calibration of the planktonic foraminiferal mg ca paleothermometer sediment trap results from the guaymas basin gulf of california 1 the mg ca ratio has been measured in two surface dwelling species of planktonic foraminifera globigerinoides ruber and globigerina bulloides from biweekly sediment trap samples collected in guaymas basin gulf of california between august 1992 and november 1997 the guaymas basin experiences significant seasonal changes in sea surface temperature sst 16 33 c and thus is an ideal location for testing the temperature dependence of mg incorporation into foraminiferal calcite the planktonic foraminiferal mg ca ratios are directly compared with concurrent temperature measurements from the study site the results from the sediment trap study reveal a strong positive correlation between sst and the mg ca ratio in both g ruber r2 0 86 and g bulloides r2 0 90 the mg ca ratio increases exponentially by 7 per 1 c change in temperature for g ruber and by 6 for g bulloides these results indicate that the mg ca ratio in g ruber and g bulloides accurately records the measured seasonal surface temperature cycle and interannual variability in the guaymas basin within 1 c the greatest deviation between mg ca estimated sst and observed sst occurs in the spring and fall for both species this variability is attributed to rapidly changing hydrographic conditions and possible offset between the time of calcification and the temperature measurements in addition g ruber and g bulloides exhibit very high mg ca ratios during the strong el nino southern oscillation years of 1992 and 1997 verifying their potential to record sst up to 33 c and 28 c respectively the trace metal data are compared with foraminiferal oxygen isotope and alkenone measurements made on the same suite of sediment trap samples to assess the internal consistency of these temperature proxies strong correlations exist between the 18o and mg ca for g ruber r2 0 86 and g bulloides r2 0 79 similarly sea surface temperature estimates from mg ca ratios are in good agreement with alkenone derived temperature estimates r2 0 89 for g ruber and r2 0 81 for g bulloides

a study of cleaning procedures used for foraminiferal mg ca paleothermometry the various cleaning steps required for preparation of foraminiferal samples for mg ca and sr ca analysis are evaluated for their relative importance and effects on measured elemental ratios it is shown that the removal of silicate contamination is the most important step for the measurement of mg ca ratios in an example bulk sample mg ca decreases from 10 5 to 2 5 mmol mol 1 during clay removal oxidation of organic material causes a lowering of sample mg ca in the order of 10 or approximately 1 c when converted to temperature use of dilute acid leaching to remove adsorbed contaminants causes partial dissolution of the sample carbonate and a corresponding decrease in mg ca reductive treatment also causes dissolution of the sample and a decrease in the mg ca ratio of up to 10 15 sample preparation for sr ca analysis does not require the same degree of rigor as is necessary for mg ca work the within run reproducibility of the method described here for g ruber in a core top sample from the arabian sea was 1 8 mean sample ratio was 4 72 mmol mol 1 when converted to temperature this becomes 28 0 2 c the equivalent result for sr ca was 0 5 mean ratio 1 44 mmol mol 1

an evaluation of controls on planktonic foraminiferal sr ca comparison of water column and core top data from a north atlantic transect sr ca in planktonic foraminifera recovered from the water column over 0 800 m along a meridional transect in the north atlantic ocean from 30 to 60 n were compared with data from core top samples on the same transect and with in situ temperatures determined from water column ctd profiles species belonging to the globorotaliid genus show significant variability in sr ca from place to place whereas non globorotaliid species show no significant variability this variability for the globorotaliid species in core top samples has already been shown to covary with calcification temperature derived from 18o but it also covaries with bottom depth symptomatic of a dissolution artifact these alternatives are distinguishable from the water column data for which the globorotaliid species show a small temperature dependence of 0 025 mmol mol c within the range 5 15 c however temperature dependence is not supported by glacial interglacial differences in sr ca for globorotaliid and non globorotaliid species and at least from this perspective a co3 2 influence seems more likely

