it is important that we improve our knowledge of the magnitude and timing of the caco3 preservation events which mark the close of episodes of glaciation and of the dissolution events which mark the onset of these episodes

u th ages obtained by mass spectrometry in corals from barbados sea level during the past 130 000 years the study of the sea level record during the last glacial cycle has primarily proceeded indirectly by means of oxygen isotope measurements on foraminifera from deep sea sediments1 2 the direct approach of dating sea level indicators stagnated during the past decade mainly because the samples required to complete our knowledge of the past glaciations are below the present day sea level3 7 using the 14c ages of acropora palmata samples collected by drilling offshore the island of barbados fairbanks8 presented the first detailed chronology for the last deglaciation this radiocarbon chronology is limited to the past 30 kyr because of the short half life of 14c 5 730 yr we must therefore rely on other dating methods to obtain information for the whole last glacial cycle during the past four years 230th 234u dating of corals by thermal ionization mass spectrometry has been shown to be significantly more precise and accurate than the classical counting method9 14 we have used this technique to measure u th ages in coral samples from the barbados collection and from subaerially exposed outcrops see also ref 15 here we present results bearing on the sea level record for the past 130 000 years we conclude that the last deglaciation started 3 000 years earlier than previously thought and confirm that there were two surges in melt water8 at about 11 kyr and 14 kyr bp before present

return of the coral reef hypothesis basin to shelf partitioning of caco3 and its effect on atmospheric co2 differences in the rate of coral reef carbonate deposition from the pleistocene to the holocene may account for the quaternary variation of atmospheric co sub 2 volumes of carbonate associated with holocene reefs require an average deposition rate of 2 0 times 10 sup 13 mol yr for the past 5 ka in light of combined riverine mid ocean ridge and ground water fluxes of calcium to the oceans of 2 3 times 10 sub 13 mol yr the current flux of calcium carbonate to pelagic sediments must be far below the pleistocene average of 1 2 times 10 sub 13 mol yr the authors suggest that sea level change shifts the locus of carbonate deposition from the deep sea to the shelves as the normal glacial interglacial pattern of deposition of quaternary global carbonates to assess the impact of these changes on atmospheric co sub 2 a simple numerical simulation of the global carbon cycle was developed atmospheric co sub 2 as well as calcite saturation depth and sediment responses to these carbonate deposition changes are examined atmospheric co sub 2 changes close to those observed in the vostok ice core approximately 80 ppm co sub 2 for the quaternary are observed as well as the approximate depth changes in percent carbonate of sediments measured in themore pacific ocean over the same time interval less

deep pacific caco 3 compensation and glacial interglacial atmospheric co 2 abstract benthic foraminiferal 13c suggests that there was a net shift of isotopically light metabolic co2 from the upper ocean into the deep ocean during the last glacial period according to the caco3 compensation hypothesis this should have caused a transient drop in deep ocean co32 that was eventually reversed by seafloor dissolution of caco3 the resulting increase in whole ocean ph may have had a significant impact on atmospheric co2 compounding any decrease that was due to the initial vertical co2 shift the opposite hypothetically occurred during deglaciation when co2 was returned to the upper ocean and atmosphere and deep ocean co32 temporarily increased followed by excess burial of caco3 and a drop in whole ocean ph the deep sea record of caco3 preservation appears to reflect these processes with the largest excursion during deglaciation as expected but various factors make quantification of deep sea paleo co32 difficult here we reconstruct deep equatorial pacific co32 over the last glacial interglacial cycle using benthic foraminiferal zn ca which is strongly affected by saturation state during calcite precipitation our data are in agreement with the caco3 compensation theory including glacial co32 concentrations similar to or slightly lower than today and a termination i co32 peak of 25 30 mol kg 1 the deglacial co32 rise precedes ice sheet melting consistent with the timing of the atmospheric co2 rise a later portion of the peak could reflect removal of co2 from the atmosphere ocean system due to boreal forest regrowth caco3 compensation alone may explain more than one third of the atmospheric co2 lowering during glacial times

ocean chemistry during glacial time abstract measurements of co2 to air ratios in the gas trapped in bubbles in ice of glacial age suggest that the co2 content of the atmosphere was considerably lower during peak glacial time than during holocene time the purpose of this paper is to show that such a change must in all likelihood be the result of alterations in the nutrient element chemistry of sea water two possible scenarios are presented one involves alternate storage and erosion of phosphorous leaving residues from shelf sediments the other involves changes in the c p ratio in the organic debris falling to the deep sea means of verifying the nutrient cycle hypothesis are also given it is shown that the 13c record as we know it in planktonic and benthic foraminifera the oxygen record as inferred from benthic foraminifera species distributions and the early post glacial caco3 preservation event as recorded by aragonitic pteropods are consistent with both of the hypotheses presented only if an early post glacial spike in the 13c record for planktonic shells could be found would it be possible to eliminate one of these hypotheses i e that involving shelf storage the implications of these nutrient hypotheses to climate theory are as follows if shelf storage is responsible for the glacial to interglacial co2 increase then the co2 change must be considered an amplifier of some primary cause the reason is that sea level changes are needed to drive deposition on and erosion from the shelves on the other hand if changes in the c p ratio for falling debris are responsible then the co2 change could either be an amplifier or a primary cause for the major glacial to interglacial climatic cycle the latter is possible as self sustained oscillations in ocean chemistry might be driven by interactions between ocean ecology and ocean nutrient chemistry

carbonate deposition climate stability and neoproterozoic ice ages the evolutionary success of planktic calcifiers during the phanerozoic stabilized the climate system by introducing a new mechanism that acts to buffer ocean carbonate ion concentration the saturation dependent preservation of carbonate in sea floor sediments before this buffering was primarily accomplished by adjustment of shallow water carbonate deposition to balance oceanic inputs from weathering on land neoproterozoic ice ages of near global extent and multimillion year duration and the formation of distinctive sedimentary cap carbonates can thus be understood in terms of the greater sensitivity of the precambrian carbon cycle to the loss of shallow water environments and co 2 climate feedback on ice sheet growth

climatic change and caco3 preservation an 800 000 year bathymetric reconstruction from the central equatorial pacific ocean sixteen deep sea cores from the central equatorial pacific are used to reconstruct a continuous 800 000 year 800 kyr record of bathymetric variations in carbonate preservation as measured by calcium carbonate caco3 content the depth of the sedimentary lysocline has fluctuated markedly in conjunction with late pleistocene climate cycles while the carbonate critical depth ccrd which is the water depth where the sediments contain 10 caco3 has remained relatively constant as a result the depth of the lysocline controls the bathymetric position and thickness of the caco3 transition zone defined as the depth from the lysocline to the ccrd modern and interglacial aged sediments show poor caco3 preservation and thick caco3 transition zones glacial aged sediments show good preservation and deep thin zones due to the deepening of the lysocline detailed comparison of the caco3 preservation and oxygen isotope records from the central equatorial pacific confirms the observation that preservation maxima and minima tend to occur during the latter half of glacial and interglacial stages and on climate transitions rather than during the middle of climatic stages during the nine major glacial stages of the last 800 kyr the lysocline deepened by at least 400 to 800 m this deepening indicates an increase in the abyssal carbonate ion concentration co3 and a depression of the calcite saturation horizon best explained by the deeper presence of a more carbonate saturated water mass the bottom of the transition zone has remained at a relatively constant depth during the brunhes chron indicating a balance between caco3 sedimentation and dissolution in the deepest waters of the central equatorial pacific

