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

mg ca ratios of single planktonic foraminifer shells and the potential to reconstruct the thermal seasonality of the water column mg ca ratios of surface and subsurface dwelling foraminifera provide valuable information about the past temperature of the water column planktonic foraminifera calcify over a period of weeks to months therefore the range of mg ca temperatures obtained from single specimens potentially records seasonal temperature changes we present solution derived mg ca ratios for single specimens of the planktonic foraminifera species globigerinoides ruber pink globigerinoides ruber white and globorotalia inflata from a sediment trap off northwest africa 20 45 6 n 18 41 9 w cleaning of single specimens was achieved using a flow through system in order to prevent sample loss mg ca ratios of surface dwelling g ruber pink show strong seasonality linked to sea surface temperature mg ca ratios of g ruber white do not show such seasonality subsurface dwelling g inflata flux is largest during the main upwelling season but mg ca ratios reflect annual temperatures at intermediate water depths the sediment trap time series suggests that changes in the range of mg ca ratios exhibited by single specimens of g ruber pink and g inflata from the sedimentary record should provide information on the past temperature range under which these species calcified statistical analysis suggests detectable changes in the mg ca range are 0 80 mmol mol g ruber pink and 0 34 mmol mol g inflata for g ruber pink such changes would indicate changes in the seasonal sea surface temperature range 4 c or a shift in the main calcification and reproductive period for g inflata such changes would indicate 1 7 c changes in the thermocline temperature or a change in the depth habitat

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

chamber formation leads to mg ca banding in the planktonic foraminifer neogloboquadrina pachyderma many species of planktonic foraminifera show distinct banding in the intratest distribution of mg ca this heterogeneity appears biologically controlled and thus poses a challenge to mg ca paleothermometry the cause of this banding and its relation with chamber formation are poorly constrained and most of what we know about intratest mg ca variability stems from culture studies of tropical symbiont bearing foraminifera here we present data on the non spinose symbiont barren neogloboquadrina pachyderma from the subpolar north atlantic where wintertime mixing removes vertical gradients in temperature and salinity this allows investigation of biologically controlled mg ca intratest variability under natural conditions we find that intratest mg ca varies between 0 1 and 7 mmol mol even in winter specimens high mg ca bands occur at the outer edge of the laminae indicating reduced mg removal at the end of chamber formation our data thus provide new constraints on the timing of the formation of such bands and indicate that their presence is intrinsic to the chamber formation process additionally all specimens are covered with an outer crust consisting of large euhedral crystals the composition of the crust is similar to the low mg ca bands in the laminar calcite in winter and summer specimens indicating a tight biological control on crust formation and composition nevertheless despite high intratest variability the median mg ca of summertime tests is higher than that of wintertime tests this provides support for mg ca paleothermometry but to improve the accuracy of paleotemperature estimates biological effects on mg incorporation need to be better accounted for

surface and subsurface seawater temperature reconstruction using mg ca microanalysis of planktonic foraminifera globigerinoides ruber globigerinoides sacculifer and pulleniatina obliquiloculata laser ablation inductively coupled plasma mass spectrometry microanalyses of mg ca across individual final chambers of three planktonic foraminifera species globigerinoides ruber g sacculifer and pulleniatina obliquiloculata reveal significant interspecies differences in test mg concentrations whereas these three species have similar mg ca values at low sea surface temperatures similar to 22 degrees c they diverge markedly at high sea surface temperatures similar to 29 degrees c explanations for these differences in species mg ca values based on detailed comparison of species intratest mg ca distributions suggest that compositional variability within tests cannot account for the observed deviation of species mg ca values in warm water equatorial regions multiple regression modeling and delta o 18 analysis of globigerinoides sacculifer tests indicate that interspecies differences in mg ca values result from different depth habitats the average mg ca values of g ruber final chambers reflect the temperature of the surface mixed layer 0 25 m whereas those of g sacculifer and pulleniatina obliquiloculata correlate best with subsurface temperatures at 50 75 m and 100 125 m water depths respectively mg ca calibration to the temperatures at these depths reveals a similar temperature control on mg test composition in all species combining our results with mg ca values from published culturing experiments we derive a generalized equation for the effect of temperature and seawater salinity on foraminiferal mg ca we also show that the mg ca composition of specific calcite layers within foraminiferal tests including the low mg ca layers of globigerinoides ruber and g sacculifer and the cortex layer of pulleniatina obliquiloculata correlates with seawater temperature and can be used as an additional proxy for seawater temperature

