role of deep sea temperature in the carbon cycle during the last glacial 1 to characterize the response of earth s climate system to increases in atmospheric co2 climate modelers define climate sensitivity as the change in global mean temperature in response to prescribed forcing here we turn this approach around and use estimates of ocean temperature change to investigate the mechanisms driving co2 variations over the last glacial new records provide evidence of a link between deep ocean temperature and atmospheric co2 over the last glacial cycle two mechanisms simultaneously couple pco2 and deep ocean temperature the temperature dependent solubility of co2 in seawater and the atmospheric co2 dependent radiative forcing of temperature each of these forcing mechanisms leaves a unique slope of covariation between co2 and deep ocean temperature which we estimate using numerical models of climate and the carbon cycle the pco2 t slopes derived from paleoclimate data differ between the deglaciation and shorter 5 kyr duration events in marine isotope stage 3 mis 3 revealing different mechanisms driving atmospheric co2 variability the amplitude of changes over the deglaciation coincides with estimates for co2 forcing of temperature however co2 changes during mis 3 can be explained solely by temperature dependent solubility driving variations in atmospheric pco2 the deep water temperature changes during mis 3 may reflect changes in the temperature or relative contribution of antarctic bottom water and play a role in the bipolar seesaw

the salinity temperature and δ18o of the glacial deep ocean we use pore fluid measurements of the chloride concentration and the oxygen isotopic composition from ocean drilling program cores to reconstruct salinity and temperature of the deep ocean during the last glacial maximum lgm our data show that the temperatures of the deep pacific southern and atlantic oceans during the lgm were relatively homogeneous and within error of the freezing point of seawater at the ocean s surface our chloride data show that the glacial stratification was dominated by salinity variations in contrast with the modern ocean for which temperature plays a primary role during the lgm the southern ocean contained the saltiest water in the deep ocean this reversal of the modern salinity contrast between the north and south atlantic implies that the freshwater budget at the poles must have been quite different a strict conversion of mean salinity at the lgm to equivalent sea level change yields a value in excess of 140 meters however the storage of fresh water in ice shelves and or groundwater reserves implies that glacial salinity is a poor predictor of mean sea level

opal accumulation rates in the equatorial pacific and mechanisms of deglaciation 1 a possible imprint on equatorial pacific sediments of a deglacial reinvigoration of the southern ocean overturning is increased opal accumulation rate this would arise from the transmission of silica rich deep water to the equatorial thermocline via subantarctic mode water and an associated increase in diatom productivity in search of this imprint sediment cores from the central tt013 pc72 and eastern v19 30 equatorial pacific have been analyzed for 230th normalized opal accumulation rates over the past five and three glacial terminations respectively equatorial opal accumulation rates sustained relatively low values over much of the records and were punctuated by large increases centered on some terminations but not all furthermore two periods of increased opal flux were observed that do not coincide with terminations sources other than the southern ocean may need to be considered in the silica budget of the equatorial pacific but the 13c of neogloboquadrina dutertrei can be used to support the presence of a deepwater nutrient signal in each case although a common deglacial mechanism or a common imprint thereof for each of the late pleistocene glaciations remains elusive the combination of opal flux and 13c of n dutertrei provides a diagnostic for past injection of deepwater nutrients into the equatorial undercurrent

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

glacial interglacial changes in subarctic north pacific stratification since the first evidence of low algal productivity during ice ages in the antarctic zone of the southern ocean was discovered there has been debate as to whether it was associated with increased polar ocean stratification or with sea ice cover shortening the productive season the sediment concentration of biogenic barium at ocean drilling program site 882 indicates low algal productivity during ice ages in the subarctic north pacific as well site 882 is located southeast of the summer sea ice extent even during glacial maxima ruling out sea ice driven light limitation and supporting stratification as the explanation with implications for the glacial cycles of atmospheric carbon dioxide concentration

constraints on the magnitude and patterns of ocean cooling at the last glacial maximum observation based reconstructions of sea surface temperature from relatively stable periods in the past such as the last glacial maximum represent an important means of constraining climate sensitivity and evaluating model simulations1 the first quantitative global reconstruction of sea surface temperatures during the last glacial maximum was developed by the climate long range investigation mapping and prediction climap project in the 1970s and 1980s refs 2 3 since that time several shortcomings of that earlier effort have become apparent4 here we present an updated synthesis of sea surface temperatures during the last glacial maximum rigorously defined as the period between 23 and 19 thousand years before present from the multiproxy approach for the reconstruction of the glacial ocean surface margo project5 we integrate microfossil and geochemical reconstructions of surface temperatures and include assessments of the reliability of individual records our reconstruction reveals the presence of large longitudinal gradients in sea surface temperature in all of the ocean basins in contrast to the simulations of the last glacial maximum climate available at present6 7

enhanced marine productivity off western north america during warm climate intervals of the past 52 k y studies of the santa barbara basin off the coast of california have linked changes in its bottom water oxygen content to millennial scale climate changes as recorded by the oxygen isotope composition of greenland ice through the use of detailed records from a sediment core collected off the magdalena margin of baja california mexico we demonstrate that this teleconnection predominantly arose from changes in marine productivity rather than changes in ventilation of the north pacific as was originally proposed

millennial scale oscillation of denitrification intensity in the arabian sea during the late quaternary and its potential influence on atmospheric n2o and global climate the intensity of denitrification in the arabian sea during the last 65 kyr is reconstructed using high resolution 15 n records of three sediment cores in conjunction with other geochemical tracers for water column oxygenation and productivity the results reveal a close link to the greenland ice core record with low or absent water column denitrification during the last glacial maximum the stadials and at the time of the heinrich events including the younger dryas in contrast denitrification was high during the holocene and the interstadials the intensification of denitrification is related to stronger sw monsoonal upwelling which enhances organic matter flux and degradation resulting in a strengthening of the midwater oxygen deficiency such a combination of enhanced upwelling and denitrification has also been implied for the eastern tropical north pacific etnp where these events occur during the holocene and to some extent during the interstadials too today the arabian sea and the etnp together contribute substantially to the global marine water column denitrification and a significant fraction of the ocean atmosphere n 2 o flux originates from these areas changes in n 2 o emissions from these areas could thus have effected the recently described stadial interstadial variations in the atmospheric concentration of this greenhouse gas as deduced from ice cores moreover denitrification is the major sink for oceanic nitrate and provides a primary control for the oceanic nutrient inventory which in turn influences global primary productivity and co 2 sequestration by the biological pump short term switches between a nondenitrification mode and a denitrification mode in these marine regions therefore have an impact on global climate

complementary constraints from carbon 13c and nitrogen 15n isotopes on the glacial ocean s soft tissue biological pump a three dimensional process based model of the ocean s carbon and nitrogen cycles including 13c and 15n isotopes is used to explore effects of idealized changes in the soft tissue biological pump results are presented from one preindustrial control run pictrl and six simulations of the last glacial maximum lgm with increasing values of the spatially constant maximum phytoplankton growth rate max which accelerates biological nutrient utilization mimicking iron fertilization the default lgm simulation without increasing max and with a shallower and weaker atlantic meridional overturning circulation and increased sea ice cover leads to 280 pg more respired organic carbon corg storage in the deep ocean with respect to pictrl dissolved oxygen concentrations in the colder glacial thermocline increase which reduces water column denitrification and with delay nitrogen fixation thus increasing the ocean s fixed nitrogen inventory and decreasing 15nno3 almost everywhere this simulation already fits sediment reconstructions of carbon and nitrogen isotopes relatively well but it overestimates deep ocean 13cdic and underestimates 15nno3 at high latitudes increasing max enhances corg and lowers deep ocean 13cdic improving the agreement with sediment data in the model s antarctic and north pacific oceans modest increases in max result in higher 15nno3 due to enhanced local nutrient utilization improving the agreement with reconstructions there models with moderately increased max fit both isotope data best whereas large increases in nutrient utilization are inconsistent with nitrogen isotopes although they still fit the carbon isotopes reasonably well the best fitting models reproduce major features of the glacial 13cdic 15n and oxygen reconstructions while simulating increased corg by 510 670 pg compared with the preindustrial ocean these results are consistent with the idea that the soft tissue pump was more efficient during the lgm both circulation and biological nutrient utilization could contribute however these conclusions are preliminary given our idealized experiments which do not consider changes in benthic denitrification and spatially inhomogenous changes in aeolian iron fluxes the analysis illustrates interactions between the carbon and nitrogen cycles as well as the complementary constraints provided by their isotopes whereas carbon isotopes are sensitive to circulation changes and indicate well the three dimensional corg distribution nitrogen isotopes are more sensitive to biological nutrient utilization