glacial versus interglacial sedimentation rates and turbidite frequency in the bahamas the southern tongue of the ocean is a 1300 m deep flat floored basin in the bahamas that receives large amounts of sediment from the carbonate platforms surrounding it on three sides we have examined five 8 13 m long piston cores and determined bulk sedimentation rates turbidite frequency and turbidite accumulation rates for the past two glacial and interglacial periods the mean of bulk sedimentation rates is four to six times higher in interglacial periods average accumulation rates of recognizable turbidites are higher by a factor of 21 to 45 and interglacial turbidite frequency is higher by a factor of 6 to 14 sediment composition indicates that increased interglacial rates are due to higher accumulation of platform derived material additional data from other bahamian basins as well as published material from the caribbean strongly suggest that highstand shedding is a general trend in pure carbonate depositional systems carbonate platforms without a siliciclastic component export more material during highstands of sea level when the platform tops are flooded and produce sediment the response of carbonate platforms to quaternary sea level cycles is opposed to that of siliciclastic ocean margins where sediment is stored on the inner shelf during highstands and passed on to continental rises and abyssal plains during lowstands of sea level

carbonate dissolution in recent sediments of the eastern equatorial indian ocean preservation patterns and carbonate loss above the lysocline abstract multiple dissolution indices from 45 sediment samples show that the foraminiferal lysocline is near 3800 m in the eastern equatorial indian ocean close to the saturation horizon with respect to calcite in the water column below the lysocline the increase in foraminiferal fragmentation decrease in absolute abundance and progressive modification of planktic foraminiferal assemblages with depth is accompanied by an increasing rate of loss of carbonate from the sediments above the lysocline some dissolution must occur in order to produce the dramatic reduction in foraminiferal numbers up to 60 and the pattern of increased fragmentation with depth however the amount of carbonate actually lost from supralysoclinal sediments reaches at most 20 30 of the total at the depth of the lysocline the principal driving force behind supralysoclinal dissolution is most likely the oxidation of organic matter incorporated into the sediments dissolution above the lysocline has a greater apparent impact on relative preservation in the coarse 150 m fraction than it does on total carbonate loss because of redistribution of carbonate to the finer size fractions as fragments though the effects of dissolution on foraminiferal preservation are clearly visible at all depths the lysocline itself does appear to mark the local onset of large scale loss of dissolved carbonate from the sediments such an interpretation is broadly consistent with models regarding the saturation state of the overlying waters as the principal driving force behind the preservation or dissolution of recent carbonate sediments on the sea floor

recent increase in pacific caco3 dissolution a mechanism for generating old 14c ages abstract western equatorial pacific box cores taken from water depths greater than 4 km show increased dissolution and anomalously old 14c ages in the upper 8 cm the temporal response of the vertical distribution of sediment carbonate fraction and 14c age to a decrease in the dissolved carbonate ion concentration of the deep sea is examined with a diffusion advection dissolution model the nature of this response is highly sensitive to both the magnitude of the dissolved carbonate ion decrease and the rate of mixing of the upper few centimeters of sediment if the sediment is initially calcareous and the increase in undersaturation is sufficient to eventually dissolve away most of the solid carbonate the system relaxes on a very long time scale greater than 10 000 years the dissolution flux in such a case temporally is greater than the total sedimentation input and chemical erosion occurs the cumulative erosion is about 4 times greater for strong sediment mixing d 200 cm 2 ka 1 than for weak mixing d 2 cm2 ka 1 the chemical erosion causes old carbonate to be transferred into the sediment mixed layer as the interface moves downwards thus the 14 c 12 c ratio initially decreases when erosion decreases because the surface carbonate content is diminished the 14c age of the sediment continues to become older in the case of weak mixing but reverses itself and becomes younger in the presence of moderate or strong mixing an attempt to predict the observed caco3 and 14 c 12 c in west equatorial pacific sediment suggests that beginning a few thousand years ago the deep pacific was 20 more undersaturated than today for about 1500 yrs this could possibly have been caused by late holocene growth of coral reefs following after the deglaciation

late pleistocene evolution of the ocean s carbonate system abstract we demonstrate that the carbonate record from a single site ocean drilling program site 1089 in the deep south atlantic represents a qualitative high resolution record of the temporal evolution of the carbonate saturation state of the deep sea the record is especially notable because it is free from many of the complications that limit other records low sedimentation rates blurring by chemical erosion bioturbation etc the pattern of carbonate variability is characteristic of indo pacific cores with high carbonate glacials and low carbonate interglacials wt carbonate lags changes in benthic 18 o by an average of 7 6 kyr and carbonate variations are in phase with the rate of change first derivative of benthic 18 o intense dissolution occurs at the transition from interglacial to glacial periods and increased preservation occurs during deglaciations these observations represent two fundamentally different responses of the marine carbonate system the lagged response of carbonate to 18 o reflects a steady state mass balance process whereby the lysocline adjusts to maintain alkalinity balance between riverine input and marine burial the site 1089 carbonate signal is remarkably similar to inferred changes in the sr ca of seawater for the past 250 kyr which implies that both carbonate dissolution and seawater sr ca may be controlled by sea level induced changes in the location of carbonate deposition shelf basin fractionation during glacial to interglacial cycles the transient change in preservation during the transitions into and out of glacial stages reflects a response of the carbonate system to a redistribution of alkalinity and dic in the ocean i e carbonate compensation comparison of the site 1089 carbonate and vostok p co 2 records suggests a role of deep sea co 3 2 variations for governing at least some second order features of the atmospheric p co 2 signal in order to quantify this role however measurement of indices of dissolution along a true depth transect will be required to estimate the magnitudes of changes in deep sea co 3 2