effect of mg ca ratio in seawater on shell composition in shallow benthic foraminifera 1 the ratio of magnesium to calcium mg ca in caco3 shells of foraminifera is widely used to determine paleotemperatures however mg ca is highly variable within and between species suggesting a strong physiological influence on the incorporation of mg2 into the shells while most field and laboratory calibrations have focused on the effect of temperature we chose to study the effect of ambient mg ca on the calcification process and the final shell composition we cultured two species of symbiont bearing benthic foraminifera amphistegina lobifera and amphistegina lessonii in seawater with different mg ca ratios electron probe analysis of the shell mg ca revealed a positive but not entirely linear correlation with mg ca in the culturing media with slightly different curves for each species partition coefficients of mg2 dmg in the calcite shells showed a decrease by a factor of roughly 2 between the lowest and highest mg ca in the ambient water this was previously demonstrated in inorganic calcite precipitation experiments however the biogenic dmg was significantly lower than the inorganic one suggesting a physiological mechanism that reduces mg ca at the calcification site unlike inorganic experiments that display a dependence of dmg on the kinetics of precipitation the biogenic dmg is not correlated with the rate of calcification both dmg and calcification rates in our experiment were sensitive to the mg ca ratio rather than the concentration of either ca2 or mg2 the largest addition of caco3 was obtained at mg ca of 1 and not at present day seawater ratio mg ca 5 this may reflect the mg ca that prevailed during the eocene mg ca 1 5 when this genus evolved

a n s receiver function profile across the variscides and caledonides in sw ireland summary teleseismic receiver functions have been calculated from data of a temporary seismological network of broad band three component stations to investigate the lithospheric and asthenospheric structure across the late caledonian iapetus suture zone isz in southern ireland the stations were deployed during the irish seismological lithospheric experiment isle 2002 3 and straddle the killarney mallow fault zone a remnant of the variscan orogeny and the isz the inferred boundary between the laurentia and eastern avalonia plates fused together during the caledonian orogeny receiver functions from the western part of the network were projected onto the n s varnet 1996 seismic refraction profile extending from the old head of kinsale to galway bay in sw ireland laterally continuous p to s conversions from the moho at delay times of about 3 8 4 1 s are clearly observed and correspond to moho depths of about 29 32 km the moho has a transitional character to the south of the isz synthetic receiver functions calculated from a 2 d velocity model of the previous varnet experiment show moho conversions and multiple crustal phases compatible to those observed in the isle data furthermore p to s conversions from the 660 km discontinuity 66 68 s delay time are well determined at the stations in comparison the conversion from the 410 km discontinuity at about 43 45 s delay time is considerably weaker delay times of stacked receiver functions from the mantle transition zone are in agreement with the standard iasp91 earth model and thus no structural changes are observed across the isz at this depth interval

effects of seawater carbonate ion concentration and temperature on shell u mg and sr in cultured planktonic foraminifera we investigate the sensitivity of u ca mg ca and sr ca to changes in seawater co3 and temperature in calcite produced by the two planktonic foraminifera species orbulina universa and globige rina bulloides in laboratory culture experiments our results demonstrate that at constant temperature u ca in o universa decreases by 25 7 per 100 mol co3 k g 1 as seawater co3 increases from 110 to 470 mol kg 1 results from g bulloides suggest a similar relationship but u ca is consistently offset by 40 at the same environmental co3 in o universa u ca is insensitive to temperature between 15 c and 25 c applying the o universa relationship to three u ca records from a related species globigerinoides sacculifer we estimate that caribbean and tropical atlantic co3 was 110 70 mol kg 1 and 80 40 mol kg 1 higher respectively during the last glacial period relative to the holocene this result is consistent with estimates of the glacial interglacial change in surface water co3 based on both modeling and on boron isotope ph estimates in settings where the addition of u by diagenetic processes is not a factor down core records of foraminiferal u ca have potential to provide information about changes in the ocean s carbonate concentration below ambient ph ph 8 2 mg ca decreased by 7 5 o universa t o 16 6 g bulloides per 0 1 unit increase in ph above ambient ph the change in mg ca was not significant for either species this result suggests that mg ca based paleotemperature estimates for the quaternary during which surface ocean ph has been at or above modern levels have not been biased by variations in surface water ph sr ca increased linearly by 1 6 0 4 per 0 1 unit increase in ph shell mg ca increased exponentially with temperature in o universa where mg ca 0 85 exp 0 096 t whereas the change in sr ca with temperature was within the reproducibility of replicate measurements copyright 2004 elsevier ltd