increased glacial age ventilation of the chilean margin by antarctic intermediate water antarctic intermediate water is an oxygen rich water mass that spreads throughout the southern hemisphere oceans marine sediment chemistry indicates that the water mass was produced at higher rates and had higher oxygen concentrations during the last glacial maximum antarctic intermediate water is at present a water mass that brings oxygen to intermediate depths throughout the southern hemisphere oceans models have suggested that intermediate waters had higher concentrations of oxygen during the last glacial period1 2 consistent with globally reduced denitrification3 and increased production of antarctic intermediate water4 however some palaeoceanographic reconstructions5 6 have indicated that production decreased in the southeast pacific ocean at this time here we analyse the concentrations of re and mn the sedimentary concentrations of which are controlled by the amount of dissolved oxygen at the sea floor from three sediment cores located along the chilean margin for the past 30 000 years our results from the cores which bracket the present day water column extent of antarctic intermediate water show that the depth range of well oxygenated antarctic intermediate water increased off chile during the last glacial maximum dissolved oxygen content began to decrease approximately 17 000 years ago coincident with rapid antarctic warming and a poleward shift of the southern westerly winds7 our estimates of productivity from accumulation rates of organic carbon and opal do not co vary with the seafloor oxygen variations ruling out local control of seafloor oxygenation we conclude that the data are best explained by a combination of increased oxygenation and increased flux of antarctic intermediate water during the last glacial maximum

north atlantic ventilation of southern sourced deep water in the glacial ocean one potential mechanism for lowering atmospheric co2 during glacial times is an increase in the fraction of the global ocean ventilated by the north atlantic which produces deep water with a low concentration of unused nutrients and thus drives the ocean s biological pump to a high efficiency however the data indicate that during glacial times a water mass low in 13c 12c and 14c c occupied the deep atlantic apparently at the expense of north atlantic deep water nadw this water is commonly referred to as southern sourced because of its apparent entry into the atlantic basin from the south prompting the inference that it was ventilated at the southern ocean surface here we propose that this deep atlantic water mass actually included a large fraction of north atlantic ventilated water the chemical characteristics of which were altered by recirculation in the deep southern and indo pacific oceans in an ocean model sensitivity experiment that reduces antarctic bottom water formation and weakens its overturning circulation we find that a much greater fraction of nadw is transported into the southern ocean without contacting the surface and is entrained and mixed into the southern sourced deep water that spreads into the global abyssal ocean thus north atlantic ventilation takes over more of the ocean interior lowering atmospheric co2 and yet the abyssal atlantic is filled from the south with old water low in 13c 12c and 14c c consistent with glacial data

enhanced stratification and seasonality in the subarctic pacific upon northern hemisphere glaciation new evidence from diatom bound nitrogen isotopes alkenones and archaeal tetraethers abstract coincident with the intensification of northern hemisphere glaciation nhg around 2 73 million years ma ago sediment cores from both the open subarctic north pacific and the antarctic indicate a rapid decline in diatom opal accumulation flux to the seabed representing one of the most abrupt and dramatic changes in the marine sediment record associated with the development of pleistocene glacial cycles in the north pacific bulk sediment nitrogen isotope data and alkenone derived sea surface temperature sst estimates suggest that the productivity decline was driven by reduced exchange between surface and deep water due to weaker wind driven upwelling and or a strengthening of the halocline i e stratification in this study of the 2 73 ma transition at ocean drilling program odp site 882 in the western subarctic north pacific diatom bound nitrogen isotopes 15 n db alkenone mass accumulation rate and alkenone and archaeal tetraether based sst reconstructions support the stratification hypothesis indicating perennially lower export production generally higher nitrate consumption and greater inter seasonal variation in sst after the 2 73 ma transition in addition the 15 n db of large and small size fractions of coscinodiscus spp suggest that these diatoms grew mostly during the spring bloom during the late pliocene switching to their current fall to winter growth period at the 2 73 ma transition this view is consistent with their decline in dominance and provides further evidence for increased stratification reduced vertical exchange in the north pacific after 2 73 ma the 15 n db data indicate that over the 100 kyr period after the 2 73 ma transition studied here nitrate consumption did not reach late pleistocene ice age levels and that nitrate consumption in post 2 73 ma warm stages was similar to that before the transition even though productivity was greatly reduced we tentatively attribute this to relatively weak dust borne iron inputs in the early post 2 73 ma period

eight glacial cycles from an antarctic ice core the antarctic vostok ice core provided compelling evidence of the nature of climate and of climate feedbacks over the past 420 000 years marine records suggest that the amplitude of climate variability was smaller before that time but such records are often poorly resolved moreover it is not possible to infer the abundance of greenhouse gases in the atmosphere from marine records here we report the recovery of a deep ice core from dome c antarctica that provides a climate record for the past 740 000 years for the four most recent glacial cycles the data agree well with the record from vostok the earlier period between 740 000 and 430 000 years ago was characterized by less pronounced warmth in interglacial periods in antarctica but a higher proportion of each cycle was spent in the warm mode the transition from glacial to interglacial conditions about 430 000 years ago termination v resembles the transition into the present interglacial period in terms of the magnitude of change in temperatures and greenhouse gases but there are significant differences in the patterns of change the interglacial stage following termination v was exceptionally long 28 000 years compared to for example the 12 000 years recorded so far in the present interglacial period given the similarities between this earlier warm period and today our results may imply that without human intervention a climate similar to the present one would extend well into the future

glacial interglacial modulation of the marine nitrogen cycle by high latitude o2 supply to the global thermocline 1 an analysis of sedimentary nitrogen isotope records compiled from widely distributed marine environments emphasizes the global synchrony of denitrification changes and provides evidence for a strong temporal coupling of these variations to changes in nitrogen fixation as previously inferred we explain the global coherence of these records by a simple physical control on the flux of dissolved oxygen to suboxic zones and the coupling to fixation via the supply of phosphorus to diazotrophs in suitable environments according to our hypothesis lower glacial stage sea surface temperature increased oxygen solubility while stronger winds in high latitude regions enhanced the rate of thermocline ventilation the resultant colder rapidly flushed thermocline lessened the spatial extent of denitrification and consequently n fixation during warm periods sluggish circulation of warmer less oxygen rich thermocline waters caused expansion of denitrification zones and a concomitant increase in n fixation local fluctuations in export productivity would have modulated this global signal

intensification of the northeast pacific oxygen minimum zone during the bolling allerod warm period although climate records from several locations around the world show nearly synchronous and abrupt changes the nature of the inferred teleconnection is still poorly understood on the basis of preserved laminations and molybdenum enrichments in open margin sediments we demonstrate that the oxygen content of northeast pacific waters at 800 m depth during the bolling allerod warm period 15 13 kyr was greatly reduced existing oxygen isotopic records of benthic and planktonic foraminifera suggest that this was probably due to suppressed ventilation at higher latitudes of the north pacific comparison with ventilation records for the north atlantic indicates an antiphased pattern of convection relative to the north pacific over the past 22 kyr perhaps due to variations in water vapor transport across central america

nitrogen isotopic evidence for deglacial changes in nutrient supply in the eastern equatorial pacific 1 the eastern equatorial pacific eep is a high nutrient low chlorophyll region of the ocean downcore nitrogen isotope records from the eep have been previously interpreted as a direct reflection of changes in nutrient consumption however the observed changes in sedimentary 15n since the last glacial maximum have no coherent relationship with export productivity or an inferred variation in the iron to nitrate ratio of the surface waters rather downcore n isotope records in the eep strongly resemble changes in the extent of water column denitrification as recorded in nearby sedimentary 15n records along the western margin of the americas this similarity is attributed to the overprinting of the n isotopic composition of nitrate in the eep through the advection of nitrate westward from the margins in the subsurface a local nitrogen isotope record of changes in the degree of nutrient consumption is extracted from the bulk sedimentary record by subtracting two different sedimentary 15n records of denitrification changes from two new eep 15n records tr163 22 and odp site 1240 the denitrification records used are from 1 the central american margin odp site 1242 and 2 the south american margin geob7139 2 the degree of consumption in the surface waters declines rapidly from elevated values during the last glacial maximum to a pair of minima around 15 and 11 13 ka and finally it increases into the holocene the derived eep nitrogen isotope record indicates that the regional peak in export productivity occurred when the supply of nutrients exceeded the apparently high demand the influx of nutrients during the deglaciation is attributed to the resumption of intense overturning in the southern ocean and the release of sequestered co2 and nutrient rich o2 poor waters from the deep ocean this has important implications for understanding the glacial interglacial scale variation in intermediate water suboxia and water column denitrification