the paradox of drowned reefs and carbonate platforms shallow water carbonate platforms and reefs are drowned when tectonic subsidence or rising sea level outpaces carbonate accumulation and benthonic carbonate production ceases drowned platforms are common in the geologic record but they present a paradox if one considers rates of processes involved during the early holocene when sea level rose at rates of 6 000 to 10 000 m yr mm 1 000 yr most reefs and platforms were outpaced by the rising sea during the late holocene with sea level rising 500 to 3 000 m yr in the atlantic caribbean area reefs and platforms started to recover built to sea level and prograded seaward 1 000 m yr is thus a conservative estimate of the average growth potential of modern reefs and platforms independently accumulation rates of prograding platforms in the geologic record suggest growth potential in excess of several hundred microns per year the growth potential of 1 000 m yr exceeds any relative rise of sea level caused by long term processes in the geologic record newly formed ocean crust subsides at a maximum of 250 m yr basin subsidence averages 10 to 100 m yr and sea level rises due to increased sea floor spreading amount to less than 10 m yr rapid pulses of relative rise of sea level or reduction of benthic growth by deterioration of the environment remain the only plausible explanations of drowning the geologic record shows examples of both of these processes global mass extinctions of reefs and platforms occurred in the middle cretaceous eustatic rise due to submarine volcanism or desiccation of a small ocean basin and the late devonian global crisis of ocean environment extraterrestrial cause drowning controlled by regional tectonics prevailed in the jurassic and early cretaceous of the tethyan realm and the drowning of mesozoic platforms in the western north atlantic seems to have been dictated by plate tectonic drift to higher latitudes

influence of variable rates of neritic carbonate deposition on atmospheric carbon dioxide and pelagic sediments short term imbalances in the global cycle of shallow water calcium carbonate deposition and dissolution may be responsible for much of the observed pleistocene change in atmospheric carbon dioxide content however any proposed changes in the alkalinity balance of the ocean must be reconciled with the sedimentary record of deep sea carbonates the possible magnitude of the effect of shallow water carbonate deposition on the dissolution of pelagic carbonate can be tested using numerical simulations of the global carbon cycle boundary conditions can be defined by using extant shallow water carbonate accumulation data and pelagic carbonate deposition dissolution data on timescales of thousands of years carbonate deposition versus dissolution is rarely out of equilibrium by more than 1 5 x 10 13 mole yr 1 results indicate that the carbonate chemistry of the ocean is rarely at equilibrium on timescales less than 10 ka this disequilibrium is probably due to sea level induced changes in shallow water calcium carbonate deposition dissolution an interpretation that does not conflict with pelagic sedimentary data from the central pacific

glacial interglacial co2 change the iron hypothesis several explanations for the 200 to 280 ppm glacial interglacial change in atmospheric co2 concentrations deal with variations in southern ocean phytoplankton productivity and the related use or nonuse of major plant nutrients an hypothesis is presented herein in which arguments are made that new productivity in today s southern ocean 7 4 1013g yr 1 is limited by iron deficiency and hence the phytoplankton are unable to take advantage of the excess surface nitrate phosphate that if used could result in total southern ocean new production of 2 3 1015 g c yr 1 as a consequence of fe limited new productivity holocene interglacial co2 levels preindustrial are as high as they were during the last interglacial 280 ppm in contrast atmospheric dust fe supplies were 50 times higher during the last glacial maximum lgm because of this fe enrichment phytoplankton growth may have been greatly enhanced larger amounts of upwelled nutrients may have been used and the resulting stimulation of new productivity may have contributed to the lgm drawdown of atmospheric co2 to levels of less than 200 ppm background information and arguments in support of this hypothesis are presented

are seawater sr ca variations preserved in quaternary foraminifera abstract high precision measurements of sr ca in planktonic foraminifera for the last 150 ka reveal sr ca variations of up to 12 on glacial interglacial time scales although records showing the largest variations appear to be strongly influenced by selective dissolution other records show sr ca variations of 3 5 that do not covary with indicators of dissolution intensity and that are reproduced in sites of contrasting quaternary dissolution histories these systematic variations are characterized by high sr ca ratios during glacial maxima followed by steep decreases during deglaciation and gradual increases through interstadial periods closely following 18 o curves foraminiferal sr ca variations may reflect changes in the sr ca ratio of seawater or they may be due to kinetically or biologically induced changes in sr partitioning coupled numerical models of the sr and ca budgets of the ocean reveal that sea level changes together with large changes in river fluxes and carbonate accumulation rates can produce seawater sr ca variations that approximate both the shape and amplitude of foraminiferal sr ca variations however such extreme changes in river and carbonate fluxes conflict with existing data on carbonate accumulation rates and sr isotopic constraints on the magnitude of variations in the river flux smaller variations 1 3 in the sr ca ratio of seawater likely characterize quaternary glacial cycles changes in sr partitioning due to glacial interglacial changes in the carbonate ion concentration and other environmental factors likely produce additional variation in the sr ca record of planktonic foraminifera

carbon burial rates in sediments and a carbon mass balance for the herbert river region of the great barrier reef continental shelf north queensland australia the largest century scale carbon reservoir in the herbert river sector of the great barrier reef continental shelf is carbonate carbon this carbonate carbon is produced by corals coralline algae and other benthic organisms and is stored on less than 13 of the area of the shelf maximum organic carbon burial rates 1 28 mol m 2 yr 1 occur within a wind protected 20 m water depth embayment 1 area of the shelf where the highest bulk sedimentation rates 1 12 kg m 2 yr 1 were determined from 210pb and137 cs profiles in 1 4 m cores sediment organic carbon oc and carbonate carbon cc accumulation rates are very low in the great barrier reef lagoon shelf and slope where most annual productivity 8 15 mol oc m 2 yr 1 is decomposed by algal and microbial respiration a carbon mass balance indicated that approximately 1 of combined river and marine organic carbon production was preserved in across shelf sedimentation but 3 of river and mangrove organic carbon input was preserved in this small wind protected embayment an across shelf carbon mass balance model predicted average shelf organic matter respiration correctly and the ratio of organic carbon fixation to respiration corrected for burial losses was 1 06

glacial interglacial rain ratio changes implications for atmospheric co2 and ocean sediment interaction abstract a reduction of the carbonate carbon to organic carbon export rain ratio during glacial times has been advanced to explain the glacial interglacial atmospheric co 2 variations this hypothesis is tested and implications for the dynamics of sedimentary carbonate preservation and dissolution are explored with a multi box model mbm of the ocean carbon cycle fully coupled to a new transient early diagenesis model called medusa a peak reduction of the rain ratio by 40 at the last glacial maximum lgm was found to produce a net atmospheric p co 2 reduction of about 40 ppm changing shelf carbonate accumulation rates and continental weathering inputs produced a 55 60 ppm reduction the combination of the two mechanisms generates a p co 2 change of 90 95 ppm which compares well with the observed data however the resulting model sedimentary record does not conform to actual sedimentary records the changes related to continental shelf processes and variable weathering flux depress the calcite saturation horizon csh by about 1 km at the lgm if rain ratio variations are also considered that depression increases by another km in addition to this large amplitude for the csh possibly due to the adopted box model approach the changing rain ratio also leads to transition zone changes in the model sedimentary record that are opposite in phase with data based reconstructions realistic changes in the aragonite fraction of the carbonate rain were found to have only a minimal impact on atmospheric p co 2 finally chemical erosion of deep sea sediment was shown to reduce the amplitude of variation of the sedimentary ccd by about 10 20 it may provide a mechanism to improve the model data agreement

