assessing the reliability of magnesium in foraminiferal calcite as a proxy for water mass temperatures though many studies on the mg contents in the calcitic tests of foraminifers exist the processes controlling its uptake are still a matter of debate laboratory cultures offer an excellent opportunity to reveal these mechanisms the mg concentrations within single chambers of the planktic foraminifer globigerinoides sacculifer brady maintained under controlled laboratory conditions were measured 1 at variable temperatures 19 5 29 5 c and constant salinity and 2 at variable salinity 22 45 and constant temperature the experimental results suggest that under natural conditions temperature is the leading mechanism controlling the mg ca ratio temperature and magnesium are related proportionally a temperature increase of ca 10 c gives rise to an increase of the magnesium concentrations of ca 130 drastic unnatural salinity changes dominate the effects of temperature a 110 change in the mg ca ratio was observed when salinity was elevated or reduced by more than ca 10 specimens which underwent gametogenesis reveal significantly higher mg concentrations than specimens that did not release gametes partition coefficients for mg in foraminiferal calcite are orders of magnitude lower than values from inorganically precipitated calcite when comparing observed mg ca ratios of foraminiferal tests with predicted mg ca ratios calculated according to empirical equations it becomes evident that foraminiferal tests are undersaturated with respect to mg for the water temperature they have experienced apparently foraminifers are capable of controlling their mg concentration the physiological processes presumably responsible for such depressed mg ca ratios appear to be temperature controlled as deduced from the close relationship of the observed mg ca ratios and water temperature this study demonstrates that variations in temperature and salinity are definitely reflected in the mg content of foraminiferal tests magnesium may thus serve as a paleo proxy for past surface water temperatures as long as postdepositional changes and salinity variations are of subordinate importance or can be excluded

seawater ph pco2 and co2 3 variations in the caribbean sea over the last 130 kyr a boron isotope and b ca study of planktic foraminifera abstract here a new analytical methodology is described for measuring the isotopic composition of boron in foraminifera using multicollector inductively coupled plasma mass spectrometry mc icpms this new approach is fast 10 samples analysed in duplicate per analytical session and accurate to better than 0 25 at 95 confidence with acceptable sample size requirements 1 3 mg of carbonate a core top calibration of several common planktic and two benthic species from geographically widespread localities shows a very close agreement between the isotopic composition measured by mc icpms and the isotopic composition of b oh 4 in seawater as predicted using the recently measured isotopic equilibrium factor of 1 0272 at the depth of habitat a down core and core top investigation of boron concentration b ca ratio shows that the partition coefficient is influenced by co2 3 complicating the application of this proxy nevertheless it is demonstrated that these two proxies can be used to fully constrain the carbonate system of surface water in the caribbean sea odp site 999a over the last 130 kyr this reconstruction shows that during much of the holocene and the last interglacial period surface water at site 999a was in equilibrium with the atmosphere with respect to co2 during the intervening colder periods although the surface water pco2 was lower than the holocene it was a minor to significant source of co2 to the atmosphere possibly due to either an expansion of the eastern equatorial atlantic upwelling zone or a more local expansion of coastal upwelling in the southern caribbean such reorganisation of the oceanic carbonate system in favour of a larger source of co2 to the atmosphere from the equatorial ocean may require mechanisms responsible for lowering atmospheric co2 during glacial periods to be more efficient than previously supposed

modern and late pleistocene b ca ratios of the benthic foraminifer planulina wuellerstorfi determined with laser ablation icp ms incorporation of boron into foraminiferal shells is thought to be primarily governed by the carbonate chemistry of the ambient seawater suggesting that it can be reconstructed from b ca ratios to this end b ca ratios of the benthic foraminifer planulina wuellerstorfi from south atlantic core top samples have been analyzed using laser ablation inductively coupled plasma mass spectroscopy la icp ms to provide additional information on intratest trace element heterogeneity results show that boron is heterogeneously distributed within and between shells with content variations of approximately 43 displayed within a single shell b ca is higher in the youngest chambers opposite to the observed between chamber variability of mg ca this may be explained by ontogenetic changes of physiological processes that increase the ph of the calcifying fluid and thus the borate concentration while decreasing mg ca to promote calcification despite this heterogeneity mean b ca ratios are positively correlated with the deepwater calcite saturation state co32 in line with previous studies we apply this empirical relationship to reconstruct co32 for the late pleistocene to holocene using samples from a depth transect in the equatorial atlantic reconstructed co32 values confirm previous studies suggesting that caco3 oversaturated north atlantic deep water was reduced during glacial periods whereas caco3 undersaturated antarctic bottom water expanded vertically and propagated northwards in summary our data demonstrate that bulk b ca in p wuellerstorfi reliably reflects variations in co32 despite the strong physiological control of boron incorporation