effects of temperature on mg ca in neogloboquadrinid shells determined by live culturing 1 new culturing protocols allowed the development of a mg ca temperature calibration equation for neogloboquadrina pachyderma d when cultured between 9 c and 19 2 c mg ca in n pachyderma d shell calcite exhibits a clear dependence on temperature shell calcite mg ca increased exponentially with temperature mg ca 0 51 0 15 0 23 exp 0 10 0 02 t limited data suggest n dutertrei exhibit similar elemental temperature relationships to n pachyderma d we applied the temperature relationship established by culturing to mg ca in neogloboquadrinid shells collected using plankton tows compared to measured sst the calculated temperatures were within 2 c for mg ca 95 ci multiple samples from single tows generally had calculated temperatures that ranged from near surface values to temperatures consistent with calcification depths down to 70 m our work indicates that mg ca temperature calibration equations for temperate and polar foraminiferal species have a similar exponential constant but a higher pre exponential constant than those for surface dwelling tropical species therefore accurate paleotemperature reconstructions from temperate and polar species require the use of an equation distinct from those used for tropical species

accurate estimation of sea surface temperatures using dissolution corrected calibrations for mg ca paleothermometry 1 paired 18o and mg ca measurements on the same foraminiferal shells offer the ability to independently estimate sea surface temperature sst changes and assess their temporal relationship to the growth and decay of continental ice sheets the accuracy of this method is confounded however by the absence of a quantitative method to correct mg ca records for alteration by dissolution here we describe dissolution corrected calibrations for mg ca paleothermometry in which the preexponent constant is a function of size normalized shell weight 1 for g ruber 212 300 m mg ca ruber 0 025 wt 0 11 e0 095t and b for g sacculifer 355 425 m mg ca sacc 0 0032 wt 0 181 e0 095t the new calibrations improve the accuracy of sst estimates and are globally applicable with this correction eastern equatorial atlantic sst during the last glacial maximum is estimated to be 2 9 0 4 c colder than today

adaptation of a flow through leaching procedure for mg ca paleothermometry 1 mg ca ratios in planktonic foraminifera reflect calcification temperatures and are thus useful for sea surface temperature sst reconstructions despite the obvious utility of this paleoceanographic tracer problems of dissolution gametogenic calcification and contaminant phases have thus far limited confidence in mg ca based reconstructions here we show strong evidence of mg heterogeneity in foraminiferal calcite by sequentially measuring the composition of different forms of calcite ontogenetic gametogenic diagenetic in the same shells while monitoring and removing contaminant phases a new flow through method combines chromatographic technology and inductively coupled plasma mass spectrometry icp ms in a series of cleaning and dissolution reactions monitored continuously with time resolved analysis tra this combination of slow controlled dissolution and tra provides a complete elemental description of contaminant phases and sorts the cleaned calcium carbonate based on dissolution sensitivity examination of partially dissolved shells with electron microscopy suggests that the flow through method simulates the natural dissolution sequence and effectively separates the different calcite domains within a single foraminiferal shell heterogeneity of mg ca in foraminiferal calcite is clearly demonstrated in flow through analysis foraminiferal shells have initially high mg levels that decrease steadily throughout dissolution later dissolution yields lower mg ca which is likely due to a combination of subsurface calcification and biomineralization effects mg ca ratios from the most dissolution sensitive high mg portions of surface dwelling species in core tops are used to calculate calcification temperatures a comparison of late holocene core top data with world ocean atlas sst data indicates that the flow through method does yield viable sst estimates furthermore a depth transect in the eastern tropical pacific suggests that this approach provides the opportunity to extract initial calcification temperatures despite partial dissolution of foraminiferal shells