mid holocene el nino southern oscillation enso attenuation revealed by individual foraminifera in eastern tropical pacific sediments holocene reconstructions of the el nino southern oscillation enso provide valuable perspective on its recent evolution and can be important for assessing its future optimal assessment of past enso variability requires observations from its center of action in the eastern equatorial pacific but these are limited due to paucity of high resolution paleoceanographic archives e g corals here we use a new approach to quantify past enso variance based on the oxygen isotopic composition 18 o of individual foraminifera globigerinoides ruber from deep sea sediments in the enso source region individual g ruber foraminifera behave as monthly recorders of sea surface conditions including enso extremes circumventing the lack of annual resolution in the sediments intrapopulation 18 o distributions derived with this method from a core near the galapagos islands reveal mid holocene reductions in variance of 50 requiring drastic attenuation of the enso amplitude furthermore mg ca thermometry indicates that mid holocene background conditions were accompanied by a stronger zonal temperature gradient that coincided with a northward displaced intertropical convergence zone itcz the results suggest that the position of the itcz is an important factor in the low frequency modulation of enso and could influence its future evolution

mid holocene climate and culture change in the atacama desert northern chile abstract twenty archaeological campsites intercalated between more than 30 debris flows caused by heavy rainfall events between 6200 and 310014c yr b p have recently been discovered at quebrada puripica in the atacama desert of northern chile this record provides detailed information about extreme short lived climatic events during the hyperarid mid holocene period for the first time we found evidence of continuous human occupation in this area filling the regional hiatus in the atacama basin silencio arqueologico between 8000 and 480014c yr b p the transformation of early archaic hunters into the complex late archaic cultural tradition was an adaptive process during this time the site was a local ecological refuge with abundant resources in a generally hostile environment

the influence of skeletal micro structures on potential proxy records in a bamboo coral assessing the physicochemical variability of the deeper ocean is currently hampered by limited instrumental time series and proxy records bamboo corals isididae form a cosmopolitan family of calcitic deep sea corals that could fill this information gap via geochemical information recorded in their skeletons here we evaluate the suitability of high resolution chemical imaging of bamboo coral skeletons for temperature and nutrient reconstruction the applied elemental mapping techniques allow to verify the suitability of the chosen transect on the sample section for paleo reconstructions and enhance the statistical precision of the reconstruction we measured mg ca via electron microprobe at 1 m resolution and ba ca via laser ablation icp ms at 35 m resolution in a historic specimen of keratoisis grayi from the blake plateau off eastern florida long term growth temperatures of 7 1 3 4 c 2 sd that are in agreement with recent ambient temperature range can be reconstructed from mg ca ratios provided that anomalously mg enriched structural features around the central axis and isolated features related to tissue attachment are avoided for reconstruction skeletal ba ca measurements reflect mean seawater barium ba sw concentrations ba sw 51 24 nmol kg 1 2 sd in agreement with instrumental data 47 nmol kg 1 we show for the first time that ba ca forms concentric structures in a bamboo coral skeleton section our investigations suggest that while bamboo coral skeletons do record environmental parameters in their mean chemical composition the magnitude of environmental variability reconstructed from high resolution chemical maps exceeds that expected from instrumental time series this necessitates additional investigation of the factors driving bamboo coral skeletal composition