the influence of caco3 dissolution on core top radiocarbon ages for deep sea sediments radiocarbon ages on caco3 from deep sea cores offer constraints on the nature of the caco3 dissolution process the idea is that the toll taken by dissolution on grains within the core top bioturbation zone should be in proportion to their time of residence in this zone if so dissolution would shift the mass distribution in favor of younger grains thereby reducing the mean radiocarbon age for the grain ensemble we have searched in vain for evidence supporting the existence of such an age reduction instead we find that for water depths of more than 4 km in the tropical pacific the radiocarbon age increases with the extent of dissolution we can find no satisfactory steady state explanation and are forced to conclude that this increase must be the result of chemical erosion the idea is that during the holocene the rate of dissolution of caco3 has exceeded the rain rate of caco3 in this circumstance bioturbation exhumes caco3 from the underlying glacial sediment and mixes it with caco3 raining from the sea surface

modeling organic carbon burial during sea level rise with reference to the cretaceous after three decades of research on the correlation between sea level and various proxies there has been very little quantification of the first order influence of sea level change on nutrient inventory marine productivity and burial of organic carbon we present a model aimed at quantifying the burial of organic carbon as a function of sea level rise the biogeochemical model explicitly considers the mean surface area distribution of the earth as a function of elevation also included is dissolved inorganic phosphate dip liberated from coastal sediments during transgression we quantify how sea level rise of magnitudes inferred for the mid cretaceous influences the phosphorus cycle and burial of organic carbon the burial efficiency is greater on the shelf therefore in the model the larger shelf area under high sea level results in more efficient burial of marine organic carbon for a given dip concentration and associated new production of organic matter np with a late cretaceous model shelf area the residence time of dip decreases by 60 relative to the present day reference thus in the final steady state dip and np in the open ocean are reduced compared to today when the biologically reactive phosphorus preac fluxes to the ocean from land are held constant the lower new production reduces the oxygen demand for respiration and results in a significant oxygenation of the global ocean finally the global organic carbon burial decreases by 30 relative to today in the model this decrease results from feedbacks between the flux of organic carbon to the seafloor and the ratio of organic carbon to preac in buried sediments in contrast during sea level rise coastal erosion may increase the preac flux to the ocean by up to 20 relative to today and cause a temporary increase in dip concentration in the ocean the resulting increase in organic carbon burial is equivalent to a carbon isotope event of 0 5 to 1 larger carbon isotope events can be triggered by sea level rise only when the ocean is sufficiently close to anoxia in the oxygen minimum zone just prior to the sea level rise

time partitioning in cratonic carbonate rocks dissimilarity in relations between thickness duration and accumulation rate in holocene sections metre scale phanerozoic cycles and epoch interval phanerozoic sequences reflects variation in the distribution of depositional and hiatal time at different scales of observation modern accumulation rates are strongly dependent on duration of deposition lower rates correspond to longer durations phanerozoic cycle thicknesses are similar to those of holocene sections suggesting that both formed while filling similar amounts of accommodation space however accumulation rates of phanerozoic cycles and sequences are about two orders of magnitude less than in modern settings and they show neither strong dependence on duration of accumulation nor significant variation over phanerozoic time hence net accumulation is primarily controlled by regional subsidence rate these relations also allow for determination of that fraction of cycle period recorded as rock and that corresponding to hiatal time at intercycle boundaries depending on subsidence rate and amount of compaction most cratonic carbonate units accumulated over 3 to 30 of the time represented by sequences in which they occur

the cause of the glacial to interglacial atmospheric co2 change a polar alkalinity hypothesis in an attempt to create a scenario for the cause of the glacial to interglacial co2 change recorded in air trapped in polar ice we call on an increase in the alkalinity of polar surface waters in this way we circumvent a major deficiency of the polar nutrient scenarios of sarmiento and toggweiler 1984 siegenthaler and wenk 1984 and knox and mcelroy 1984 namely our scenario does not require a drop in the nutrient content of polar surface waters in conformity with the demonstration by boyle 1988a b that the cadmium content of planktonic foraminifera from polar regions did not decrease from late glacial to holocene time the rise in alkalinity required by our model is a natural consequence of the demise during glacial time of north atlantic deep water as a major force in ocean circulation and of the nutrient maximum deepening of boyle 1988b rather than being original our hypothesis builds on the concept basic to the polar nutrient hypotheses namely that the co2 partial pressure in polar waters controls that for both the atmosphere and warm surface ocean it also requires the alkalinity increase in surface waters produced by boyle s nutrient deepening

production and accumulation of calcium carbonate in the ocean budget of a nonsteady state present day production of caco3 in tne world ocean is calculated to be about 5 billion tons bt per year of which about 3 bt accumulate in sediments the other 40 is dissolved nearly half of the carbonate sediment accumulates on reefs banks and tropical shelves and consists largely of metastable aragonite and magnesian calcite deep sea carbonates predominantly calcitic coccoliths and planktonic foraminifera have orders of magnitude lower productivity and accumulation rates than shallow water carbonates but they cover orders of magnitude larger basin area twice as much calcium is removed from the oceans by present day carbonate accumulation as is estimated to be brought in by rivers and hydrothermal activity 1 6 bt suggesting that outputs have been overestimated or inputs underestimated that one or more other inputs have not been identified and or that the oceans are not presently in steady state one missing calcium source might be groundwater although its present day input is probably much smaller than that of rivers if as seems likely caco3 accumulation presently exceeds terrestial and hydrothermal input this imbalance presumably is offset by decreased accumulation and increased input during lowered sea level shallow water accumulation decreases by an order of magnitude with a 100 m drop in sea level while groundwater influx increases because of heightened piezometric head and the diagenesis of metastable aragonite and magnesian calcite from subaerially exposed shallow water carbonates