systematic change of foraminiferal mg ca ratios across a strong salinity gradient abstract the mg ca ratio of foraminiferal calcite is an important proxy for estimating past ocean temperatures used in conjunction with 18 o of foraminiferal calcite it allows deconvolution of temperature and ice volume signals to infer past ocean temperatures and salinities assuming the relationship between seawater 18 o and salinity is known such work assumes that temperature is the only or at least the dominant environmental controller of foraminiferal mg ca the semi enclosed mediterranean sea where salinity varies from 36 to 40 psu over a seasonal temperature range of between only 5 c to 8 c provides a relevant setting to test this assumption outside the laboratory in this study planktonic foraminifera o universa g siphonifera g bulloides and g ruber white and pink were picked from 11 box core tops spanning the mediterranean salinity gradient and analysed for their trace element concentrations mg ca ratios are higher for the associated calcification temperatures than in other regions where calibrations have been conducted and correlate poorly with calcification temperature mg ca ratios are particularly high for samples from the eastern mediterranean where salinity is unusually high correlations of mg ca with the calcification salinity are statistically significant with mg ca changing by 15 59 per psu suggesting that salinity may act as a control on mg ca ratios in addition to the dominant temperature control we show that contamination by non carbonate material and diagenetic high mg carbonate overgrowths cannot account for the observed trend of increasing mg ca with salinity a relationship between mg ca and salinity is also suggested by re analysis of calibrations from open ocean settings these new mediterranean results are from a region with unusually high salinity but suggest that the effects of salinity on the mg ca palaeothermometer should be considered even in open ocean settings particularly where large salinity changes occurred in the past

sr mg ratios of modern marine calcite empirical indicators of ocean chemistry and precipitation rate holocene biotic and abiotic marine calcite have a similar range of mg contents 0 to 22 and 4 to 21 mol mgco3 respectively yet biotic calcite has sr2 concentrations that are consistently 1250 ppm higher than those of abiotic calcite as in laboratory experiments a positive linear relation is observed between dsr and calcite mg content this produces two distinct linear trends on a plot of sr2 vs mg2 concentrations principal axes of variation for both trends have similar slopes yet distinctly different sr2 concentration intercepts biotic y 0 024x 1298 r2 0 70 abiotic y 0 027x 47 r2 0 77 the similar slopes of these trends reflect the constancy of mgca and srca ratios of modern seawater equations describing the dependence of dsr on calcite mg content are derived from both trends biotic dsr 3 16 x 10t 6 ppm mg 0 169 abiotic dsr 3 52 x 10 6 ppm mg 0 0062 characterization of sr mg trends for holocene materials allows comparison with analogous trends from ancient samples to estimate relative changes in seawater mgca and srca ratios the relatively high sr contents of biotic calcite result from rapid precipitation rates associated with shell accretion in marine organisms calcites precipitated from seawater in laboratory experiments have dsr values that are similar to those of biotic marine calcite suggesting that both precipitate at approximately the same rate our estimates of surface area normalized precipitation rates in planktonic and benthonic foraminifera are comparable to those of seeded ph stat experiments we conclude that the dsr values for biotic and experimental marine calcite are kinetically controlled whereas the lower precipitation rates of abiotic marine calcite yield dsr values that approximate equilibrium conditions experimentally derived equations describing the relation between dsr and calcite precipitation rate indicate that the offset in sr content between biotic and abiotic calcite is the result of abiotic precipitation rates that are two to five orders of magnitude lower than those of biotic precipitates however observations of naturally occurring marine cements suggest that the five order of magnitude offset best represents natural system processes