microdistribution of mg ca sr ca and ba ca ratios in pulleniatina obliquiloculata test by using a nanosims implication for the vital effect mechanism the mg ca ratio within foraminiferal calcareous tests shells is widely used to reconstruct past seawater temperature however recent studies reported that the organic components within a test affect the mg ca distribution in this study we have measured the mg ca sr ca and ba ca ratios within the planktonic foraminifera pulleniatina obliquiloculata by using a nanosims secondary ion mass spectrometer sims which has excellent spatial resolution 1 m and allows us to compare the distribution of chemical compositions with that of the organic components element compositions show banding distributions composed of alternately higher and lower values of those elemental ratios the mg ca ratios previously considered to be mainly controlled by calcification temperature show larger variations than the values expected from the seawater temperature at the habitat depth of p obliquiloculata comparison of the elemental distribution with the test microstructure reveals that the bands of high mg ca and sr ca ratios correspond with layers of the organic components such coincidence suggests that the organic components strongly affect the mg ca and sr ca ratios within a test in spite of the heterogeneous distribution temperature estimated from the averaged mg ca ratio within a test is consistent with seawater temperature at the habitat depth of p obliquiloculata indicating that whole mg ca ratio of foraminiferal test may be useful as paleotemperature proxy in contrast to the mg ca ratio the heterogenity in ba ca ratio which previously has been considered to be mainly controlled by the ambient seawater composition is not fully matched with the layers of the organic compositions although the organic components concentrate ba other unknown factors appear to also cause heterogenity in ba incorporation

reevaluation of the oxygen isotopic composition of planktonic foraminifera experimental results and revised paleotemperature equations cultured planktonic foraminifera orbulina universa symbiotic and globigerina bulloides nonsymbiotic are used to reexamine temperature 18o relationships at 15 25 c relationships for both species can be described by linear equations equations for o universa grown under low light ll and high light hl share a slope of 4 80 0 21 c 1 with a hl ll offset of 0 33 due to symbiont photosynthetic activity the effect of co32 on o universa is 0 002 mol 1 kg 1 and is insensitive to temperature for g bulloides ontogenetic effects produce size related trends in temperature 18o whereby larger shells are enriched in 18o relative to smaller specimens the o universa temperature 18o relationships are more accurate than previously published equations for describing plankton tow data our equations do not explain planktonic core top data with the same precision but provide a good fit to benthic cibicidoides data below 10 c temperature 18o relationships for g bulloides provide good agreement with field data for this species from the northeast pacific

reconstructing the stable isotope geochemistry and paleotemperatures of the equatorial atlantic during the last 150 000 years results from individual foraminifera this study represents an attempt to extract paleoclimatic data from the deep sea record by analyzing foraminiferal shells individually using the oxygen 18o and carbon 13c isotopic composition of individual orbulina universa and neogloboquadrina dutertrei we present an approach to reconstruct the 18o of seawater 18ow the 13c of co2 and seasonal maximum sea surface temperatures sst in the western and eastern equatorial atlantic we examine the glacial and interglacial extremes of the last 150 000 years isotope stages 1 2 5e and 6 comparison of recent water column hydrography with reconstructions from core top assemblages shows that o universa and n dutertrei 18o and 13c values accurately record hydrographic conditions in the mixed layer and upper thermocline at both sites by analyzing shells individually we can evaluate the effect of bioturbation on the range of 18o and 13c values in each interval and take it into consideration in our data interpretations downcore results show that n dutertrei 18o values in the western equatorial atlantic reflect glacial to interglacial changes in 18ow due to continental ice formation 18o 1 30 we use changes in n dutertrei 18o values between core intervals to estimate the ice volume effect in paleotemperature calculations for the mixed layer to validate the use of o universa for mixed layer reconstructions we have added individual globigerinoides sacculifer data for stages 1 and 2 at both sites paleotemperature reconstructions from o universa 18o values indicate that maximum seasonal mixed layer temperatures in the equatorial atlantic decreased by at most 2 6 c between isotope stages 1 and 2 and by no more than 3 4 c between stages 1 and 6 individual shell data from g sacculifer yield similar results indicating that maximum o universa 18o values reflect the mixed layer environment in agreement with climate long range investigation mapping and prediction climap 1981 sst reconstructions for stage 2 these data indicate little change between glacial and interglacial paleotemperatures in the equatorial atlantic an electronic supplement of this material may be obtainedon a diskette or anonymous ftp from kosmos agu org login to agu s ftp account using anonymous as theusername and guest as the password go to the rightdirectory by typing cd apend type ls to see what files areavailable type get and the name of the file to get it finally type exit to leave the system paper 95pa03773 reconstructing the stable isotope geochemistry andpaleotemperatures of the equatorial atlantic during the last150 000 years results from individual foraminifera katharina billups and howard j spero diskette may beordered from american geophysical union 2000 floridaavenue n w washington dc 20009 15 00 paymentmust accompany order