the sequence of events surrounding termination ii and their implications for the cause of glacial interglacial co2 changes events surrounding termination ii as preserved in the vostok ice core provide a number of clues about the mechanisms controlling glacial to interglacial climate change antarctic temperature and the atmosphere s co2 content increased together over a period of 8000 years this increase is bounded by a drop in dust flux at its onset and by a drop in the 18o of trapped air at its finish a similar lag between dust flux and foraminiferal 18o is seen in a southern ocean marine record suggesting that the 18o in air trapped in vostok ice is a valid proxy for ice volume the synchronous change of atmospheric co2 and southern hemisphere temperature thus preceded the melting of the northern hemisphere ice sheets this observation coupled with the fact that nutrient reorganization in the north atlantic occurs with or after the sea level rise eliminates many scenarios proposed to explain the co2 rise including those which rely on sea level change conveyor related nutrient redistribution or north atlantic cooling southern ocean scenarios become the front runners but the most popular mechanism iron fertilization has two problems in explaining the co2 rise before termination ii first much of the dust demise occurs prior to the change in co2 so if iron is the villain a threshold value of its supply must be called upon above which productivity does not continue to increase second the co2 rise continues for some 4 5 kyr after the dust flux has fallen to close to zero these problems may be solved if the increased iron supply in dust caused higher rates of nitrogen fixation during the glacial periods in this case the residence time of oceanic nitrate of a few thousand years would enable decreasing productivity to be a global rather than a local phenomenon and would explain the slow rampup of atmospheric co2

variability in the uranium isotopic composition of the oceans over glacial interglacial timescales uranium series mass spectrometric analyses of corals from the uplifted last glacial terraces at huon peninsula papua new guinea that grew from 50 000 years ago to 30 000 years ago show systematically low values of 234u 238u at the time of coral growth compared with modern corals when combined with coral data from other studies a systematic trend emerges indicating shifts in the 234u 238u ratio at times of major glacial interglacial transitions that involve large variations in sea levels from last glacial to holocene the rate of change in 234u is approximately 1 per thousand years the variations in the u budget of the oceans appear to be due to accumulation of excess 234u in near shore areas in anoxic and suboxic sediments in salt marshes and mangroves in estuaries and in continental margins during periods of warm climate and high sea levels these near shore areas are exposed during periods of low sea level resulting in rapid oxidation of u into highly soluble phases the subsequent release of 234u enriched uranium into the oceans occurs over a sustained period in step with rising sea levels

modeling the response of the oceanic si inventory to perturbation and consequences for atmospheric co2 1 it has been suggested that much of the observed glacial interglacial variability in the atmospheric mixing ratio of co2 xco2 could potentially be driven by a perturbation of the marine si cycle to date only relatively simple steady state analysis has been made of this hypothesis in this study we develop a description of the ocean carbon cycle incorporating novel descriptions for the recycling of si both within the water column and in deep sea sediments a high degree of computational efficiency enables model integrations over multiple glacial interglacial cycles driven by a time varying input of dissolved si to the ocean due to the long time constant 23 ka of atmospheric xco2 response to perturbation in si supply and the highly nonlinear nature of opal preservation in deep sea sediments we find that reduction in the deposition rate of aeolian silicates at the surface ocean can explain little 3 ppm of the rapid 90 ppm rise in atmospheric xco2 observed at glacial termination however increased si supply has the potential to make an important contribution to the decline in atmospheric xco2 associated with the much slower transition from interglacial to full glacial conditions

toward explaining the holocene carbon dioxide and carbon isotope records results from transient ocean carbon cycle climate simulations records of atmospheric co2 and d 13 c as well as the spatiotemporal evolution of d 13 c and carbonate ion concentration in the deep sea deposition of shallow water carbonate carbonate compensation of land uptake during the glacial termination land carbon uptake and release during the holocene and the response of the ocean sediment system to marine changes during the termination contribute roughly equally to the reconstructed late holocene pco2 rise of 20 ppmv the 5 ppmv early holocene pco2 decrease reflects terrestrial uptake largely compensated by carbonate deposition and ocean sediment responses additional small contributions arise from holocene changes in sea surface temperature ocean circulation and export productivity the holocene pco2 variations result from the subtle balance of forcings and processes acting on different timescales and partly in opposite direction as well as from memory effects associated with changes occurring during the termination different interglacial periods with different forcing histories are thus expected to yield different pco2 evolutions as documented by ice cores

geodynamics of the divergent double subduction along the bangong nujiang tethyan suture zone insights from late mesozoic intermediate mafic rocks in central tibet abstract bangong nujiang suture zone bnsz in central tibet plays an important role in evaluating the formation and uplift mechanism of tibetan plateau however its mesozoic tectonic evolution is ambiguous and intensely debated in this study early cretacesous adakites and sodium rich arc rocks are identified in western qiangtang wq and northern lhasa nl sub terranes forty four adakite samples from both wq and nl have akin geochemical features and are derived from partial melting of subducted oceanic crust with amphibole residual nineteen sodium rich samples originated from a mixed source region between crustal sediment and enriched lithospheric mantle these two parallel arc belts separated by the bangong nujiang suture zone bnsz represent the divergent double subduction of the bangong nujiang tethyan ocean bnto combined with the previous studies our new data suggest three significant magmatic flare ups at 240 140 ma 135 105 ma and 92 60 ma in the wq and bnsz and two at 135 105 ma and 92 60 ma in the nl these asymmetrical magmatic activities indicate that the southern subduction may have commenced at about 135 ma and experienced slab breakoff at the latest early cretaceous and the northern subduction could trace back to l triassic 228 ma and experienced episodic low angle subduction slab rollback 190 140 ma and oceanic ridge subduction 135 100 ma the 100 92 ma magmatic gap 92 60 ma magmatic flare up and l cretaceous angular unconformities indicate that the double sided subduction of the bnto resulted in soft collision with oceanic lithosphere detachment

pacific caco3 preservation and δ18o since 4 ma paleoceanic and paleoclimatic implications the pliocene pleistocene history of caco3 preservation in the central equatorial pacific is reconstructed from a suite of deep sea cores and is compared to fluctuations in global ice volume inferred from 18o records the results are highlighted by 1 a strong covariation between caco3 preservation and ice volume over 104 to 106 year time scales 2 a long term increase in ice volume and caco3 preservation since 3 9 ma demonstrated by a deepening of the lysocline and the carbonate critical depth 3 a dramatic shift to greater caco3 preservation at 2 9 ma 4 distinctive ice volume growth and caco3 preservation events at 2 4 ma which are associated with the significant intensification of northern hemisphere glaciation 5 a mid pleistocene transition to 100 kyr cyclicity in both caco3 preservation and ice volume and 6 a 600 kyr brunhes dissolution cycle superimposed on the late pleistocene glacial interglacial 100 kyr cycles caco3 preservation primarily reflects the carbonate chemistry of abyssal waters and is controlled by long term 106 year and short term 104 to 105 year biogeochemical cycling and by distinct paleoclimatic events we attribute the long term increase in caco3 preservation primarily to a fractionation of caco3 deposition from continental shelf to ocean basin and secondarily to a gradual rise in the riverine and glaciofluvial flux of ca on shorter time scales the fluctuations in caco3 preservation slightly lag ice volume fluctuations and are attributed to climatically induced changes in the circulation and chemistry of pacific deep water