reevaluation of the caco3 size index paleocarbonate ion proxy measurements of the caco3 size index broecker and clark 1999 and of whole foraminifera shell weights lohmann 1995 on glacial age sediment from a series of water depths on the ceara rise in the west equatorial atlantic clearly demonstrate that the relationship between size index and pressure normalized carbonate ion concentration established for holocene equatorial sediments does not apply to glacial sediments rather it appears that the ratio of fine to coarse caco3 raining to the seafloor was greater during glacial time than during the holocene this finding squelches our previous enthusiasm regarding the application of the size index as a paleocarbonate ion proxy

oceanic ph control on the boron isotopic composition of foraminifera evidence from culture experiments culture experiments were carried out with the species orbulina universa at four different ph values 7 70 0 05 8 15 0 05 8 60 0 05 and 9 00 0 10 in order to establish the ph dependence of boron isotope fractionation between seawater and foraminifera a clear relationship between the boron isotopic composition of the foraminifera and the ph of the seawater culture solutions was found showing heavier boron isotopic composition at higher ph this finding supports the viability of boron isotopes as a paleo ph tool it is important to note that orbulina universa cultured in natural seawater as well as those obtained from coretop samples have a significantly lighter boron isotopic ratio than globigerinoides sacculifer from coretop samples suggesting that at least for this species a vital effect is active

alkenone and boron based pliocene pco2 records abstract the pliocene period is the most recent time when the earth was globally significantly 3 c warmer than today however the existing pco2 data for the pliocene are sparse and there is little agreement between the various techniques used to reconstruct palaeo pco2 this disagreement coupled with the general low temporal resolution of the published records does not allow a robust assessment of the role of declining pco2 in the intensification of the northern hemisphere glaciation inhg and a direct comparison to other proxy records are lacking for the first time we use a combination of foraminiferal 11b and organic biomarker alkenone derived carbon isotopes proxies to determine the concentration of atmospheric co2 over the past 5 ma both proxy records show that during the warm pliocene pco2 was between 330 and 400 ppm i e similar to today the decrease to values similar to pre industrial times 275 285 ppm occurred between 3 2 ma and 2 8 ma coincident with the inhg and affirming the link between global climate the cryosphere and pco2

seawater ph control on the boron isotopic composition of calcite evidence from inorganic calcite precipitation experiments experiments involving boron co precipitation with calcite have been carried out inorganically under controlled ph conditions 7 9 0 05 8 3 0 05 and 8 6 0 05 to determine the dependence of the boron isotopic composition 11b of calcite on the ph of seawater another purpose of these experiments was to estimate the magnitude of the biogenic influence on the 11b value of foraminifera by comparing their boron isotopic composition with that of the inorganic calcite over a common ph range the results show a clear relationship between 11b of inorganic calcite and the ph of artificial seawater the variation of boron isotopic fractionation between seawater and calcite with ph estimated from these experiments is similar to that estimated for cultured o universa and the theoretically predicted trend the results also support the hypothesis that b oh 4 is the dominant species incorporated into the calcite structure however the boron isotopic fractionation between seawater and inorganic calcite is lower than that estimated for o universa indicating the presence of a biogenic effect on the boron isotopic composition at least of this species of foraminifera most importantly the results imply that in spite of a small biogenic influence on the boron isotopic composition of foraminifera the variation in 11b of foraminiferal shells with ph at least for o universa is comparable to that for inorganic calcite supporting the potential of this isotopic signature in foraminifera as a reliable paleo ph proxy

evaluating the utility of b ca ratios in planktic foraminifera as a proxy for the carbonate system a case study of globigerinoides ruber b ca ratios in foraminifera have attracted considerable scientific attention as a proxy for past ocean carbonate system however the carbonate system controls on b ca ratios are not straightforward with inline image inline image in situ inline image at saturation correlating best with b ca ratios in benthic foraminifera rather than ph inline image or inline image as a simple model of boron speciation in seawater and incorporation into caco3 would predict furthermore culture experiments have shown that in planktic foraminifera properties such as salinity and b sw can have profound effects on b ca ratios beyond those predicted by simple partition coefficients here we investigate the controls on b ca ratios in g ruber via a combination of culture experiments and core top measurements and add to a growing body of evidence that suggests b ca ratios in symbiont bearing foraminiferal carbonate are not a straightforward proxy for past seawater carbonate system conditions we find that while b ca ratios in culture experiments covary with ph in open ocean sediments this relationship is not seen in fact our b ca data correlate best with inline image a previously undocumented association and in most regions salinity these findings might suggest a precipitation rate or crystallographic control on boron incorporation into foraminiferal calcite regardless our results underscore the need for caution when attempting to interpret b ca records in terms of the ocean carbonate system at the very least in the case of mixed layer planktic foraminifera