novel observations on biomineralization processes in foraminifera and implications for mg ca ratio in the shells stable isotopes and trace elements in foraminifera shells are important for determining the paleochemistry of the ocean and mg ca ratios and 1 8 o values in foraminifera have recently been used to determine simultaneously the temperature and salinity of past oceans however large variations between species and significant mg intra shell heterogeneity indicate a major role for biological factors in determining the mg ca ratio in foraminifera our novel in vivo observations on the biomineralization process of perforate foraminifera show that their calcareous wall is composed of two different calcite types a thin high mg primary layer and low mg layers that cover the primary layer on both sides the data may suggest that two biomineralization pathways are employed in the formation of the different calcite types a new conceptual framework is provided to explain part of the mg heterogeneity in foraminiferal shells and the variable sensitivity of the mg ca ratio to temperature in different species

variability of mg ca and sr ca between and within the planktonic foraminifers globigerina bulloides and globorotalia truncatulinoides the variability in mg ca and sr ca within individual tests and chambers of tests and samples consisting of differing numbers of individuals was determined for globigerina bulloides and globorotalia truncatulinoides in a north atlantic core top sample 52 918 n 16 917 w the variability in mg ca and sr ca within individual tests and chambers was determined by electron microprobe and samples consisting of variable sample size were measured using inductively coupled plasma optical emission spectrometer icp oes large compositional heterogeneity was found within individual chambers and within the test as a whole of the two species and the presence of regions with up to 10 mmol mol mg ca especially in g bulloides mean mg ca decreases in successive chambers of g bulloides especially the 300 355 m fraction and is accompanied by decreasing variance but is not statistical significant sr ca is much more homogeneously distributed with a normal distribution and shows no differences from chamber to chamber the variability of mg ca and sr ca decreases with increasing sample size from single to five to twenty tests per sample approximately as for a normal distribution with greater variability for g bulloides than for g truncatulinoides equivalent to uncertainties in temperature n 20 of 1 1 c and 0 7 c for the two species within the whole of the sediment mixed layer

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

constraining past seawater δ18o and temperature records developed from foraminiferal geochemistry paired measurements of magnesium to calcium ratios mg ca and the stable oxygen isotopic composition 18o in foraminifera have significantly advanced our knowledge of the climate system by providing information on past temperature and seawater 18o 18osw a proxy for salinity and ice volume however multiple sources of uncertainty exist in transferring these downcore geochemical data into quantitative paleoclimate reconstructions here we develop a computational toolkit entitled paleo seawater uncertainty solver psu solver that performs bootstrap monte carlo simulations to constrain these various sources of uncertainty psu solver calculates temperature and 18osw and their respective confidence intervals using an iterative approach with user defined errors calibrations and sea level curves our probabilistic approach yields reduced uncertainty constraints compared to theoretical considerations and commonly used propagation exercises we demonstrate the applicability of psu solver for published records covering three timescales the late holocene the last deglaciation and the last glacial period we show that the influence of salinity on mg ca can considerably alter the structure and amplitude of change in the resulting reconstruction and can impact the interpretation of paleoceanographic time series we also highlight the sensitivity of the records to various inputs of sea level curves transfer functions and uncertainty constraints psu solver offers an expeditious yet rigorous approach to test the robustness of past climate variability inferred from paired mg ca 18o measurements