the role of vertical chemical fractionation in controlling late quaternary atmospheric carbon dioxide the 30 decrease in atmospheric carbon dioxide during glacial maxima must be driven by some change in the chemical circulation of the ocean here a new model for late quaternary co2 variability is presented which resolves some problems occurring in previous models including the timing of carbon dioxide response and changes in the oxygen content of the deep ocean the primary driving factor in this model is a rearrangement of chemical distributions in the ocean whereby labile nutrients and metabolic co2 are concentrated in deep waters rather than in intermediate waters as observed in the modern ocean this new bottom heavy chemical structure does not affect atmospheric carbon dioxide directly instead co2 induced acidity lowers the deep ocean carbonate ion concentration and temporarily increases carbonate dissolution rates oceanic alkalinity then rises until the deep ocean carbonate ion is restored to its steady state value the resulting increase in oceanic alkalinity draws co2 out of the atmosphere into the ocean alkalinity and atmospheric co2 lag several thousand years behind the change in oceanic chemical structure this delayed response is determined by the limited rate of continental weathering and deep ocean carbonate dissolution relative to the oceanic alkalinity inventory it is proposed that characteristic deglacial and preglacial states of the ocean are leading factors driving glacial interglacial climate changes this concept reinterprets the carbon isotope contrast between surface water and deep waters 13c p b as due to a shift of light metabolic carbon from intermediate waters into deep waters the process is illustrated here by a simple equilibrium five box ocean model the observed intermediate depth nutrient depletion is not sufficient in itself to determine which of several possible mechanisms are operating and some mechanisms are not as effective in changing atmospheric co2 as others the largest response is seen from deepening the regeneration cycle of organic carbon the least response is seen from converting north atlantic deep water into intermediate water

milankovitch theory viewed from devils hole variations in the oxygen isotope content 18o of late quaternary deep sea sediments mainly reflect changes in continental ice mass1 and hence provide important information about the timing of past ice ages because these sediments cannot yet be dated directly beyond the range of radiocarbon dating 40 50 kyr ages for the 18o record have been generated2 3 by matching the phase of the changes in 18o to that of variations in the earth s precession and obliquity adopting this timescale yields a close correspondence between the time varying amplitudes of these orbital variations and those of a wide range of climate proxies4 lending support to the milankovitch theory that the earth s glacial interglacial cycles are driven by orbital variations recently winograd et al 5 reported a record of 18o variations in a fresh water carbonate sequence from devils hole nevada dated by u th disequilibrium6 they concluded that the timing of several of the features in the record which reflects changes in the temperature of precipitation over nevada as well as changes in the isotopic composition of the moisture source5 7 showed significant deviations from that predicted by milanko vitch theory here we demonstrate that applying the devils hole chronology to ocean cores requires physically implausible changes in sedimentation rate moreover spectral analysis of the devils hole record shows clear evidence of orbital influence we therefore conclude that transfer of the devils hole chronology to the marine record is inappropriate and that the evidence in favour of milankovitch theory remains strong

calibration of the c 14 timescale over the past 30 000 years using mass spectrometric u th ages from barbados corals uranium thorium ages obtained by mass spectrometry from corals raised off the island of barbados confirm the high precision of this technique over at least the past 30 000 years comparison of the u th ages with 14c ages obtained on the holocene samples shows that the u th ages are accurate because they accord with the dendrochronological calibration before 9 000 yr bp the 14c ages are systematically younger than the u th ages with a maximum difference of 3 500 yr at 20 000 yrbp the u th technique thus provides a way of calibrating the radiocarbon timescale beyond the range of dendrochronological calibration

effects of quaternary sea level cycles on strontium in seawater abstract the effects of quaternary sea level changes on the sr budget of the ocean are investigated using coupled numerical models of the seawater sr and ca budgets glacial interglacial sea level cycles influence the sr concentration of seawater directly through the periodic exposure and weathering of aragonite on continental shelves and indirectly by modulating the location and extent of carbonate deposition in the ocean as sea level recedes brief pulses of sr are added to the ocean from recrystallization of shelf aragonite this flux at its maximum is nearly ten times larger than the combined riverine and hydrothermal influx the large shelf recrystallization fluxes during glacial maxima produce rapid increases in the sr ca ratio of seawater despite the long residence time of sr in the ocean variations in the ratio of aragonitic vs calcitic sedimentation also influence on the sr content of seawater because the sr partitioning coefficient is higher in aragonite however this effect is minor compared to shelf aragonite recrystallization based on a variety of sensitivity tests the amplitude of sr ca variations ranges from 1 to 3 and is maximized by constant rates of total carbonate deposition extensive aragonite recrystallization and carbonate budgets which include dissolution of shelf carbonates such variation is sufficient to produce up to 1 5 c errors in paleotemperatures calculated from coral sr ca ratios since the last glacial maximum

surface sediment carbonate mineralogy and water column chemistry nicaragua rise versus the bahamas abstract periplatform surface sediments were studied for carbonate mineralogy in conjunction with analyses of the water column for carbonate chemistry on the eastern northern nicaragua rise nnr in the caribbean sea the results show a strong correspondence between variations and disappearance with increasing water depth of metastable carbonate minerals fine aragonite and magnesian calcite and their respective saturation levels in the overlying waters similar correspondence between variations in sediment proportions of fine aragonite and magnesian calcite and their respective saturation levels has previously been established in the bahamas there are however significant differences between the two areas the sharp decrease in aragonite content and the measured aragonite saturation level occur at 4000 m in the bahamas compared to 1800 m on the eastern nnr in both areas magnesian calcite minima correspond to the in situ pco 2 maxima in the water column the magnesian calcite minimum however is at 950 m in the bahamas and 750 m on the eastern nnr magnesian calcite disappears in the bahamas at 3800 m and at 2000 m on the eastern nnr these results demonstrate the importance of the influence of overlying water chemistry on the preservation of metastable carbonate minerals in off bank periplatform sediments and they clearly demonstrate the difference in terms of carbonate preservation between the poorly ventilated waters of the caribbean sea and the well oxygenated waters of the adjacent atlantic ocean they also open the possibility of obtaining paleoceanographic information on the depth of the co 2 maximum o 2 minimum and its separation from the aragonite saturation depth in at least some areas

paleoproductivity from benthic foraminifera abundance glacial to postglacial change in the west equatorial pacific surface productivity is correlated with the rate of accumulation of benthic foraminifera on the deep sea floor as a rule of thumb for each 1 mg of organic carbon arriving at the sea floor one benthic foram shell 150 m is deposited the correlation can be used to reconstruct organic flux to the sea floor in the past and hence the productivity of past oceans applying the appropriate equations to box core data from the ontong java plateau in the western equatorial pacific we found that productivity during the last glacial maximum exceeded present productivity by a factor of between 1 5 and 2 0 with intermediate values for the mid transition period accumulation of benthic foraminifera was depressed on top of the plateau during the glacial and transitional period presumably because increased winnowing removed part of the food supply