deep circulation change linked to heinrich event 1 and younger dryas in a middepth north atlantic core a core from the mid atlantic ridge at 43 5 n and 3 km water depth shows distinct evidence of the deglacial events known as heinrich event 1 probably the marine equivalent of oldest dryas cooling in europe and the younger dryas the heinrich event dated at three levels to between 14 3 and 15 0 ka is marked by a minimum in foraminifera per gram by maxima in rates of sedimentation ice rafted debris per gram and relative abundance of n pachyderma s and by a 18o minimum in planktonic foraminifera the younger dryas event is marked by peak abundance of n pachyderma s and a planktonic 18o maximum benthic foraminiferal 13c reaches minimum values during both the heinrich event and the younger dryas our data indicate pronounced changes in surface water properties were coupled with reduced production of north atlantic deep water at each of these times

intense reducing conditions during the last deglaciation and heinrich events h1 h2 h3 in sediments from the oxygen minimum zone off goa eastern arabian sea abstract two sediment cores abp 32 gc 01r and abp 32 gc 03 were collected at a water depth of 642 m and 1086 m off goa from the present day oxygen minimum zone omz of eastern arabian sea eas cover time span of last 18 ka and 32 ka respectively were analysed for multi proxy redox sensitive elements to understand the variation in the redox conditions and factors responsible for its development redox sensitive elements concentration and their normalized ratios mn al u th mo al and ce ce suggest that sediment core abp 32 gc 01r is under more reducing conditions due to its location within the centre of omz compared to core abp 32 gc 03 which is at the base of omz sediments from the eas are of non euxinic environments where dissolved sulfide is present but restricted to the sediment pore waters lack of significant correlation r n yb n ratio is 1 during the last 10 ka holocene 14 10 ka includes younger dryas and b lling aller d 18 14 ka last deglaciation and heinrich events suggesting less reducing terrigenous dominated and intense reducing condition respectively

expansion of pelagic denitrification during early pleistocene cooling bioavailable nitrogen is removed from the oceans in oxygen deficient benthic and pelagic environments by denitrification future warming is predicted to reduce ocean oxygenation and to cause hypoxic regions to expand potentially accelerating denitrification a compilation of high resolution sedimentary nitrogen isotope delta n 15 records from the eastern tropical pacific north pacific and the arabian sea and a global multi site survey are presented as evidence for weak pelagic denitrification at the end of the pliocene warm period mean delta n 15 values increased in the major oxygen minimum zones omzs between 2 1 and 1 5 ma pelagic denitrification strengthened during a period of long term global cooling despite solubility driven increases in initial oxygen contents of antarctic intermediate and subantarctic mode waters ventilating the omzs this trend is opposite to the predicted mean trend for a cooling ocean as well as to the observed glacial interglacial variation several alternatives to explain the shift are proposed including a rise in net respiration a progressive increase in the ventilation age of the deep ocean associated with million year scale secular cooling and a shoaling of the remotely ventilated thermocline to shallow depths corresponding to the zone of peak subsurface respiration given no evidence for a net increase in production we assert that large scale climate driven changes in ocean circulation regulate long timescale variations in the extent of pelagic denitrification additional data and modeling are required to fully explain the observations c 2013 elsevier b v all rights reserved

a deeper respired carbon pool in the glacial equatorial pacific ocean article i nfo atmospheric pco2 was approximately 80 ppm lower during the last glacial period than during pre industrial times identifying the fate of that carbon has been one of the great challenges in paleoceanography we present evidence from ten equatorial pacific ocean sediment cores to show that the deep pacific ocean likely stored more carbon during the last glacial period than the holocene the concentration of the redox sensitive metal uranium u in sediments was systematically greater during the last glacial period than during the holocene indicating more reducing conditions in glacial age sediments reconstructions of biogenic opal flux indicate that changes in u distribution were not the result of changes in biological productivity and the ensuing rain of organic carbon to the sea floor which also affects the redox conditions of the sediments together these results lead to the interpretation that bottom water in the equatorial pacific during the glacial period had significantly lower oxygen concentration than during the holocene and a correspondingly greater level of respired co2 this conclusion is supported by evidence for greater preservation of brassicasterol a biomarker produced by diatoms in glacial age sediments of the eastern equatorial pacific the presence of additional respired co2 in the glacial deep ocean would have lowered atmospheric pco2 by 1 increasing the total storage of co2 in the glacial ocean and 2 increasing ocean alkalinity following a transient carbonate dissolution event our results are consistent with recently published data from the north pacific ocean this suggests that increased carbon storage in the glacial deep pacific ocean was a basin wide phenomenon consistent with a large scale transfer of carbon to the deep ocean during glacial periods

extreme deepening of the atlantic overturning circulation during deglaciation glacial terminations during the late pleistocene epoch are associated with changes in insolation they are also punctuated by millennial scale climate shifts characterized by a weakening and subsequent strengthening of the atlantic meridional overturning circulation this ubiquitous association suggests that these oscillations may be a necessary component of deglaciation model simulations have suggested that the period of weakened circulation during these terminal oscillations would be followed by an overshoot of the circulation on its resumption but this phenomenon has not yet been observed here we use radiocarbon measurements of benthic foraminifera and carbonate preservation indices to reconstruct ventilation changes in the deep south atlantic ocean over the past 40 000 years we find evidence for a particularly deep expansion of the atlantic overturning cell directly following the weak mode associated with heinrich stadial 1 our analysis of an ocean general circulation model simulation suggests that north atlantic deep water export during the expansion was greater than that of interglacial conditions we find a similar deep expansion during dansgaard oeschger interstadial event 8 38 000 years ago which followed heinrich stadial 4 we conclude that the rise in atmospheric co2 concentrations and resultant warming associated with an especially weak overturning circulation are sufficient to trigger a switch to a vigorous circulation but a full transition to interglacial conditions requires additional forcing at an orbital scale

germanium silicon fractionation in a river influenced continental margin the northern gulf of mexico abstract in this study we have sampled the water column and sediments of the gulf of mexico to investigate the effects of high riverine terrigenous load and sediment redox conditions on the cycling of ge and si water column ge si ratios across the gulf of mexico continental shelf range from 1 9 to 25 mol mol which is elevated compared to the global ocean value of 0 7 mol mol the ge enrichment in the gulf of mexico seawater is primarily due to anthropogenic contamination of the mississippi river which is the main ge and si source to the area and to a smaller extent due to discrimination against ge during biogenic silica bsi production ge si 1 2 1 8 mol mol especially by radiolarians and siliceous sponges ge si 0 6 1 1 mol mol most sediment pore waters ge si 0 3 4 5 mol mol and sediment incubation experiments benthic flux ge si 0 9 1 2 mol mol indicate precipitation of authigenic phases that sequester ge from pore waters non opal sink this process appears to be independent of oxidation reduction reactions and suggests that authigenic aluminosilicate formation reverse weathering may be the dominant ge sink in marine sediments compilation of previously published data shows that in continental margins non opal ge burial flux is controlled by bsi supply while in open ocean sediments it is 10 100 times lower and most likely limited by the supply of lithogenic material we provide a measurement based estimate of the global non opal ge burial flux as 4 32 mmol yr 1 encompassing the 2 16 mmol yr 1 needed to keep the global marine ge cycle at steady state

a review of nitrogen isotopic alteration in marine sediments key points use of sedimentary nitrogen isotopes is examined on average sediment 15n 14n increases approx 2 per mil during early burial isotopic alteration scales with water depth abstract nitrogen isotopes are an important tool for evaluating past biogeochemical cycling from the paleoceanographic record however bulk sedimentary nitrogen isotope ratios which can be determined routinely and at minimal cost may be altered during burial and early sedimentary diagenesis particularly outside of continental margin settings the causes and detailed mechanisms of isotopic alteration are still under investigation case studies of the mediterranean and south china seas underscore the complexities of investigating isotopic alteration in an effort to evaluate the evidence for alteration of the sedimentary n isotopic signal and try to quantify the net effect we have compiled and compared data demonstrating alteration from the published literature a 100 point comparison of sediment trap and surface sedimentary nitrogen isotope values demonstrates that at sites located off of the continental margins an increase in sediment 15n 14n occurs during early burial likely at the seafloor the extent of isotopic alteration appears to be a function of water depth depth related differences in oxygen exposure time at the seafloor are likely the dominant control on the extent of n isotopic alteration moreover the compiled data suggest that the degree of alteration is likely to be uniform through time at most sites so that bulk sedimentary isotope records likely provide a good means for evaluating relative changes in the global n cycle