seasonal changes in species composition numbers mass size and isotopic composition of planktonic foraminifera settling into the deep sargasso sea abstract planktonic foraminifera recovered from six successive sediment trap samples collected over fourteen months at a depth of 3200 m near bermuda show varied responses to seasonal changes in the near surface hydrography these include changes in species composition and within species changes in number of individuals collected per unit time average size and weight of individuals and in oxygen and carbon isotopic composition a total of seventeen species were identified and eleven were sufficiently abundant for isotopic analysis in at least some of the samples the accumulations on the sea floor of some of these species can be expected to contain a strong seasonal component in their oxygen isotopic composition which may be utilized in paleoclimatic and paleo oceanographic reconstructions best suited to this purpose are those species which form their tests in isotopic equilibrium with surface water and whose abundance is confined to a portion of the year only the best examples are pulleniatina o bliguiloculata globigerinoides conglobatus and neogloboquadrina dutertrei globigerinoides ruber is a good estimator of the average surface water temperature because it occurs in rather even abundance throughout the year hastigerina pelagica though very abundant in surface water is practically eliminated even before arrival on the sea floor by partial resorption and structural weakening of the tests during gametogenesis orbulina universa globorotalia truncaltulinoides and globorotalia hirsuta show morphological and istopic evidence for contibnued calcification in deeper water after initial test formation near ther surface globigerina bulloides represents the most striking example of oxygen isotopic disequilibrium with sea water

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

salinity bias on the foraminifera mg ca thermometry correction procedure and implications for past ocean hydrographic reconstructions 1 mg ca in foraminiferal calcite has recently been extensively used to estimate past oceanic temperatures here we show however that the mg ca temperature relationship of the planktonic species globigerinoides ruber is significantly affected by seawater salinity with a 1 psu change in salinity resulting in a 1 6 c bias in mg ca temperature calculations if not accounted for such a bias could lead for instance to systematic overestimations of mg ca temperatures during glacial periods when global ocean salinity had significantly increased compared to today we present here a correction procedure to derive unbiased sea surface temperatures sst and 18osw from g ruber tmg ca and 18of measurements this correction procedure was applied to a sedimentary record to reconstruct hydrographic changes since the last glacial maximum lgm in the western pacific warm pool while uncorrected tmg ca data indicate a 3 c warming of the western pacific warm pool since the lgm the salinity corrected sst result in a stronger warming of 4 c

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

mg ca in the benthic foraminifera cibicidoides wuellerstorfi and cibicidoides mundulus temperature versus carbonate ion saturation magnesium calcium mg ca ratios in two widely used benthic foraminiferal species cibicidoides wuellerstorfi and cibicidoides mundulus cibicidoides kullenbergi picked from global ocean core tops and from six cores in the north atlantic ocean have been measured to investigate mg ca variability cleaning effect and influences from bottom water temperature bwt and deep water carbonate ion saturation co32 replicate measurements of the two species reveal mg ca variability of 0 07 0 07 mmol mol compared with mg ca in samples cleaned by oxidative cleaning mg ca ratios are significantly lowered by 0 10 0 09 mmol mol in samples cleaned by reductive cleaning likely due to preferential leaching during the reductive cleaning step the cleaning influence is large relative to glacial interglacial mg ca changes 0 05 0 31 mmol mol by this study regression of core top data from a wide range of locations show that c wuellerstorfi mg ca is strongly affected by deep water co32 with a sensitivity of 0 009 mmol mol per mol kg when bwt is included in regressions the correlation is slightly more significant with a weak bwt sensitivity on mg ca of between 0 03 0 01 and 0 07 0 02 mmol mol per c because co32 and bwt co vary for most core top samples an alternate method of separating the two effects was made by comparing glacial to interglacial changes in mg ca from a depth transect of north atlantic cores where the bwt and carbonate ion histories since the last glacial period have been well constrained results from this transect suggest that the bwt effect is 0 03 mmol mol per c weaker than inferred from the core top study therefore core top and down core data suggest that c wuellerstorfi mg ca is insensitive to bwt changes the weak bwt effect when compared with natural variability complicates the use of mg ca in this species to reconstruct past bwt taking all measured samples from various environments into account c mundulus mg ca ratios show no correlation with bwt or deep water co32