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

relative importance of the saturated and the unsaturated zones in the hydrogeological functioning of karst aquifers the case of alta cadena southern spain summary from analysis of the hydrodynamic and hydrochemical responses of karst springs it is possible to know the behaviour of the aquifers they drain this manuscript aims to contribute to the characterization of infiltration process and to determine the relative importance of the saturated zone and of the unsaturated zone in the hydrogeological functioning of carbonate aquifers using natural hydrochemical tracers thus chemical components together with temperature and electrical conductivity both punctual and continuous records have been monitored in three springs which drain alta cadena carbonate aquifer southern spain an evaluation of the percentage of the electrical conductivity frequency peaks determined for each of the three springs is linked to the chemical parameters that comprise the conductivity signal one of these springs responds rapidly to precipitation conduit flow system due to the existence of a high degree of karstification in the unsaturated zone and in the saturated zone both of which play a similar role in the functioning of the spring another spring responds to precipitation with small increases in water flow somewhat lagged because the aquifer has a low degree of karstification even in the unsaturated zone which seems to influence its functioning more strongly than does the saturated zone the third spring drains a sector of the aquifer with a moderately developed degree of karstification one that is intermediate between the other two in which both the unsaturated zone and the saturated zone participate in the functioning of the spring but with the latter zone having a stronger influence these three springs show different hydrogeological functioning although they are in similar geological and climatic contexts which show the heterogeneity of karst media and the importance of an adequate investigation for groundwater management and protection in karst areas

coccolith sr ca as a new indicator of coccolithophorid calcification and growth rate 1 polyspecific coccolith separates from core top sediments in the eastern equatorial pacific show variations of 15 in sr ca ratios across the equatorial upwelling zone with sr ca highest at the equator and decreasing off axis these variations cannot be due to changes in the sr ca of seawater which varies by less than 2 in the surface ocean variations in sr ca of coccolith sediments are similar to variations in primary productivity and alkenone estimated coccolithophorid growth rates in overlying surface waters and to caco3 rain rates measured in sediment traps because of these relationships and because calcification rate exerts a strong control on sr ca in abiogenic calcites we suggest that the observed sr ca variations in coccoliths may be strongly controlled by coccolithophorid growth and calcification rates although temperature may also influence coccolith sr ca to a lesser degree changes in dissolution intensity and coccolith assemblages appear to exert a minor influence if any on coccolith sr ca in these sediment core tops if further work confirms relationships between coccolith sr ca and coccolithophorid productivity sr ca records of past changes in coccolithophorid productivity may be useful in reconstructing past variations in the rain ratio of organic to carbonate carbon an important control on deep ocean ph and partitioning of co2 between the atmosphere and ocean in addition coccolith sr ca might provide an independent record of past changes in coccolithophorid growth rates which in combination with data on the carbon isotopic fractionation in coccolithophorid organic matter may permit more reliable calculations of past dissolved co2 in the surface ocean

pleistocene variability of the subtropical convergence at east tasman plateau evidence from planktonic foraminiferal mg ca odp site 1172a combined measurements of mg ca and stable oxygen isotopes in tests of the planktonic foraminifer g bulloides from ocean drilling program odp site 1172a east tasman plateau allowed us to reconstruct sea surface temperature sstmg ca sea surface salinity sss and hence variations in the subtropical convergence stc in the southwestern tasman sea over the last four major glacial interglacial changes during interglacials the commonly enhanced sstmg ca and sss correspond to a lowered marine productivity and a lowered terrigenous flux implying that the stc separating cool high nutrient subantarctic surface water from warm saline oligotrophic subtropical surface water and hence the band of zonal westerlies responsible for the eolian dust flux were located south of east tasman plateau the warm east australian current was well established during warm periods and propagated far south during glacial times sstmg ca and sss were lower while both marine productivity and eolian flux increased such conditions prevailed during glacial marine isotope stages mis 12 mis 10 and to a lesser degree mis 6 and implied the extended northward influence of subantarctic surfacewater and a shift of the stc to 44 s the overall climatic signal at site 1172a appears to be largely attenuated when compared to published climate records from comparable latitudes to the west and to the east sstmg ca amplitudes were more pronounced in the subantarctic indian ocean and at chatham rise they exhibit a consistent pattern suggesting that latitudinal shifts of the stc occurred synchronously in the subantarctic indian ocean and at chatham rise but were largely damped at east tasman plateau due to the influence of the east australian current