boron isotopes in different grain size fractions exploring past and present water rock interactions from two soil profiles strengbach vosges mountains abstract in the present study we test the ability of b isotopes to trace past and present weathering reactions in the case of two forest soils formed by a polyphasic sequence involving early hydrothermal alteration of the bedrock and pedogenesis we provide b chemical and isotopic compositions in two 2 m soil profiles sampled in the strengbach watershed vosges france the two soils belong to different soil series an ochreous podzol haplorthod and a brown acidic soil dystrochrept developed on the same granitic bedrock but differently affected by hydrothermal alteration separated granulometric fractions and bulk soil samples have been analyzed coarse particles are mostly composed of primary minerals and show a clear anti correlation between 11 b and mg al reflecting various grades of the early hydrothermal alteration the finest particles clay size fractions deviate from this hydrothermal trend and are diagnostic of pedogenic processes occurring after b exchange with the surrounding 11 b rich soil solution examination of the b distribution in different particle size fractions also indicates that b is transferred from the coarse sand fraction in deeper soil layers to the clay fraction in the upper layers the intermediate size fractions are found to play only a secondary role in the soil forming reactions the two soils show distinct b isotope profiles which are consistent with the different pedogenic processes that govern their formation in the podzolic soil 11 b can be explained by a simple model in which pedogenesis occurs by continuous dissolution of primary minerals and precipitation of secondary ones in the brown acid soil a more complex model that includes the precipitation of clay minerals in the deep horizon and their gradual dissolution in the upper soil layers accounts for the observed results additionally residual hydrothermal illites are more resistant to weathering and are found in the clay fraction where they were directly inherited from the dislocation of coarser grains in which they were encapsulated on a broader scale the large b isotopic fractionation during water rock interactions greatly facilitates the quantification of matter exchange between soil solutions and solids and the determination of global weathering rates the data from the present study demonstrate that the determination of b isotopes in different particle size fractions can reveal the relative importance of source and process effects during weathering

incorporation and preservation of mg in globigerinoides sacculifer implications for reconstructing the temperature and 18o 16o of seawater using bathymetric transects of surface sediments underlying similar sea surface temperatures but exposed to increasing dissolution we examined the processes which affect the relationship between foraminiferal mg ca and 18o we found that globigerinoides saccculifer calcifies over a relatively large range of water depth and that this is apparent in their mg content on the seafloor foraminiferal mg ca is substantially altered by dissolution with the degree of alteration increasing with water depth selective dissolution of the chamber calcite formed in surface waters shifts the shell s bulk mg ca and 18o toward the chemistries of the secondary crust acquired in colder thermocline waters the magnitude of this shift depends on both the range of temperatures over which the shell calcified and the degree to which it is subsequently dissolved in spite of this shift the initial relationship between mg ca and 18o determined by their temperature dependence is maintained we conclude that paired measurements of 18o and mg ca can be used for reconstructing 18owater though care must be taken to determine where in the water column the reconstruction applies

variations in mg ca and sr ca ratios of planktonic foraminifera caused by postdepositional dissolution evidence of shallow mg dependent dissolution a comparative study has been made of two species of planktonic foraminifera g tumida and g sacculifer in a depth transect on the ontong java plateau western equatorial pacific g tumida tests from core top sediments showed decreasing mg ca 2 65 1 25 mmol mol and sr ca 1 50 1 16 mmol mol ratios with increasing water depth 1600 4400 m while no such variation was found in g sacculifer tests in excess of 355 m average mg ca 3 6 mmol mol sr ca 1 4 mmol mol artificial dissolution of g tumida tests led to a decrease in both mg ca and sr ca but in g sacculifer there was no significant change in the ratios analyses by electron microprobe revealed that mg ca of the inner chamber calcite in g tumida tests was much higher than that of the calcite crust keel whereas sr ca was only slightly elevated there were no consistent spatial differences in either mg ca or sr ca for g sacculifer tests dissolution in the oceans gives rise to the removal of the chamber calcite in g tumida about 30 of the total calcite leaving the keel calcite although g tumida is thought of as a dissolution resistant form the majority of mg ca and sr ca depletion and chamber loss occurs above the lysocline it is also possible that much of the mg enriched gametogenic calcite has been lost by dissolution from g sacculifer above 1600 m mg content has a significant effect on the dissolution susceptibility of planktonic foraminifera calculations show that the saturation horizon for mg rich parts of tests may be elevated by several hundred meters compared with normal calcite