planktic foraminifers as recorders of seawater ba ca abstract recent studies have used the ba ca ratio of planktic foraminifer shells as a proxy for river run off at oceanic sites near estuaries such studies assume that the ba ca ratio in planktic foraminifer shells is primarily controlled by the ba ca concentration of seawater and that other parameters such as salinity temperature and ph do not compromise the primary ba concentration relationship here we provide new insights from culture experiments and review published studies to confirm that environmental parameters including ph temperature salinity and symbiont photosynthesis do not affect ba substitution into planktic foraminiferal calcite the partition coefficient for ba in spinose planktic foraminifers is estimated as d ba 0 15 0 05 95 confidence limits the same factor also seems applicable to the non spinose genus neogloboquadrina but not to specimens of the non spinose genus globorotalia

the carbonate clastic cycles of the east alpine raibl group result of third order sea level fluctuations in the carnian abstract the carnian raibl group of the eastern alps consists of three 50 100 m thick alternating carbonate and clastic third order cycles each of which can be traced for hundreds of kilometers tectono eustatic sea level fluctuations of a few tens of metres spanning a few millions of years are the driving mechanism of this cyclicity the carbonate intervals represent restricted marginal marine tidal and evaporitic environments the clastic intervals represent inner and outer shelf facies and are related to the fluviatile schilfsandstein of the germanic facies belt in the raibl group contrary to other carbonate clastic depositional settings relative sea level lowstands are dominated by carbonate production and highstands are dominated by clastic deposition each of the three raibl cycles corresponds to a type 2 sequence containing shelf margin transgressive and highstand systems tracts during sea level lowstands deltaic point sources were near the shelf margin allowing clastics to bypass the carbonate platform this setting corresponds to a shelf margin systems tract transgressive and highstand systems tracts developed during the subsequent sea level rise as deltaic clastics were reworked and redistributed over the carbonate platform and the deltas retrograded to the inner shelf the highstand systems tracts are capped by a type 2 sequence boundary which is conformable in the study area the systems tracts can be further subdivided into shallowing upward subcycles caused by fourth order sea level fluctuations believed to represent milankovitch rhythms the middle raibl cycle is consistently thinner and may represent a shorter termed third order sea level fluctuation our data also corroborate a second order transgressive trend for the carnian

seasonal changes in the isotopic composition of planktonic foraminifera collected in panama basin sediment traps abstract isotopic analyses have been made on five species of planktonic foraminifera collected in two deployments of parflux mark ii time series sediment traps in the panama basin the automated sampling system on the traps provided 4 one month samples from 29 july to 16 november 1979 and 6 two month samples from december 1979 to november 1980 the 18o values of globigerinoides ruber and globigerinoides sacculifer in this region are primarily affected by a low salinity surface layer that forms during the early winter these species each show a 1 total range in 18o the 18o values of the colder water species globorotalia menardii neogloboquadrina dutertrei and globorotalia theyeri show smaller seasonal changes in 18o the 13c values of g ruber and g sacculifer exhibit small seasonal changes 0 35 and 0 4 respectively despite large seasonal changes in surface water productivity the colder water species exhibit only slightly larger changes in 13c up to 0 55 throughout the year all colder water species exhibit minimum or near minimum 13c values during february and march which is the period of maximum upwelling and primary productivity seasonal variations in the flux of foraminifera in the water column at this location will have only a small effect on the isotopic composition of the sediment assemblage extreme values of 18o and 13c do not occur during the periods which are associated with the high flux of foraminiferal tests