productivity climate coupling recorded in pleistocene sediments off prydz bay east antarctica abstract export production in the southern ocean is thought to be tightly correlated with atmospheric co2 fluctuations over geological times relevant studies are however mainly confined to the atlantic and pacific sectors of the southern ocean and often only cover the last glacial interglacial cycle here we present a sediment record retrieved off prydz bay east antarctica spanning the last 520 kyrs we show that the distribution pattern of local export production is closely coupled with global climate change on orbital time scales we propose that the dominant factors controlling local export production include the amount of nutrients supply from the ocean interior and the extent of sea ice cover thus representing the combined history of deep water exposure ventilation and the sea ice coverage in the studied area sharp increases in the local export production coincide with abrupt increase in atmospheric co2 concentrations during deglacial periods indicating drastic outgassing of the upwelled deep water in the southern ocean gradually decrease in the export production following interglacial peaks concurs with decrease in deep water exposure ventilation and increase in sea ice cover explaining the early decline in atmospheric co2 over a glacial interglacial cycle

latitudinal variations in intermediate depth ventilation and biological production over northeastern pacific oxygen minimum zones during the last 60 ka abstract mechanisms affecting past variability in the oxygen minimum zone omz in the eastern tropical north pacific etnp are poorly known we analyzed core md02 2524 obtained from the nicaragua margin in the present etnp omz for major and minor elements titanium ti brome br silicon si potassium k and calcium ca using an x ray fluorescence xrf core scanner and redox sensitive trace elements uranium u molybdenum mo and nickel ni determined by icp ms the u and mo content was higher during the deglaciation than during the holocene and the last glacial maximum whereas enrichment was not observed for ni an element closely associated with organic matter high resolution xrf scanning indicated that the ca based carbonate content had millennial scale variability inversely correlated with br based organic matter and si k based opal content during the last glacial period the available data suggest no clear regional trend in biological productivity during the last deglaciation but significant local variability in the coastal eastern equatorial pacific the trace element enrichment and the lack of a concomitant increase in biogenic phases indicated that an enhanced etnp omz at least between 15 n and 12 n at a water depth of 500 900 m was principally caused by a reduced oxygen supply driven by oceanic circulation to the nicaragua basin during the deglaciation the observed patterns can be interpreted as the distinct changes in the oxygenation state of northern and southern water masses at intermediate depths we also found evidence for a decoupling between local productivity and pore water oxygenation for several millennial scale events during marine isotopic stage 3 indicating that remote oxygen consumption and or oceanic ventilation impacted omz intensity multi millennial scale variations of the productivity at papagayo upwelling cell displayed an opposite trend from productivity at the costa rica dome in relation with the latitudinal shift of the inter tropical convergence zone itcz latitudinal variations of the omz intensity reflected the relative influence of the northern and southern intermediate water masses whose oxygenation was driven by high latitude climates and productivity over the intermediate water pathway

i ca in epifaunal benthic foraminifera a semi quantitative proxy for bottom water oxygen in a multi proxy compilation for glacial ocean deoxygenation abstract the decline in dissolved oxygen in global oceans ocean deoxygenation is a potential consequence of global warming which may have important impacts on ocean biogeochemistry and marine ecosystems current climate models do not agree on the trajectory of future deoxygenation on different timescales in part due to uncertainties in the complex linked effects of changes in ocean circulation productivity and organic matter respiration more semi quantitative reconstructions of oceanic oxygen levels over the pleistocene glacial cycles may provide a critical test of our mechanistic understanding of the response of oceanic oxygenation to climate change even the most promising proxies for bottom water oxygen bwo have limitations which calls for new proxy development and a multi proxy compilation to evaluate glacial ocean oxygenation we use holocene benthic foraminifera to explore i ca in cibicidoides spp as a bwo proxy we propose that low i ca e g 15 may provide semi quantitative estimates of low bwo in past oceans e g

neodymium isotopic evidence for linked changes in southeast atlantic and southwest pacific circulation over the last 200 kyr knowledge of the geometry and strength of the deep overturning circulation is central to the understanding of past climate variability on glacial interglacial g i timescales in this study neodymium nd isotopic ratios on planktonic foraminifera are used to reconstruct the water mass source and mixing history of intermediate and deep water in the southeast se atlantic and southwest sw pacific over the past 200 kyr from five sediment cores nd isotopes from a depth transect of cores in the se atlantic displayed a stronger geochemical gradient around 3 5 km at the lgm with higher end values of 6 0 below that boundary than those of 7 8 above in contrast a similar end value 9 5 is observed at both the intermediate and abyssal depths in the holocene the glacial upper ocean is 1 8 end units less radiogenic than the lower ocean reflecting an increase in the amount of north atlantic component water nacw in the upper se atlantic a coherent nd isotope change was observed in the se atlantic and sw pacific intermediate and deep water with major excursion to more radiogenic end values during marine isotope stage mis 2 4 and 6 this suggests the flux of nacw to the southern ocean was reduced during cold marine stages possibly accompanied by changes in the water mass geometry the constant 2 end unit offset between intermediate water in the se atlantic and sw pacific suggests the persistent propagation of less radiogenic nacw to the upper pacific ocean over the last glacial cycle moreover the larger glacial vertical end gradients between the intermediate and deep waters in both the se atlantic and sw pacific indicate a decreased proportion of nacw entrainment into the deep oceans consistent with studies proposing reduced mixing between the upper and lower meridional overturning cells

ventilation of the deep southern ocean and deglacial co2 rise past glacial interglacial increases in the concentration of atmospheric carbon dioxide co2 are thought to arise from the rapid release of co2 sequestered in the deep sea primarily via the southern ocean here we present radiocarbon evidence from the atlantic sector of the southern ocean that strongly supports this hypothesis we show that during the last glacial period deep water circulating around antarctica was more than two times older than today relative to the atmosphere during deglaciation the dissipation of this old and presumably co2 enriched deep water played an important role in the pulsed rise of atmospheric co2 through its variable influence on the upwelling branch of the antarctic overturning circulation

high resolution record of northern hemisphere climate extending into the last interglacial period high resolution record of northern hemisphere climate extending into the last interglacial period

ocean mixing and ice sheet control of seawater 234u 238u during the last deglaciation seawater 234u 238u provides global scale information about continental weathering and is vital for marine uranium series geochronology existing evidence supports an increase in 234u 238u since the last glacial period but the timing and amplitude of its variability has been poorly constrained here we report two seawater 234u 238u records based on well preserved deep sea corals from the low latitude atlantic and pacific oceans the atlantic 234u 238u started to increase before major sea level rise and overshot the modern value by 3 per mil during the early deglaciation deglacial 234u 238u in the pacific converged with that in the atlantic after the abrupt resumption of atlantic meridional overturning we suggest that ocean mixing and early deglacial release of excess 234u from enhanced subglacial melting of the northern hemisphere ice sheets have driven the observed 234u 238u evolution

variations in tropical convection as an amplifier of global climate change at the millennial scale the global expression of millennial scale climatic change during the glacial period and the persistence of this signal in holocene records point to atmospheric teleconnections as the mechanism propagating rapid climate variations we suggest rearrangements in the tropical convection system globally affected the concentration and location of atmospheric water vapour and modulated terrestrial and marine emissions of ch4 and n2o providing a tropical mechanism of amplifying and perpetuating millennial scale climate changes a multi proxy reconstruction reflecting various aspects of the intensity of the arabian sea summer monsoon shows strong millennial scale variability over the past 90 kyr in which low intensity is associated with a southern shift of the intertropical convergence zone itcz and an eastward shift in the equatorial convergence zone the monsoon reconstruction which is based on new data from a somali margin sediment core is supported by previously reported tropical paleoclimatic records and suggests that global scale millennial climatic variability is in part driven by modulations in the tropical hydrological cycle and tropical emissions of the greenhouse gases ch4 and n2o