coprecipitation and isotopic fractionation of boron in modern biogenic carbonates abstract the abundances and isotopic composition of boron in modern biogenic calcareous skeletons from the gulf of elat israel the great barrier reef australia and in deep sea sediments have been examined by negative thermal ionization mass spectrometry the selected species foraminifera pteropoda corals gastropoda and pelecypoda yield large variations in boron concentration that range from 1 ppm in gastropod shells to 80 ppm in corals the boron content of the biogenic skeletons is independent of mineralogical composition and is probably related to biological vital effects the 11 b values of the carbonates range from 14 2 to 32 2 relative to nbs srm 951 and overlap with the 11 b values of modern deep sea carbonate sediments 11 b 8 9 to 26 2 the variations of 11 b may be controlled by isotopic exchange of boron species in which 10 b is preferentially partitioned into the tetrahedral species and coprecipitation of different proportions of trigonal and tetrahedral species in the calcium carbonates carbonates with low 11 b values 15 may indicate preferential incorporation of tetrahedral species whereas the higher 11 b values 30 may indicate 1 1 uptake of both boron species assuming equilibrium with seawater 2 2 preferential incorporation of b oh 4 from in situ high ph internal fluids of organisms that are isolated from seawater the b content and 11 b values of deep sea sediments foraminifera tests and corals are used to estimate the global oceanic sink of elemental boron by calcium carbonate deposition as a result of enrichment of b in corals a substantially higher biogenic sink of 6 4 0 9 10 10 g yr is calculated for carbonates this is only slightly lower than the sink for desorbable b in marine sediments 10 10 10 g yr and approximately half that of altered oceanic crust 14 10 10 g yr thus carbonates are an important sink for b in the oceans being 20 of the total sinks the preferential incorporation of 10 b into calcium carbonate results in oceanic 11 b enrichment estimated as 1 2 0 3 10 12 per mil g yr the boron isotope composition of authigenic well preserved carbonate skeletons may provide a useful tool to record secular boron isotope variations in seawater at various times in the geological record the potential use of boron isotope geochemistry in skeletons as a tracer for palaeoenvironments is demonstrated in ostracoda and foraminifera from the gulf of carpentaria australia the 11 b values of glacial age buried skeletons 4 0 and 4 9 respectively are lower than that of their modern equivalents 17 6 and 13 3 respectively this may reflect a terrestrial boron isotope signature of the water in the gulf during the late quaternary when it was isolated from the ocean

mid pliocene warmth stronger greenhouse and stronger conveyor abstract three million years ago prior to the onset of northern hemisphere glaciation global mean temperatures may have been as much as 3 5 c warmer than at present we present evidence based on the carbon isotopic composition of marine organic matter that atmospheric co2 levels at this time were on average only about 35 higher than the preindustrial value of 280 ppm we also present carbon isotopic evidence for stronger thermohaline circulation in the atlantic ocean during the warmest intervals and propose that the north atlantic conveyor belt may act as a positive feedback to global warming by enhancing sea ice retreat and decreasing high latitude albedo based on our results it seems unlikely that the mid pliocene warm period was a doubled co2 world