ecological and temperature controls on mg ca ratios of globigerina bulloides from the southwest pacific ocean we present mg ca data for globigerina bulloides from 10 core top sites in the southwest pacific ocean analyzed by laser ablation inductively coupled plasma mass spectrometry la icpms mg ca values in g bulloides correlate with observed ocean temperatures 7 degrees c 19 degrees c and when combined with previously published data an integrated mg ca temperature calibration for 7 degrees c 31 degrees c is derived where mg ca mmol mol 0 955 x e 0 068 x t r 2 0 95 significant variability of mg ca values 20 30 was found for the four visible chambers of g bulloides with the final chamber consistently recording the lowest mg ca and is interpreted in part to reflect changes in the depth habitat with ontogeny incipient and variable dissolution of the thin and fragile final chamber and outermost layer concomitantly added to all chambers caused by different cleaning techniques prior to solution based icpms analyses may explain the minor differences in previously published mg ca temperature calibrations for this species if the lower mg ca of the final chamber reflects changes in depth habitat then la icpms of the penultimate or older chambers will most sensitively record past changes in near surface ocean temperatures mean size normalized g bulloides test weights correlate negatively with ocean temperature t 31 8 x e 30 5xwtn r 2 0 90 suggesting that in the southwest pacific ocean temperature is a prominent control on shell weight in addition to carbonate ion levels

exploring the dissolution effect on the intrashell mg ca variability of the planktic foraminifer globigerinoides ruber the mg ca ratio of the planktic foraminifer globigerinoides ruber is widely used for reconstructing past sea surface temperatures the shell mg ca ratio is also lowered by dissolution which results in lower sea surface temperature estimates in partially dissolved shells here we use an electron microprobe image mapping technique to map the intrashell variability of the mg ca ratio in g ruber white sensu stricto shells to explore changes in the intrashell mg ca ratio associated with dissolution we examine shells from shallow and deep cores ceara rise western tropical atlantic from the holocene and last glacial maximum that represent a preservational gradient image map results show that the mg ca ratio is highly variable both within a single shell and among samples obtained from the same sediment interval our results show that intrashell mg ca variability is retained in samples that have undergone dissolution quantitative analysis of the data from mg ca mapping suggests that preferential loss of high mg ca calcite alone cannot account for the difference in intrashell mg ca variability of shells from shallow and deep cores in both time periods rather the data imply that in g ruber analyzed in this study there is a loss of high mg ca ratios accompanied by a more uniform lowering of mg ca over the range of intershell mg ca variability of shells subjected to dissolution at the 1 m resolution of the microprobe analysis in this study

calibration of the mg ca of globorotalia truncatulinoides r for the reconstruction of marine temperature gradients 1 recent work has provided useful mg ca to water temperature calibrations for shallow dwelling planktonic foraminifer species globorotalia truncatulinoides right coiling r is a deep dwelling species that can serve as a source of information about the temporal variability in the water characteristics of the thermocline we present a temperature calibration for the mg ca in the shell of g truncatulinoides r and examine some of the practical issues associated with evaluating the usefulness of the technique the mg ca in the primary and the secondary calcite of individual g truncatulinoides r correlates exponentially with water column temperatures showing a change of 10 in the mg ca per 1 c r2 0 92 a limited comparison with plankton tow samples demonstrates that the average mg ca temperature was offset 1 c from the average temperature calculated using the 18o calibration of o neil et al 1969 and the mg ca temperatures have a range similar to the 18o temperatures comparisons of the mg in the core top samples to water depth of deposition indicates that dissolution does not alter the measured value of mg in the primary calcite

mg ca variation in planktonic foraminifera tests implications for reconstructing palaeo seawater temperature and habitat migration the nature of compositional variability within the tiny calcitic shells tests that are precipitated by planktonic foraminifera has been investigated using laser ablation inductively coupled plasma mass spectrometry la icp ms systematic large and correlated variation of mg ca mn ca ba ca and zn ca but relatively uniform sr ca are observed through the test walls of analysed species globigerinoides sacculifer globigerinoides ruber neogloboquadrina pachyderma and neogloboquadrina dutertrei distinct chamber and chamber wall layer compositions can be resolved within individual tests and mg ca compositional differences observed in sequentially precipitated test components of the different species analysed are consistent with seawater temperature changes occurring with habitat migration during their adult life cycle stages estimated test calcification temperatures are in keeping with available seawater temperature constraints indicating the potential for accurate seawater temperature reconstruction using la icp ms mg rich 1 6 mol mg surface veneers that are also enriched in mn ba and zn have been found on all species and all fossil tests as well as on live sampled tests of g ruber with the latter suggesting a possible biogenic origin these mg rich surfaces bias bulk test compositions toward higher mg ca values by between 5 and 35