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

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

western caribbean sea surface temperatures during the late quaternary 1 mg ca ratios in the planktonic foraminifera globigerinoides ruber from colombian basin core odp 999a suggest that caribbean sea surface temperatures ssts were from 2 1 to 2 7 c colder than the present during the last three glacial maximums in comparison faunal derived ssts simmax method show that august ssts in the caribbean varied 2 c over the past 360 kyr whereas february ssts varied between 21 0 c and 26 5 c changes in the mg ca sst record contain a strong 23 kyr periodicity suggesting the mg ca sst record reflects a warm season weighted sst average rather than an annual mean sst combining several dissolution indices we identify brief periods of decreased carbonate preservation in our record and show that mis 11 stands out as the most intensive dissolution cycle in the caribbean over the last 460 kyr comparison of caribbean sst change with a similar estimate of tropical sst variability in the western pacific over the past 360 kyr reveals shifts in the east west tropical sst gradient that are coeval with glacial interglacial climate change and consistent both with a southward migration of the glacial itcz and with a glacial el nino like mode of tropical circulation

controls on shell mg ca and sr ca in cultured planktonic foraminiferan globigerinoides ruber white mg ca and sr ca ratios were determined on a single species of planktonic foraminiferan globigerinoides ruber white collected from the gulf of eilat and cultured in seawater at five different salinities 32 to 44 five temperatures 18 to 30 c and four ph values 7 9 to 8 4 the mg ca temperature calibration of cultured g ruber with an exponential slope of 8 3 c agrees well with previously published calibrations from core tops and sediment traps however the dependence of mg ca on salinity with an exponential slope of 5 3 psu is also significant and should be included in the calibration equation with this purpose we calculated a calibration equation for g ruber dependent on both temperature and salinity within the 95 confidence limits mg ca mmol mol exp 0 06 0 02 s psu 0 08 0 02 t c 2 8 1 0 r2 0 95 the influence of ph on mg ca ratios is negligible at ambient seawater ph 8 1 to 8 3 however we observe a dominating ph control on shell mg ca when the ph of seawater is lower than 8 0 sr ca in g ruber shows a significant positive correlation with average growth rate presumably part of the variability in shell sr ca in the geological record is linked to changes in growth rates of foraminifera as a response to changing environmental conditions

response of planktic foraminiferal size to late quaternary climate change 1 geographical size distribution within entire holocene foraminiferal assemblages is related to global environmental gradients such as temperature primary productivity and environmental variability this study demonstrates that these correlations are also recognizable in late quaternary assemblages from three locations in the south atlantic on temporal and latitudinal scales the size response to temporal paleoenvironmental changes during glacial interglacial cycles mimics the geographic holocene size variability the amplitude of size variability is directly related to the amplitude of the climatic fluctuations as shown by the stable size temperature relationship over time the documented changes in the assemblage size are caused by species replacement and intraspecific size variability the relative importance of these processes depends on the environmental setting species have been shown to reach their maximum size and abundance under certain optimum conditions and decrease in size if environmental conditions differ from these optima we confirm that late quaternary species sizes were largest at paleotemperatures identical to holocene ones

a core top assessment of proxies for the ocean carbonate system in surface dwelling foraminifers we have assessed the reliability of several foraminifer hosted proxies of the ocean carbonate system 11b b ca and u ca using holocene samples from the atlantic and pacific oceans we examined chemical variability over a range of test sizes for two surface dwelling foraminifers globigerinoides sacculifer and globigerinoides ruber measurements of 11b in g ruber show no significant relationship with test size in either atlantic or pacific sites and appear to provide a robust proxy of surface seawater ph likewise there is no significant variability in the 11b of our atlantic core top g sacculifer but we find that 11b increases with increasing test size for g sacculifer in the pacific these systematic differences in 11b are inferred to be a consequence of isotopically light gametogenic calcite in g sacculifer and its preferential preservation during postdepositional dissolution the trace element ratio proxies of ocean carbonate equilibria u ca and b ca show systematic increases in both g ruber and g sacculifer with increasing test size possibly as a result of changing growth rates this behavior complicates their use in paleoceanographic reconstructions in keeping with several previous studies we find that mg ca ratios increase with increasing size fraction in our well preserved atlantic g sacculifer but not in g ruber in contrast to previous interpretations we suggest that these observations reflect a proportionally larger influence of compositionally distinct gametogenic calcite in small individuals compared to larger ones as with 11b this influences g sacculifer but not g ruber which has negligible gametogenic calcite