rift shear architecture and tectonic development of the ghana margin deduced from multichannel seismic reflection and potential field data abstract the ghana margin displays one of the best known transform margins studies of the margin have provided the framework for a number of conceptual models aimed at understanding transform margin development worldwide however the deep structure of the margin is poorly known as knowledge is based only on wide angle refraction measurements obtained from two separate localities on the margin consequently complexities in the rift shear margin architecture have been overlooked by current interpretations of margin development based on combined analysis of a detailed grid of 2710 km multichannel mcs lines and potential field data we provide new insights into the structural architecture and tectonic development of the ghana margin in particular we outline the deep structure of the entire margin using a series of 2d gravity modelled transects constrained by mcs and published wide angle data our study reveals more complex rift shear margin architecture than previously envisaged we demonstrate that the main transform boundary representing the continental extension of the romanche fracture zone is actually composed of two distinct margin segments i e the ene wsw trending sheared margin segment of the cote d ivoire ghana ridge and the ne sw trending rift influenced sheared margin segment of the ghana platform these segments evolved under varying stress regimes and during different time intervals west of the transform margin divergent rifting during the early cretaceous initiated the development of the deep ivorian basin essentially as a single major pull apart structure however east of the shear zone oblique rifting resulted in the development of the eastern ghana slope basin as a composite of at least two coalescing pull apart basins displaced along strike slip faults our structural interpretation of the transform boundary geometry shows that the ridge and platform margin segments were each subjected to separate thermal influences from two different migrating spreading centres tectonic uplift of the ridge began through transpression during mid albian time following a change in relative direction of plate motion from ne sw to ene wsw however the ridge uplift was amplified by thermal heating from a previously undocumented spreading centre whose progressive westward migration along the ridge followed closely after the albian transpressional phase the structural architecture of the ghana margin resulted from a combination of factors notably pre existing basement structure plate boundary geometry the relative direction of plate motion and thermal heating

the boron isotopic composition of altered oceanic crust samples of drilled oceanic crust from dsdp holes 417a 417d and 418a and odp hole 735b and oceanic crust from the oman and cyprus ophiolites were analyzed for b contents and 11b composite samples from dsdp holes 417a 417d and 418a were used to represent the upper 550 m of altered oceanic crustal layer 2a whole rock samples from the troodos ophiolite cyprus and the oman ophiolite wer selected to represent crustal layer 2b dikes composite samples from odp hole 735b were used to represent crustal layer 3 the b content of the dsdp composites ranges from 7 2 ppm to 104 ppm and correlates with both 18o and k showing that it is a good indicator of the extent of low temperature alteration the 11b of the dsdp composites varies between 2 5 and 5 4 the b content of the samples from the troodos ophiolite ranges from 2 4 ppm to 8 1 ppm 11b varies from 0 9 to 7 8 the b content of the oman ophiolite samples ranges from 5 0 ppm to 11 1 ppm 11b varies from 1 6 to 16 9 the b content of the samples from odp hole 735b ranges from 1 1 ppm to 7 1 ppm 11b varies from 4 3 to 24 9 the general pattern displayed by these samples is one of greatest and most variable b enrichment at the top of the crust and least enrichment at the bottom of the section all of these samples are enriched compared to unaltered morb which is believed to have a b content of approximately 0 5 ppm the 11b values of deeper samples from layers 2b and 3 are more variable and generally higher than those from layer 2a boron contents and 11b are not correlated the data from the dsdp site 417418 composites indicate that the 11b of fluid circulating in the upper crust changes only slightly during alteration increasing by an average of 5 1 with an accompanying decrease in b concentration of 7 low temperature alteration appears to be a water dominated process resulting in minor modification of circulating seawater a minimum water rock ratio of 400 is calculated for these samples implying a minimum low temperature seawater flux through the upper oceanic crust of 3 4 1014 l y the average b content of altered oceanic crust as represented by these samples is 5 2 1 7 ppm and the average 11b is 3 4 1 1 this average isotopic composition is measurably different from the apparent average of oceanic sediments supporting the idea that 11b could be useful for identifying the source s of b in island arcs

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

boron calcium ratios in globigerinoides ruber from the arabian sea implications for controls on boron incorporation abstract culture and downcore studies have been used to argue that b ca ratios in planktic foraminifera are correlated with seawater ph and may record seawater borate bicarbonate ratios although other factors may also control b ca specimens of globigerinoides ruber from the ocean drilling program odp site 723a western arabian sea and core aas9 21 eastern arabian sea from the last 22 kyr were analysed for b ca 18 o and mg ca b ca was compared to reconstructed salinity and sea surface temperature sst records to gain insight into the processes controlling the incorporation of boron in both cores b ca and mg ca are positively correlated which suggests that temperature governs the incorporation of boron in g ruber to some extent higher b ca ratios at the site affected by upwelling odp 723a than in the non upwelling region core aas9 21 and a positive correlation between b ca and shell size in g ruber are observed we observe no significant correlation between b ca in g ruber and salinity ph or dissolved inorganic carbon dic in either the western or eastern arabian sea which throws considerable doubt on the utility of b ca ratios as a ph or pco 2 proxy