late quaternary deep stratification climate coupling in the southern ocean implications for changes in abyssal carbon storage the southern ocean plays an important role in modulating pleistocene atmospheric co2 concentrations but the underlying mechanisms are not yet fully understood here we report the laser grain size distribution and mn geochemical data of a 523 kyr long sediment record core ant30 p1 02 off prydz bay east antarctica to trace past physical changes in the deep southern ocean the core sediments are predominantly composed of clay and silt sized material three grain size end members em as well as three sensitive grain size classes sc were discerned interpreted as ice rafted debris em1 and sc1 and coarse em2 and sc2 and fine em3 sc3 materials deposited from bottom nepheloid layers respectively ratios of em2 em2 em3 and sc2 sc3 reveal changes in the local bottom current strength which is related to the deep ocean diapycnal mixing rate showing higher values during interglacial periods and lower values during glacial periods mno was enriched at each glacial termination probably caused by abrupt elevations in antarctic bottom water aabw formation rate lower aabw formation rate and reduced deep diapycnal mixing during glacial periods enhanced deep southern ocean stratification contributing to glacial atmospheric co2 drawdown the elevated aabw formation and enhanced deep diapycnal mixing during glacial terminations alleviated such deep stratification promoting deeply sequestered co2 to outgas

geochemical response of the mid depth northeast atlantic ocean to freshwater input during heinrich events 1 to 4 heinrich events are intervals of rapid iceberg sourced freshwater release to the high latitude north atlantic ocean that punctuate late pleistocene glacials delivery of fresh water to the main north atlantic sites of deep water formation during heinrich events may result in major disruption to the atlantic meridional overturning circulation amoc however the simple concept of an amoc shutdown in response to each freshwater input has recently been shown to be overly simplistic here we present a new multi proxy dataset spanning the last 41 000 years that resolves four heinrich events at a classic mid depth north atlantic drill site employing four independent geochemical tracers of water mass properties boron calcium carbon and oxygen isotopes in foraminiferal calcite and neodymium isotopes in multiple substrates we also report rare earth element distributions to investigate the fidelity by which neodymium isotopes record changes in water mass distribution in the northeast north atlantic our data reveal distinct geochemical signatures for each heinrich event suggesting that the sites of fresh water delivery and or rates of input played at least as important a role as the stage of the glacial cycle in which the fresh water was released at no time during the last 41 kyr was the mid depth northeast north atlantic dominantly ventilated by southern sourced water instead we document persistent ventilation by glacial north atlantic intermediate water gnaiw albeit with variable properties signifying changes in supply from multiple contributing northern sources

sensitivity to the representation of microphysical processes in numerical simulations during tropical storm formation abstractan analysis of in situ observations from the nondeveloping tropical disturbance named tcs025 revealed that a combination of unfavorable system scale and environmental factors limited further development in this study a multiphysics ensemble of high resolution simulations of tcs025 are analyzed and compared a simulation that overdeveloped the tcs025 disturbance is compared with one that correctly simulated nondevelopment and reveals that convection was stronger and diabatic heating rates were larger in the developing simulation this led to continued spinup of the low level circulation primarily through vorticity stretching in contrast convection was much weaker in the nondeveloping simulation and after an initial period of deep convection average vorticity tendencies from stretching became weakly negative which allowed for the frictional spindown of the low level circulation convective scale differences identified early in the simulations appear to have resulted from the explicit represent

mid depth oxygen drawdown during heinrich events evidence from benthic foraminiferal community structure trace fossil tiering and benthic δ13c at the portuguese margin abstract the distribution of trace fossils and benthic foraminiferal assemblages in two sediment cores from 2160 m water depth at the northern and 1100 m at the southern portuguese continental margin was used to reconstruct the bottom water oxygenation during the last 40 ka emphasis was given to the heinrich events during which enhanced meltwater flux associated with the iceberg surges reduced or even halted deep water formation in the north atlantic condensed trace fossil tiering structures and high proportions of low oxygen tolerant benthic foraminifera suggest a major drawdown of bottom water oxygenation during heinrich events using the benthic foraminiferal oxygenation index bfoi of kaiho 1991 1994 that links benthic foraminiferal communities to ambient bottom water oxygenation we extracted apparent oxygen concentrations from benthic assemblages bfoi values suggest low oxic conditions during heinrich events 1 and 4 with mean oxygen levels of 2 6 to 2 8 ml l 1 and high oxic conditions with 4 1 ml l 1 during heinrich event 2 at the shallower site high proportions of low oxygen tolerant foraminiferal species and bfoi minima are recorded a few centimetres below the maximum concentrations of ice rafted debris indicating that the original microhabitat depth of dysoxic species is preserved beneath the heinrich layers even though bioturbation continued during the events trace fossil tiering calibrated with the redox boundary in low oxic environments and dysoxic ichnotaxa commonly associated with black shales indicate oxygen levels lower than those implied by the bfoi oxygenation estimates derived from trace fossil tiering denote low oxic conditions during h1 13 3 ka with oxygen concentrations slightly above 1 ml l 1 and dysoxic conditions during h2 20 6 ka h3 27 ka and h4 33 5 ka with oxygen concentrations between 0 1 and 1 ml l 1 during the younger dryas bottom waters likely were low oxic negative excursions of benthic carbon isotope values provide independent control on the oxygen drawdown during heinrich events considering a bottom water oxygenation of 6 1 to 6 5 ml l 1 during the last glacial the benthic 13 c minima reveal an oxygen depletion to values between 3 4 and 5 0 ml l 1 during h1 through h4 at the shallower core site differences between estimates from benthic 13 c bfoi and trace fossil tiering suggest that benthic foraminiferal communities are rather robust to oxygen depletion if the level does not fall below 3 ml l 1 whereas burrowing organisms react sensitively to depth variations of the redox boundary in near surface sediments due to even small changes of bottom water oxygenation

glacial holocene δ15n record from the gulf of tehuantepec mexico implications for denitrification in the eastern equatorial pacific and changes in atmospheric n2o 1 the intensity of denitrification in the gulf of tehuantepec along the mexican margin of the eastern tropical north pacific etnp was reconstructed for the last 23 000 years using the nitrogen isotopic composition of sediment organic matter 15norg in conjunction with other geochemical tracers of water column productivity during the last glacial period 15norg values ranged from 6 5 to 8 6 with values increasing between 23 and 17 ka deglaciation was marked by an abrupt increase in 15norg with maximum values 9 9 occurring during the bolling allerod period and the earliest holocene a decline in 15norg values occurred over the last 10 000 years with late holocene values being similar to those of the glacial period our data suggest that denitrification in this region was minimal during the last glacial and is consistent with the deposition of bioturbated sediments at the study site the intensity of denitrification increased dramatically during deglaciation and the early holocene signaling the presence of a strong oxygen minimum zone this period is also marked by the deposition of laminated sediments in the region the 15norg records display similar temporal trends to those seen in the greenland ice core record of atmospheric n2o concentrations at present denitrification within the eastern tropical pacific and arabian sea accounts for a major portion of the global marine loss of fixed nitrogen and a significant fraction of the ocean atmosphere n2o flux originates from these areas large changes in n2o emissions from these regions in the past would have directly impacted global greenhouse gas concentrations

large fluctuations of dissolved oxygen in the indian and pacific oceans during dansgaard oeschger oscillations caused by variations of north atlantic deep water subduction a s and s h were supported by the paleoclimate program of the national science foundation as part of the paleovar project atm 0602395

deep south atlantic carbonate chemistry and increased interocean deep water exchange during last deglaciation abstract carbon release from the deep ocean at glacial terminations is a critical component of past climate change but the underlying mechanisms remain poorly understood we present a 28 000 year high resolution record of carbonate ion concentration a key parameter of the global carbon cycle at 5 km water depth in the south atlantic we observe similar carbonate ion concentrations between the last glacial maximum and the late holocene despite elevated concentrations in the glacial surface ocean this strongly supports the importance of respiratory carbon accumulation in a stratified deep ocean for atmospheric co 2 reduction during the last ice age after 9 mol kg decline during heinrich stadial 1 deep south atlantic carbonate ion concentration rose by 24 mol kg from the onset of bolling to pre boreal likely caused by strengthening north atlantic deep water formation bolling or increased ventilation in the southern ocean younger drays or both pre boreal the 15 mol kg decline in deep water carbonate ion since 10 ka is consistent with extraction of alkalinity from seawater by deep sea caco 3 compensation and coral reef growth on continental shelves during the holocene between 16 600 and 15 000 years ago deep south atlantic carbonate ion values converged with those at 3 4 km water depth in the western equatorial pacific as did carbon isotope and radiocarbon values these observations suggest a period of enhanced lateral exchange of carbon between the deep south atlantic and pacific oceans probably due to an increased transfer of momentum from southern westerlies to the southern ocean by spreading carbon rich deep pacific waters around antarctica for upwelling invigorated interocean deep water exchange would lead to more efficient co 2 degassing from the southern ocean and thus to an atmospheric co 2 rise during the early deglaciation