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

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

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

trace element cartography of globigerinoides ruber shells using particle induced x ray emission 1 micro particle induced x ray emission pixe is a nondestructive elemental analysis technique that can be used to map the distribution of elements with a spatial resolution of 4 m2 and a penetration depth of 2 m in a calcite matrix to test its potential to improve our understanding of trace element distribution in foraminifera shells we mapped the mg distribution across individual chambers of the planktonic species globigerinoides ruber g ruber shells were picked from equatorial atlantic surface sediments sierra leone rise they ranged from well preserved to heavily dissolved tests the mapping of trace elements across test chambers made it possible to discriminate between variability inherent to the shell material and heterogeneity linked to contaminant phases contaminating mineral phases were characterized by high mg concentrations mg ca 19 7 mmol mol and high levels of si al and fe mg ca values of well preserved shells ranged from 3 9 to 4 5 mmol mol the mg to ca ratios of partially dissolved shells varied between 1 8 and 3 4 mmol mol between outer and inner chambers low and homogeneous mg ca values of 2 0 and 2 3 mmol mol were determined for chambers of a severely dissolved test

variation of foraminiferal sr ca over quaternary glacial interglacial cycles evidence for changes in mean ocean sr ca 1 records of sr ca changes in planktonic and benthic foraminifera from diverse hydrographic settings reveal coherent variability 5 1 between ocean basins and between surface and deep waters over the past 300 kyr there is a general increase in foraminiferal sr ca over the penultimate glaciation declining to minimum values during stage 5 and an increase in sr ca from stage 5 through stage 2 coincident changes in benthic foraminifera records from the atlantic and pacific basins imply that sr ca variations are not dominated by dissolution planktonic culturing data provide evidence that the downcore sr ca variations are not controlled by temperature changes and suggest only a small influence of salinity and ph variation common to the records is most readily explained by changes in mean ocean sr ca if fossil foraminifera reliably record higher glacial seawater sr ca coral sr paleothermometry would underestimate sea surface temperature during glacialepisodes

interlaboratory comparison study of mg ca and sr ca measurements in planktonic foraminifera for paleoceanographic research thirteen laboratories from the usa and europe participated in an intercomparison study of mg ca and sr ca measurements in foraminifera the study included five planktonic species from surface sediments from different geographical regions and water depths each of the laboratories followed their own cleaning and analytical procedures and had no specific information about the samples analysis of solutions of known mg ca and sr ca ratios showed that the intralaboratory instrumental precision is better than 0 5 for both mg ca and sr ca measurements regardless whether icp oes or icp ms is used the interlaboratory precision on the analysis of standard solutions was about 1 5 and 0 9 for mg ca and sr ca measurements respectively these are equivalent to mg ca based temperature repeatability and reproducibility on the analysis of solutions of 0 2 c and 0 5 c respectively the analysis of foraminifera suggests an interlaboratory variance of about 8 rsd for mg ca measurements which translates to reproducibility of about 2 3 c the relatively large range in the reproducibility of foraminiferal analysis is primarily due to relatively poor intralaboratory repeatability about 1 2 c and a bias about 1 c due to the application of different cleaning methods by different laboratories improving the consistency of cleaning methods among laboratories will therefore likely lead to better reproducibility even more importantly the results of this study highlight the need for standards calibration among laboratories as a first step toward improving interlaboratory compatibility