interpreting transient carbonate compensation depth changes by marine sediment core modeling 1 with the advent of computationally fast intermediate complexity models of earth s climate and carbon cycle the marine record can be interpreted much more directly than before specifically the mechanistic simulation of deep sea sediment cores provides an important step in bridging the model data divide here i use this methodology to help interpret the excursion in carbonate compensation depth ccd during the paleoceneeocene thermal maximum that is recorded in cores recovered from walvis ridge in the south atlantic by explicitly simulating the expected geological record of a massive co2 release in an earth system model i show how reduction in the intensity of subsurface mixing of the sediment by benthic animals substantially magnifies the recorded shoaling of the ccd conversely to quantify correctly the carbon release consistent with the observed ccd changes one must account for any bioturbational changes a reduction in sediment mixing intensity also appears to be important to reproducing the sharpness of the contact between carbonate rich late paleocene sediments and the overlying early eocene clay layer at walvis ridge assuming a relatively rapid approximately 1 ka duration co2 release further helps to account for some of the paleoceanographic observations finally interbasin differences in bioturbational regime help resolve some of the observed disparity in carbonate preservation between walvis ridge and sites outside of the atlantic although changes in ocean ventilation and circulation are also likely to play a critical role in this

pacific carbonate dissolution revisited in order to understand the global co2 cycle it is important to be able to infer past ocean chemistry from the sedimentary carbonate record using a simple box model we show that the modern sedimentary lysocline in the equatorial pacific appears to be out of steady state equilibrium with respect to water chemistry as first suggested by kier 1984 we attribute large excursions in lysocline depth to changes in carbonate chemistry and or productivity fluxes if carbonate ion changes in the atmospheric pco2 change about a quarter of the glacial interglacial amplitude we attribute the relative invariance of the depth of the ccd over the past 800 ka to slow accumulation rates accompanying high dissolution fluxes relaxation times of the sediment mixed layer in these highly dissolved sediments are considerably longer than the timescale of glacial interglacial cycles a radiocarbon dilemma is manifested by an increase in the age of coretop calcite with water depth and thus also with dissolution flux below 4500 m in the equatorial pacific we present radiocarbon data from the atlantic that suggest that this phenomenon is not produced by chemical erosion as has been previously suggested broecker et al 1991 a fraction of the dissolution flux must occur at the sediment water interface or by an equivalent mechanism

vostok ice core provides 160 000 year record of atmospheric co2 direct evidence of past atmospheric co2 changes has been extended to the past 160 000 years from the vostok ice core these changes are most notably an inherent phenomenon of change between glacial and interglacial periods besides this major 100 000 year cycle the co2 record seems to exhibit a cyclic change with a period of some 21 000 years

equatorial pacific calcite preservation cycles production or dissolution in the equatorial pacific ocean the depth and shape of the calcite lysocline appears to have changed significantly in response to climate forcing farrell and prell 1989 taking the farrell and prell record at face value the lysocline apparently became steeper during each of the last eight glacial stages also the accumulation rate of calcite during the last glacial maximum was 2 4 times higher than it was during the previous interglacial arrhenius 1952 1988 broecker 1971 farrell 1991 a numerical model for calcite dissolution in sediment is used to interpret these observations the model was validated by comparison with observations from the present day ocean these results are presented elsewhere if the lysocline fluctuations in the equatorial pacific are primarily a dissolution record then changes in the glacial pacific co3 of 20 40 m can be inferred here i offer the alternative explanation that cycles in equatorial production are responsible for the observations higher rates of calcite and organic carbon rain to the sediment in the equatorial region would have depressed the calcite lysocline and increased the calcite accumulation rate as observed a twofold increase in glacial production appears to be adequate to explain the observations but a precise determination is prevented by uncertainties in some of the model parameters

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

the age and origin of the younger dryas climate event in greenland ice cores 230th 234u and 14c dating of barbados corals has extended the calibration of 14c years b p to calendar years b p beyond the 9200 year tree ring series bard et al 1990 this now permits the conversion of 14c chronozones which delimit major climate shifts in western europe to calendar years the younger dryas chronozone defined as 11 000 to 10 000 14c years b p corresponds to 13 000 to 11 700 calendar years b p this calibration affects the interpretation of an intensely studied example of the younger dryas climate event the 18o anomaly between 1785 and 1793 m in dye 3 ice core the end of the 18o anomaly in dye 3 ice core has been dated by measurements of 14c in air bubbles andree et al 1984 1986 and by annual layer counting hammer et al 1986 the older 14c dates fall out of the range of the tree ring calibration series but can now be calibrated to calendar years using the barbados 230th 234u calibration the 14ccorrected age for the end of the 18o event is 10 300 400 calendar years b p compared to the annual layer counting age of 10 720 150 years b p thus the younger dryas event in the dye 3 ice core ends in the preboreal chronozone 11 700 to 10 000 calendar years b p and is not correlative with the end of the younger dryas event identified in pollen records marking european vegetation changes the end of the dye 3 18o event is however correlative with the end of meltwater pulse ib fairbanks 1989 marking a period of intense deglaciation with meltwater discharge rates exceeding 13 000 km yr

glacial interglacial variability of atmospheric co2 due to changing continental silicate rock weathering a model study an 11 box model of the oceanic carbon cycle including sedimentary processes is used to explore the role chemical weathering of continental silicate rocks might play in driving atmospheric co2 levels on glacial interglacial timescales histories for the consumption of co2 by silicate rock weathering processes are derived from the marine ge si record taking the major uncertainties in the knowledge of the ge and si cycles into account several histories for the evolution of the riverine dissolved silica fluxes are calculated from this record the investigation of the systematics between riverine dissolved silica and bicarbonate fluxes under different weathering regimes leads us to the tentative conclusion that although there is no correlation between dissolved silica and total bicarbonate concentrations in the major rivers there may exist a negative correlation between weathering intensity and the ratio of dissolved silica to bicarbonate derived from silicate weathering alone with this correlation as a working hypothesis it is possible to interpret the dissolved silica fluxes in terms of equivalent co2 consumption rates the calculated histories indicate that glacial rates of co2 consumption by chemical silicate rock weathering could have been twice and possibly up to 3 5 times as high as they are today when used to force the carbon cycle model they are responsible for glacial interglacial pco2 variations in the atmosphere of typically 50 60 ppm and up to 95 110 ppm these variations are superimposed to a basic oscillation of 60 ppm generated by the model mainly in response to coral reef buildup and erosion processes the total pco2 signal has an amplitude of about 80 90 ppm and up to 125 135 ppm although these large amplitudes indicate that silicate weathering processes should be taken into account when studying glacial interglacial changes of co2 in the atmosphere it also raises new problems such as too high co2 levels during the period from 110 70 kyr b p requiring further study