deglacial variability in okhotsk sea intermediate water ventilation and biogeochemistry implications for north pacific nutrient supply and productivity highlights multi proxy multi site reconstruction of okhotsk sea palaeo productivity and mid depth ventilation changes from 8 to 18 ka link between hinterland river discharge and downstream okhotsk sea intermediate water osiw ventilation nutrient signatures surplus fe si oh 4 export in osiw during bolling allerod to pelagic pacific supported transient nutrient replete conditions subarctic and subtropical pacific gyres disconnected during bolling allerod with restricted osiw flow to lower latitudes deglacial osiw export and mid depth pacific biogeochemistry modulate millennial scale regional co2 source sink conditions the modern north pacific plays a critical role in marine biogeochemical cycles as an oceanic sink of co2 and by bearing some of the most productive and least oxygenated waters of the world ocean the capacity to sequester co2 is limited by efficient nutrient supply to the mixed layer particularly from deeper water masses in the pacific s subarctic and marginal seas the region is in addition only weakly ventilated by north pacific intermediate water npiw which receives its characteristics from okhotsk sea intermediate water osiw here we present reconstructions of intermediate water ventilation and productivity variations in the okhotsk sea that cover the last glacial termination between eight and 18 ka based on a set of high resolution sediment cores from sites directly downstream of osiw formation in a multi proxy approach we use total organic carbon toc chlorin biogenic opal and caco3 concentrations as indicators for biological productivity c n ratios and xrf scanning derived elemental ratios si k and fe k as well as chlorophycean algae counts document changes in amur freshwater and sediment discharge that condition the osiw stable carbon isotopes of epi and shallow endobenthic foraminifera in combination with 14c analyses of benthic and planktic foraminifera imply decreases in osiw oxygenation during deglacial warm phases from c 14 7 to 13 ka bolling allerod and c 11 4 to 9 ka preboreal no concomitant decreases in okhotsk sea benthic planktic ventilation ages are observed in contrast to nearby but southerly locations on the japan continental margin we attribute okhotsk sea mid depth oxygenation decreases in times of enhanced organic matter supply to maxima in remineralization within osiw in line with multi proxy evidence for maxima in primary productivity and supply of organic matter sedimentary c n and fe k ratios indicate more effective entrainment of nutrients into osiw and thus an increased nutrient load of osiw during deglacial warm periods correlation of palynological and sedimentological evidence from our sites with hinterland reference records suggests that millennial scale changes in osiw oxygen and nutrient concentrations were largely influenced by fluvial freshwater runoff maxima from the amur caused by a deglacial northeastward propagation of the east asian summer monsoon that increased precipitation and temperatures in conjunction with melting of permafrost in the amur catchment area we suggest that osiw ventilation minima and the high lateral supply of nutrients and organic matter during the allerod and preboreal are mechanistically linked to concurrent maxima in nutrient utilization and biological productivity in the subpolar northwest pacific in this scenario increased export of nutrients from the okhotsk sea during deglacial warm phases supported subarctic pacific shifts from generally fe limiting conditions to transient nutrient replete regimes through enhanced advection of mid depth nutrient and fe rich osiw into the upper ocean this mechanism may have moderated the role of the subarctic pacific in the deglacial co2 rise on millennial timescales by combining the upwelling of old carbon rich waters with a transient delivery of mid depth derived bio available fe and silicate

sulfur isotope characteristics of metamorphosed zn cu volcanogenic massive sulfides in the areachap group northern cape province south africa zn and cu rich massive sulfide ores of volcanogenic origin volcanogenic massive sulfide vms deposits occur as stratiform stratabound lenses of variable size hosted by gneisses amphibolites and schists of the areachap group in the northern cape province of south africa the areachap group represents the highly deformed and metamorphosed remnants of a mesoproterozoic volcanic arc that was accreted onto the western margin of the kaapvaal craton during the 1 0 1 2 ga namaquan orogeny sulfur isotope data 34s are presented for 57 sulfide separates and one barite sample from five massive sulfide occurrences in the areachap group although sulfides from each site have distinct sulfur isotope values all 34s values fall within a very limited range 3 0 to 8 5 barite has a 34s value of 18 5 very different from that of associated sulfides at one of the studied sites kantienpan a distinct increase in 34s of sulfides is observed from the massive sulfide lens into the disseminated sulfides associated with a distinct footwall alteration zone sulfide sulfide and sulfide barite mineral pairs which recrystallized together during amphibolite and lower granulite facies metamorphism are not in isotopic equilibrium sulfur isotope characteristics of sulfides and sulfates of the zn cu ores in the areachap group are however very similar to base metal sulfide accumulations associated with modern volcanic arcs and unsedimented mid ocean ridges it is thus concluded that profound recrystallization and textural reconstitution associated with high grade regional metamorphism of the massive sulfide ores of the areachap group did not result in extensive sulfur isotopic homogenization this is similar to observations in other metamorphosed vms deposit districts and confirms that massive sulfide ores remain effectively a closed system for sulfur isotopes for both sulfides and sulfates during metamorphism

subarctic pacific evidence for a glacial deepening of the oceanic respired carbon pool abstract measurements of benthic foraminiferal cadmium calcium cd ca have indicated that the glacial interglacial change in deep north pacific phosphate po4 concentration was minimal which has been taken by some workers as a sign that the biological pump did not store more carbon in the deep glacial ocean here we present sedimentary redox sensitive trace metal records from ocean drilling program odp site 882 nw subarctic pacific water depth 3244 m to make inferences about changes in deep north pacific oxygenation and thus respired carbon storage over the past 150 000 yr these observations are complemented with biogenic barium and opal measurements as indicators for past organic carbon export to separate the influences of deep water oxygen concentration and sedimentary organic carbon respiration on the redox state of the sediment our results suggest that the deep subarctic pacific water mass was depleted in oxygen during glacial maxima though it was not anoxic we reconcile our results with the existing benthic foraminiferal cd ca by invoking a decrease in the fraction of the deep ocean nutrient inventory that was preformed rather than remineralized this change would have corresponded to an increase in the deep pacific storage of respired carbon which would have lowered atmospheric carbon dioxide co2 by sequestering co2 away from the atmosphere and by increasing ocean alkalinity through a transient dissolution event in the deep sea the magnitude of change in preformed nutrients suggested by the north pacific data would have accounted for a majority of the observed decrease in glacial atmospheric pco2

the impact of ocean deoxygenation on iron release from continental margin sediments in the oceans high nitrate low chlorophyll regions such as the peru humboldt current system and the adjacent eastern equatorial pacific1 primary productivity is limited by the micronutrient iron within the peruvian upwelling area bioavailable iron is released from the reducing continental margin sediments2 the magnitude of this seafloor source could change with fluctuations in the extension or intensity of the oxygen minimum zones3 4 here we show that measurements of molybdenum uranium and iron concentrations can be used as a proxy for sedimentary iron release and use this proxy to assess iron release from the sea floor beneath the peru upwelling system during the past 140 000 years we observe a coupling between levels of denitrification as indicated by nitrogen isotopes trace metal proxies for oxygenation and sedimentary iron concentrations specifically periods with poor upper ocean oxygenation are characterized by more efficient iron retention in the sediment and a diminished iron supply to the water column we attribute efficient iron retention under more reducing conditions to widespread sulphidic conditions in the surface sediment and concomitant precipitation of iron sulphides we argue that iron release from continental margin sediments is most effective in a narrow redox window where neither oxygen nor sulphide is present we therefore suggest that future deoxygenation in the peru upwelling area would be unlikely to result in increased iron availability whereas in weaker oxygen minimum zones partial deoxygenation may enhance the iron supply