foraminiferal mg ca increase in the caribbean during the pliocene western atlantic warm pool formation salinity influence or diagenetic overprint we constructed a high resolution mg ca record on the planktonic foraminifer globigerinoides sacculifer in order to explore the change in sea surface temperature sst due to the shoaling of the isthmus of panama as well as the impact of secondary factors like diagenesis and large salinity fluctuations the study covers the latest miocene and the early pliocene 5 6 3 9 ma and was combined with 18o to isolate changes in sea surface salinity sss before 4 5 ma sstmg ca and sss show moderate fluctuations indicating a free exchange of surface ocean water masses between the pacific and the atlantic the increase in 18o after 4 5 ma represents increasing salinities in the caribbean due to the progressive closure of the panamanian gateway the increase in mg ca toward values of maximum 7 mmol mol suggests that secondary influences have played a significant role evidence of crystalline overgrowths on the foraminiferal tests in correlation with aragonite sr ca and productivity cyclicities indicates a diagenetic overprint on the foraminiferal tests laser ablation inductively coupled plasma mass spectrometry analyses however do not show significantly increased mg ca ratios in the crystalline overgrowths and neither do calculations based on pore water data conclusively result in significantly elevated mg ca ratios in the crystalline overgrowths alternatively the elevated mg ca ratios might have been caused by salinity as the 18o record of site 1000 has been interpreted to represent large fluctuations in sss and cultivating experiments have shown an increase in mg ca with increasing salinity we conclude that the mg ca record 4 5 ma can only reliably be considered for paleoceanographical purposes when the minimum values not showing any evidence of secondary influences are used resulting in a warming of central caribbean surface water masses after 4 5 ma of 2 c

magnesium and strontium compositions of recent benthic foraminifera from the coral sea australia and prydz bay antarctica analyses of the mg ca and sr ca ratios of the modern benthic foraminifera cibicides wuellerstorfi epifaunal and uvigerina species infaunal from the coral sea and cibicides refulgens epifaunal and trifarina angulosa infaunal from prydz bay antarctica revealed relationships with temperature that have possible applications for reconstructions of bottom water paleotemperatures a positive relationship exists between the mg ca and sr ca ratios of cibicides wuellerstorfi and cibicides refulgens and ambient temperatures at least within the range of 2 and 6 c for the correlation between mg ca compositions and temperature the r2 values range from 0 78 c wuellerstorfi alone to 0 88 c wuellerstorfi and c refulgens together at present the mg ca temperature relationship must be regarded as tentative because of significant overlap of standard error values the relationship between the sr ca compositions of c wuellerstorfi and bottom water temperature yields an r2 value of 0 95 these results indicate that sr ca and possibly mg ca ratios of cibicides wuellerstorfi may provide useful information for the assessment of paleotemperature single species data are presently insufficient to assess the influence of ambient temperature on trace element compositions of uvigerina species trifarina angulosa may have mg ca compositions which are positively related to temperature but sr ca values seem unaffected by temperature this may be due to pore water influences on infaunal tests or to vital effects although more modern data are needed our present results suggest that sr ca ratios and possibly mg ca ratios of some benthic foraminifera have the potential to be useful paleothermometers at least within a temperature range of 2 to 6 c

the relationship between shell size and mg ca sr ca δ18o and δ13c of species of planktonic foraminifera the relationship between shell size and mg ca sr ca 18o and 13c of planktonic foraminiferal calcite has been investigated using seventeen species in six different size fractions mg ca increases and sr ca decreases with increasing size except for two globorotaliid species which show the opposite trend the changes in mg ca broadly follow 18o calcification temperatures except that surface and near surface dwelling species show larger changes in mg ca than can be accounted for by differences in calcification temperature derived from 18o the increases in mg ca and decreases in sr ca vary linearly with the well established increase in 13c with size this is consistent with smaller individuals calcifying faster than larger individuals and larger individuals forming calcite that more closely reflects seawater temperature and composition it appears that variations in calcification rate affect mg and sr shell chemistry the observations may account for part of the temporal variability in foraminiferal sr ca within a single size fraction that has been attributed to changes in seawater sr ca

surface ocean ph response to variations in pco2 through two full glacial cycles abstract knowledge of past atmospheric pco 2 is important for evaluating the role of greenhouse gases in climate forcing ice core records show the tight correlation between climate change and pco 2 but records are limited to the past 900 kyr we present surface ocean ph and pco 2 data reconstructed from boron isotopes in planktonic foraminifera over two full glacial cycles 0 140 and 300 420 kyr the data co vary strongly with the vostok pco 2 record and demonstrate that the coupling between surface ocean chemistry and the atmosphere is recorded in marine archives allowing for quantitative estimation of atmospheric pco 2 beyond the reach of ice cores