carbon stocks and isotopic budgets of the terrestrial biosphere at mid holocene and last glacial maximum times abstract the carbon fluxes stocks and isotopic budgets of the land biosphere at mid holocene 6 ka bp and last glacial maximum 21 ka bp times are reconstructed with the carbon assimilation in the biosphere caraib model forced with two different sets of climates simulated by the european centre hamburg echam and lmd general circulation models it is found that the trends predicted on the basis of both sets of gcm climatic fields are generally consistent with each other although substantial discrepancies in the magnitude of the changes may be observed actually these discrepancies in the biospheric results associated with the use of different gcm climatic fields are usually smaller than the differences between biospheric runs performed while considering or neglecting the co2 fertilization effect which might however be overestimated by the model due to uncertainties concerning changes in nutrient availability the calculated changes with respect to the present of the biosphere carbon stock range from 132 to 92 gt c for the mid holocene and from 710 to 70 gt c for the last glacial maximum it is also shown that the relative contribution of the material synthesized by c4 plants to the total biomass of vegetation litter and soils was substantially larger at mid holocene and last glacial maximum times than today this change in the relative importance of the c3 and c4 photosynthetic pathways induced changes in the 13 c fractionation of the land biosphere these changes in the average biospheric fractionation resulting from the redistribution of c3 and c4 plants were partly compensated for by changes of opposite sign in the fractionation of c3 plants due to the modification of the intercellular co2 pressure within their leaves with respect to present times the combination of both processes reduced the 13 c discrimination i e less negative fractionation of the land biosphere by 0 03 to 0 32 during the mid holocene and by 0 30 to 1 86 at the last glacial maximum

holocene sediments of wistari reef towards a global quantification of coral reef related neritic sedimentation in the holocene wistari reef within the southern great barrier reef is a shallow coral reef platform featuring a very clearly defined leeward accretionary wedge of carbonate sediments the total global area of shallowly submerged coral reef has been quantified as 255 000 km 2 the question then becomes what additional area of sediment of significant thickness is associated with the measured shallow reef areas t at wistari reef the leeward sedimentary wedge has an area and a thickness that are roughly equal to the holocene sediments that have accumulated on the platform several important observations can be made from these data firstly the area of significant neritic carbonate sedimentation 1 m ka associated with coral reefs is near 500000 km 2 secondly the production rate of neritic carbonates at wistari reef is almost 50 less than the accumulation rate needed to obtain the volume of holocene reef sediments observed this implies that both production and accumulation neritic carbonate must have been more than a factor of two higher in the early to mid holocene c 2001 elsevier science b v all rights reserved

increase of atmospheric co2 during deglaciation constraints on the coral reef hypothesis from patterns of deposition 1 the coral reef hypothesis asserts that carbonate production on newly flooded shelves contributes importantly to the rise of atmospheric carbon dioxide during deglaciation we seek to constrain the timing and strength of such carbon dioxide flux by re assessing reef and platform distribution in the world ocean the pattern of reef growth that emerges suggests that emission of co 2 resulting from carbonate production was important particularly during the late stages of deglaciation the effect peaked during the early holocene and presumably contributed to the warming in the climatic optimum

reconstruction of atmospheric co2 from ice core data and the deep sea record of ontong java plateau the milankovitch chron we provide a reconstruction of atmospheric co2 from deep sea sediments for the past 625000 years milankovitch chron our database consists of a milankovitch template of sea level variation in combination with a unique data set for the deep sea record for ontong java plateau in the western equatorial pacific we redate the vostok ice core data of barnola et al 1987 to make the reconstructions we employ multiple regression between deep sea data on one hand and ice core co2 data in antarctica on the other the patterns of correlation suggest that the main factors controlling atmospheric co2 can be described as a combination of sea level state and sea level change for best results squared values of state and change are used the square of sea level rule agrees with the concept that shelf processes are important modulators of atmospheric co2 e g budgets of shelf organic carbon and shelf carbonate nitrate reduction the square of change rule implies that on short timescales any major disturbance of the system results in a temporary rise in atmospheric co2

a comparison of multiple proxies for export production in the equatorial pacific 1 several commonly used paleoproductivity proxies were compared to evaluate the validity of assumptions and limitations associated with each proxy export production fluxes cexport over glacial interglacial timescales were calculated from previously developed proxy specific algorithms at ttn013 pc72 and ttn013 pc114 both located in the equatorial pacific comparison of data from the same core intervals yields conflicting results despite calibrations based on the same core top samples the periodicity of marine barite excess ba and excess al based cexport records is similar the relative magnitude of cexport when calculated using excess ba and algorithms based on sediment trap data is significantly different than records based on core top calibrations particularly during glacial intervals at both sites bulk sedimentary al ti and ba ti ratios covary however these ratios do not correspond with the downcore records of their respective excess concentrations and their accumulation rates or with contemporaneous records based on marine barite excess ba and excess al accumulation although downcore records based on sediment mass accumulation rates may be compromised by sediment focusing this process cannot explain all the differences observed among the various data sets presented here this implies that some or all of these proxies do not exclusively respond to changes in export production the contradictions among these data highlight the importance of addressing inconsistencies among paleoproxies and re examining assumptions imbedded in proxy fundamentals prior to applying paleoproductivity proxies and interpreting paleoceanographic records

late pleistocene paleoclimatology of the central equatorial pacific flux patterns of biogenic sediments high resolution records of the concentration and mass accumulation rate mar or flux of biogenic sediments from core rc11 210 in the central equatorial pacific are compared for the entire late pleistocene the fluxes of calcium carbonate and organic carbon correlate well the opal flux pattern shows no direct correlation with the other two rather opal flux maxima correlate with slopes of i e both precede and follow the organic carbon and carbonate mar peaks organic carbon and calcite therefore may both be better indicators of past productivity than opal which is an indicator of transition at this location we interpret the sequence low biogenic fluxes high opal fluxes high carbonate carbon and opal fluxes as representing the transition from low to high sea surface biological productivity the phase relationships for eccentricity of the biogenic sedimentation records were compared to those of other climatic indications including the oxygen isotope record of ice volume the ice core co2 record the pacific 13c record the deep nutrient cd ca record and the eolian grain size record of wind intensity we find that starting from maximum ice volume phase angle of 0 the phase relationships of the 100 000 year periodicity show in the first quadrant maximum wind intensity 30 and maximum calcite and carbon flux 45 occurring first followed by maximum opal flux 75 and then maximum deep nutrients 95 minimum pacific 13c occurs at a phase angle of 155 the maximum co2 in the vostok record and minimum ice volume is at 180 thus in the eccentricity climate cycle glacial conditions lead to stronger wind driven circulation which enhances productivity which in turn results in enhanced oceanic and atmospheric carbon dioxide and minimum ice volume