atmospheric nitrous oxide during the last 140 000 years article i nfo reconstructions of past atmospheric concentrations of greenhouse gases provide unique insight into the biogeochemical cycles and the past radiative forcing in the earth s climate system we present new measurements of atmospheric nitrous oxide along the ice cores of the north greenland ice core project and talos dome sites using records of several other ice cores we are now able to establish the first complete composite nitrous oxide record reaching back to the beginning of the previous interglacial about 140 000 yr ago on the basis of such composite ice core records we further calculate the radiative forcing of the three most important greenhouse gases carbon dioxide methane and nitrous oxide during more than a full glacial interglacial cycle nitrous oxide varies in line with climate reaching very low concentrations of about 200 parts per billion by volume during marine isotope stages 4 and 2 and showing substantial responses to millennial time scale climate variations during the last glacial a large part of these millennial time scale variations can be explained by parallel changes in the sources of methane and nitrous oxide however as revealed by high resolution measurements covering the dansgaard oeschger events 17 to 15 the evolution of these two greenhouse gases may be decoupled on the centennial time scale carbon dioxide and methane concentrations do not reach interglacial levels in the course of millennial time scale climate variations during the last glacial in contrast nitrous oxide often reaches interglacial concentrations in response to both glacial terminations and dansgaard oeschger events this indicates from a biogeochemical point of view similar drivers in both temporal cases while carbon dioxide and methane concentrations are more strongly controlled by climate changes in high latitudes nitrous oxide emissions changes may mainly stem from the ocean and or from soils located at low latitudes accordingly we speculate that high latitudes could play the leading role to trigger glacial terminations

climatically related millennial scale fluctuations in strength of california margin oxygen minimum zone during the past 60 k y a strong oxygen minimum zone omz currently exists along the california margin because of a combination of high surface water productivity and poor intermediate water ventilation however the strength of this omz may have been sensitive to late quaternary ocean circulation and productivity changes along the margin although sediment lamination strength has been used to trace ocean oxygenation changes in the past oxygen levels on the open margin are not sufficiently low for laminations to form in these regions benthic foraminifera are highly sensitive monitors of omz strength and their fossil assemblages can be used to reconstruct past fluctuations benthic foraminiferal assemblages from ocean drilling program site 1017 off point conception exhibit major and rapid faunal oscillations in response to late quaternary millennial scale climate change dansgaard oeschger cycles on the open central california margin these faunal oscillations can be correlated to and are apparently synchronous with those reported from santa barbara basin together they represent major fluctuations in the strength of the omz which were intimately associated with global climate change weakening perhaps disappearing during cool periods and strengthening during warm periods these rapid major omz strength fluctuations were apparently widespread on the northeast pacific margin and must have influenced the evolution of margin biota and altered biogeochemicalmore cycles with potential feedbacks to global climate change less

glacial interglacial changes in nutrient supply and stratification in the western subarctic north pacific since the penultimate glacial maximum abstract in piston cores from the open subarctic pacific and the okhotsk sea diatom bound 15n 15ndb biogenic opal calcium carbonate and barium were measured from coretop to the previous glacial maximum mis 6 glacial intervals are generally characterized by high 15ndb 8 and low productivity whereas interglacial intervals have a lower 15ndb 5 7 6 3 and indicate high biogenic productivity these data extend the regional swath of evidence for nearly complete surface nutrient utilization during glacial maxima consistent with stronger upper water column stratification throughout the subarctic region during colder intervals an early deglacial decline in 15ndb of 2 at 17 5 ka previously observed in the bering sea is found here in the open subarctic pacific record and arguably also in the okhotsk and a case can be made that a similar decrease in 15ndb occurred in both regions at the previous deglaciation as well the early deglacial 15ndb decrease best explained by a decrease in surface nutrient utilization appears synchronous with southern hemisphere associated deglacial changes and with the heinrich 1 event in the north atlantic this 15ndb decrease may signal the initial deglacial weakening in subarctic north pacific stratification and or a deglacial increase in shallow subsurface nitrate concentration if the former it would be the north pacific analogue to the increase in vertical exchange inferred for the southern ocean at the time of heinrich event 1 in either case the lack of any clear change in paleoproductivity proxies during this interval would seem to require an early deglacial decrease in the iron to nitrate ratio of subsurface nutrient supply or the predominance of light limitation of phytoplankton growth during the deglaciation prior to bolling allerod warming

influence of northwest pacific productivity on north pacific intermediate water oxygen concentrations during the bolling allerod interval 14 7 12 9 ka elevated productivity in the northwest pacific is suggested as a new possible control driving past intervals of low o2 intermediate water along the western continental margin of north america according to this mechanism o2 consumption would occur near the site of formation of north pacific intermediate water npiw due to increased respiration of organic carbon in response to a high productivity event evidence is provided for such a productivity increase during the bolling allerod interval 14 7 12 9 ka a time when laminated sediments were deposited along the northern california margin by this mechanism low o2 events in intermediate waters off the western north american margin could occur without significant changes in the rate of npiw ventilation

large climate driven changes of oceanic oxygen concentrations during the last deglaciation during the last glacial termination the solubility of gases in the ocean decreased as ocean temperatures rose however marine sediments have not unanimously recorded ocean deoxygenation throughout this time some records show increasing oxygenation since the last glacial maximum particularly in the deep sea while many document abrupt oxygenation changes often associated with apparent changes in the formation rate of north atlantic deep water here we present a global compilation of marine sediment proxy records that reveals remarkable coherency between regional oxygenation changes throughout deglaciation the upper ocean generally became less oxygenated but this general trend included pauses and even reversals reflecting changes in nutrient supply respiration rates and ventilation the most pronounced deoxygenation episode in the upper ocean occurred midway through the deglaciation associated with a reinvigoration of north atlantic deep water formation at this time the upper indo pacific ocean was less oxygenated than today meanwhile the bulk of the deep ocean became more oxygenated over the deglaciation reflecting a transfer of respired carbon to the atmosphere the observed divergence from a simple solubility control emphasizes the degree to which oxygen consumption patterns can be altered by changes in ocean circulation and marine ecosystems

centennial to millennial scale changes in oxygenation and productivity in the eastern tropical south pacific during the last 25 000 years oxygen minimum zones omz have expanded in all tropical oceans during the last 50 years resulting in habitat contraction and considerable changes in marine biogeochemistry however for a better understanding of the omz dynamics under the current climate change two questions are relevant 1 how do the magnitude and temporal changes in oceanic dissolved oxygen of the last few decades compare to the natural variability on longer timescales and 2 what were the local and remote factors driving omz changes in the past in the present study we use a stacked record covering the last 25 kyr from the eastern tropical south pacific etsp omz to reconstruct changes in oxygenation and productivity we use a suite of proxies including the presence of laminations redox sensitive metals u mo re ni and cu total organic carbon and 15 n measurements water column denitrification and sediment redox conditions show pronounced centennial to millennial scale variability during the last 25 kyr with oxygenation levels as low as at present global cold periods at different timescales such as the last glacial maximum 23 19 kyr bp and the little ice age 1500 1850 ad were associated with a weak omz and low export production while warm intervals such as the deglaciation part of the medieval climate anomaly and the last 100 years are associated with a stronger omz and high export production water column denitrification and sediment redox conditions were strongly coupled during the last 25 kyr bp apart from one remarkable exception during the antarctic cold reversal sediments were less reducing but the water column denitrification was high resulting in a strong but shallow omz this may have been produced by an enhanced antarctic intermediate water flow contrary to our expectations and modeling predictions for the next few decades we observe a weak etsp omz during the warm mid holocene which may have been the result of a stronger walker circulation that brought oxygen rich waters to intermediate depths off peru via equatorial undercurrents in combination with other paleoceanographic reconstructions our results show that oxygenation variability in the etsp omz was influenced by ocean circulation changes in the tropical pacific high latitude oceanographic and climatic changes and local productivity

the dynamics of the marine nitrogen cycle across the last deglaciation 1 we use a geochemical box model to investigate the changes in marine n fixation and denitrification required to match the observed sedimentary 15n changes between 30 kyr b p and the late holocene this is achieved by optimizing a set of seven parameters that describe the strengths of three ocean internal n feedbacks and the response of the oceanic n cycle to four external forcings scenarios that best match the 15n constraints indicate a strong transient decrease in n fixation in the early deglacial in response to the decrease in iron input by dust around 15 kyr b p n fixation rebounds primarily in response to an abrupt increase in water column denitrification caused by an expansion of anoxia benthic denitrification is not well constrained by our model but tends to increase in sync with water column denitrification as a result of the transient imbalance between n fixation and denitrification we infer a glacial to interglacial decrease in the marine n inventory of between 15 and 50 the model diagnoses this reduction in order to simultaneously fit the data from all ocean basins requiring it to reduce the degree by which water column denitrification in the oxygen minimum zones is influencing the 15n of nitrate of the whole ocean dilution effect our optimal solution suggests a glacial n cycle that operated at nearly the same rates as that in pre industrial times but sensitivity cases with substantially lower rates fit the data only marginally worse an important caveat of our study is the assumption of an unchanging ocean circulation an initial sensitivity experiment shows that this affects primarily the magnitude of the change in the n inventory while the diagnosed deglacial dynamics with global marine n fixation taking a dip before the onset of denitrification remains a robust result