possible roles of ph temperature and partial dissolution in determining boron concentration and isotopic composition in planktonic foraminifera 1 we present the first continuous records from 0 to 5 ma in 0 333 m y integrated time steps of paired boron calcium b ca ratios and boron isotopes 11b in the planktonic foraminifera globogerinoides sacculifer without sacc from a site in the western equatorial pacific ocean ocean drilling program site 806 these measurements the first made in conjunction with calcification temperature magnesium calcium ratios and average shell mass measurements indicate that ph is not the sole environmental variable controlling b in planktonic foraminiferal calcite our data are consistent with calcification temperature exerting a primary control on b concentration and isotopic composition in planktonic foraminifera if so calcification temperature must be taken into account if ph for past oceans and atmospheric pco2 are to be estimated from b isotope measurements in foraminiferal calcite doing so will substantially increase the uncertainty of ph estimates although this work was designed as a temporal study its results define new aspects of calibrating the 11b paleo ph tracer

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

miocene evolution of atmospheric carbon dioxide changes in pco2 or ocean circulation are generally invoked to explain warm early miocene climates and a rapid east antarctic ice sheet eais expansion in the middle miocene this study reconstructs late oligocene to late miocene pco2 from ep values based on carbon isotopic analyses of diunsaturated alkenones and planktonic foraminifera from deep sea drilling project sites 588 and 608 and ocean drilling program site 730 our results indicate that highest pco2 occurred during the latest oligocene 350 ppmv but decreased rapidly at 25 ma the early and middle miocene was characterized by low pco2 260 190 ppmv lower intervals of pco2 correspond to inferred organic carbon burial events and glacial episodes with the lowest concentrations occurring during the middle miocene there is no evidence for either high pco2 during the late early miocene climatic optimum or a sharp pco2 decrease associated with eais growth paradoxically pco2 increased following eais growth and obtained preindustrial levels by 10 ma although we emphasize an oceanographic control on miocene climate low pco2 could have primed the climate system to respond sensitively to changes in heat and vapor transport

changes in ph in the eastern equatorial pacific across stage 5 6 boundary based on boron isotopes in foraminifera estimates of paleo ph for the eastern equatorial pacific ocean across the oxygen isotopic stage 5 6 boundary have been made based on the boron isotopic composition of planktonic orbulina universa and benthic mixed species foraminifera from core v19 28 the estimated deep ocean ph during the penultimate glacial period was about 0 3 0 1 ph units higher compared to the modern deep ocean this is consistent with previously estimated deep ocean ph changes across the stage l 2 boundary in the western equatorial pacific and tropical atlantic thus arguing against the possibility that the benthic foraminifera analyzed to estimate deep ocean ph changes have been significantly affected by anomalous local environment and or diagenesis the estimated changes in the deep ocean carbonate chemistry require a decoupling of several kilometers between the saturation horizon and the lysocline during the glacial periods though such a decoupling could be achieved by enhanced respiration co2 driven calcite dissolution in sediments during glacial periods it lacks support from the calcite sedimentary records the boron isotopic compositions of planktonic foraminifera on the other hand indicate no significant ph change in the eastern equatorial pacific surface ocean during the glacial interglacial transition this is inconsistent with an expected higher surface ocean ph during the glacial period due to lower atmospheric pco2 and is also in contrast with the previously estimated boron isotope based glacial interglacial ph change of 0 2 0 1 ph units in the western equatorial pacific and tropical atlantic the lack of change in eastern equatorial pacific surface ocean ph between glacial interglacial periods could be attributed to less nutrient utilization efficiency and or enhanced calcite production during glacial periods such a decrease in nutrient utilization efficiency and or increase in calcite production would lead to a greater disequilibrium between the pco2 of eastern equatorial pacific surface ocean and that of the atmosphere making this part of the ocean a greater source of co2 to the atmosphere during glacial periods compared to today

planktonic foraminiferal cd ca paleonutrients or paleotemperature records of cd ca in planktonic foraminiferal calcite of globigerinoides bulloides in cores from the subantarctic region of the southern ocean show large glacial interglacial variations with lower cd ca by 0 06 0 10 mol mol 1 at glacial times interpretation of these records in terms of lower dissolved phosphate and inferred higher glacial nutrient utilization has significant implications for glacial atmospheric carbon dioxide pco2 draw down however box core top data for g bulloides in the north atlantic suggest that the incorporation of cd into planktonic foraminifera relative to seawater dcd is temperature sensitive dcd 0 637 exp 0 15t when the subantarctic planktonic cd ca records are corrected for this temperature dependence they show little or no glacial interglacial diferences if as seems likely this observation can be interpreted to indicate a minimal change 0 5 mol kg 1 in surface water phosphate concentrations then the explanation for lowered glacial pco2 must be looked for elsewhere