deglacial weakening of the oceanic soft tissue pump global constraints from sedimentary nitrogen isotopes and oxygenation proxies abstract among the many potential explanations for the 80 ppm rise of atmospheric co2 concentrations at the end of the last ice age most involve a weakening of the oceanic soft tissue pump here we use global data compilations of sedimentary nitrogen isotopes and benthic oxygenation proxies to provide a synoptic global perspective on the deglacial soft tissue pump weakening the net change between the last glacial maximum and holocene shows a removal of respired carbon everywhere that proxy data is available with the exception of the upper 1 5 km of the north pacific while excess nitrate accumulated in polar oceans these observations could be explained by intensifying iron limitation a shoaling of organic matter remineralization and or a change in ocean circulation but are inconsistent with a change in the magnitude or position of the southern mid latitude westerlies the net soft tissue pump weakening was front loaded in the early deglaciation 17 5 14 ka when atmospheric 13c and 14c were changing rapidly and appears to have contributed little net change thereafter superimposed on the overall deglacial trend were pronounced transient changes that coincided with variability in the atlantic meridional overturning circulation amoc and bipolar seesaw the seesaw variability is most clearly expressed as anti phased oxygenation changes between the upper 1 5 km of the north pacific and the deep north atlantic consistent with an atlantic pacific ventilation seesaw but it dominated transient variability in records throughout the world although the soft tissue pump seesaw made little contribution to the contrast between the glacial and interglacial states it could have contributed to deglacial variability in atmospheric co2 and might have catalyzed the deglaciation

movement of deep sea coral populations on climatic timescales during the past 40 000 years global climate has moved into and out of a full glacial period with the deglaciation marked by several millennial scale rapid climate change events here we investigate the ecological response of deep sea coral communities to both glaciation and these rapid climate change events we find that the deep sea coral populations of desmophyllum dianthus in both the north atlantic and the tasmanian seamounts expand at times of rapid climate change however during the more stable last glacial maximum the coral population globally retreats to a more restricted depth range holocene populations show regional patterns that provide some insight into what causes these dramatic changes in population structure the most important factors are likely responses to climatically driven changes in productivity o 2 and co 3 2

direct ventilation of the north pacific did not reach the deep ocean during the last deglaciation 1 despite its tremendous size the deep north pacific has received relatively little attention by paleoceanographers it was recently suggested that the deep north pacific was directly ventilated by dense waters formed in the subarctic pacific during heinrich stadial 1 hs1 of the early deglaciation here we present new redox sensitive trace metal data from a sediment core at 2393 m in the subarctic pacific in comparison with previously published data from elsewhere in the region the combined picture shows no sign of ventilation during the early deglaciation in any available core from water depths of 2393 m and deeper while the deepest core to display clear signs of enhanced ventilation during hs1 was raised from 1366 m water depth thus it appears likely that although the north pacific was well ventilated to intermediate depths during hs1 the deep ocean did not receive a significant input of dense waters from a local source but remained isolated from the surface waters above

surface nitrate utilization in the bering sea since 180 ka bp insight from sedimentary nitrogen isotopes we present high resolution records of sedimentary nitrogen 15nbulk and carbon isotope ratios 13cbulk from piston core so201 2 85kl located in the western bering sea the records reflect changes in surface nitrate utilization and terrestrial organic matter contribution in submillennial resolution that span the last 180 kyr the 15nbulk record is characterized by a minimum during the penultimate interglacial indicating low nitrate utilization 62 80 despite the relatively high export production inferred from opal concentrations along with a significant reduction in the terrestrial organic matter fraction mterr this suggests that the consumption of the nitrate pool at our site was incomplete and even more reduced than today 84 15nbulk increases from marine isotope stage mis 5 4 and culminates during the last glacial maximum which indicates that nitrate utilization in the bering sea was raised during cold intervals mis 5 4 5 2 4 and almost complete during mis 3 and 2 93 100 this is in agreement with previous hypotheses suggesting that stronger glacial stratification reduced the nutrient supply from the subeuphotic zone thereby increasing the iron to nutrient ratio and therefore the nitrate utilization in the mixed surface layer large variations in 15nbulk were also recorded from 180 to 130 ka bp mis 6 indicating a potential link to insolation and sea level forcing and its related feedbacks millennial scale oscillations were observed in 15nbulk and 13cbulk that might be related to greenland interstadials

peruvian sediments as recorders of an evolving hiatus for the last 22 thousand years highlights review of sediment archives from the peruvian margin since the lgm focus on the evolutionary feature of the hiatus found in archives modern analogue for current dominated environments for paleo reconstructions new results for erosional potential of the non linear internal waves nliws abstract the peruvian continental margin is characterized by the presence of one of the strongest and most distinct oxygen minimum zones omzs in today s oceans therefore it has long been in the focus of oceanographic and geological investigations observations indicate that omzs are expanding in relation with currently changing climate to advance understanding of the temporal evolution of omzs and climate change complete paleoceanographic and palaeoclimatological reconstructions are needed however the development of paleoenvironmental scenarios for the period since the last glacial maximum at this region was hampered by a ubiquitous hiatus and short term interruptions of the stratigraphical record in the present study we combined the stratigraphical information from 31 sediment cores from the peruvian margin located between 3 and 18 s and water depths of 90 to 1300 m within and below today s omz in order to determine the extent of the hiatus and assess the responsible mechanisms a widespread unconformity and related erosional features omission surfaces and phosphorites were observed in sediment cores from the area south of 7 s depicting a prograding feature on the continental slope from south to north during the deglaciation combining recent oceanographic and sedimentological observations it is inferred that tide topography interaction and resulting non linear internal waves nliws shape the slope by erosion carry sediments upslope or downslope and leave widespread phosphoritic lag sediments while the peru chile undercurrent pcuc transports the resuspended sediments southward causing non deposition this exceptional sedimentary regime makes the peruvian margin a modern analogue for such environments overall our compilation of downcore records showed that enhanced bottom currents due to tide topography interaction were progressively evolving and affected a wider area with the onset of the last deglaciation elevated tidal amplitudes and variability of mid depth water masses i e density changes and hydrodynamics in relation with changing climate were potential reasons of this evolving feature of erosion and reworking additionally erosion and non deposition was observed widest and even was encountered on the continental shelf during the early holocene potentially indicating a strong phase of the pcuc mirroring today s el nino like conditions

the acceleration of oceanic denitrification during deglacial warming the marine nitrogen cycle was altered during the transition from glacial to interglacial conditions an analysis of 15n records throughout the world s oceans suggests that rates of denitrification in the water column accelerated during the last deglaciation

determination of the mg mn ratio in foraminiferal coatings an approach to correct mg ca temperatures for mn rich contaminant phases the occurrence of manganese rich coatings on foraminifera can have a significant effect on their bulk mg ca ratios thereby biasing seawater temperature reconstructions the removal of this mn phase requires a reductive cleaning step but this has been suggested to preferentially dissolve mg rich biogenic carbonate potentially introducing an analytical bias in paleotemperature estimates in this study the geochemical composition of foraminifera tests from mn rich sediments from the antarctic southern ocean odp site 1094 was investigated using solution based and laser ablation icp ms in order to determine the amount of mg incorporated into the coatings the analysis of planktonic and benthic foraminifera revealed a nearly constant mg mn ratio in the mn coating of 0 2 mol mol consequently the coating mg mn ratio can be used to correct for the mg incorporated into the mn phase by using the down core mn ca values of samples that have not been reductively cleaned the consistency of the coating mg mn ratio obtained in this study as well as that found in samples from the panama basin suggests that spatial variation of mg mn in foraminiferal mn overgrowths may be smaller than expected from mn nodules and mn ca carbonates however a site specific assessment of the mg mn ratio in foraminiferal coatings is recommended to improve the accuracy of the correction