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

vertical distribution and isotopic fractionation of living planktonic foraminifera from the panama basin a model1 2 which explains the vertical and seasonal distribution of planktonic foraminifera was developed using data from the western north atlantic and is comprised of three tenets 1 the conditions in the photic zone upper 80 100 m exclusively dictate planktonic foraminifera species composition and abundance throughout the water column 2 species are vertically stratified within the photic zone according to their temperature preference depth distribution according to temperature preference has been proposed by several authors3 based on isotope analyses of sediments due to seasonal temperature variations seasonal variations in the 18o composition of seawater and species specific isotope fractionation rigorous proof of this hypothesis cannot be provided from sediment analyses alone 3 the chlorophyll maximum is a major food source zone which is preferentially exploited by foraminifera our data from the panama basin which are presented here are confirmation of this model the panama basin in the eastern equatorial pacific which has a shallow and steep thermocline was sampled for living planktonic foraminifera a multiple opening closing net and environmental sensing system mocness 4 was used to collect 13 sets of eight vertically stratified oblique samples we report here the quantitative distribution and stable isotopic composition of planktonic foraminifera from four mocness tows taken over 5 days during august 1979 rv knorr cruise 73 at 5 20 n 8 50 w each tow consisted of eight samples which integrated 12 5 m intervals from 0 to 100 m for moc 126 25 m intervals from 0 to 200 m for moc 127 100 150 m intervals from 0 to 1 000 m on moc 128 and 250 m intervals from 0 to 2 000 m on moc 131

on the fidelity of shell derived δ18oseawater estimates article i nfo 18 oseawater a robustproxyforsurfacesalinity we assessthe fidelity of shell derived 18 oseawater estimates for the surface dwelling foraminifer globigerinoides ruber white using an atlantic meridional coretop transect spanning basin scale temperature and salinity gradients shell derived and observed 18 oseawater values are well correlated r 2 0 77 but a large systematic bias is observed shell mg ca ratios are significantly elevated above values expected from observed and isotopic calcification temperatures in the saline subtropical gyres of both hemispheres this temperature independent shell mg ca ratio variability termed excess mg ca i s highly correlated with surface salinity r 2 0 77 and the observed salinity dependence 27 4 is much higher than indicated by culture studies 6 2 our coretop data are used to develop new atlantic basin temperature and salinity calibration equations that are accurate 1 1 c and 0 20 respectively precise r 2 0 82 and 0 81 respectively and verifiable using previously published data these results are valid for the relatively high salinities of the subtropical atlantic 35 5 37 3 we discover that inclusion of other published data from lower salinity regions b35 indicates little or no excess mg ca taken together these results point to a strongly non linear positive salinity effect on shell mg ca ratios that significantly affects the accuracy of sst and 18

seasonal and interannual variation in santa barbara basin water temperatures observed in sediment trap foraminiferal mg ca 1 we have generated a santa barbara basin sediment trap mg ca record to evaluate culture based calibration equations for the temperate subpolar planktonic foraminiferal species globigerina bulloides and neogloboquadrina pachyderma dextral g bulloides and n pachyderma mg ca are significantly correlated with seasonal variations in temperature of the near surface and subthermocline depths respectively the average deviation between mg based and 18o based temperature estimates is 0 6 c for g bulloides and 0 8 c for n pachyderma differences between mg derived temperatures and instrumental temperatures may be due to cleaning methods environmental factors such as seasonal variations in foraminiferal depth habitats or possible secondary effects on mg ca core top mg ca of both g bulloides and n pachyderma is in excellent agreement with average values from the sediment trap lending strong support for the interpretation of downcore mg ca from these species as annual average near surface and thermoclinal temperatures

the source of ions for biomineralization in foraminifera and their implications for paleoceanographic proxies the global carbon cycle is strongly perturbed by fossil fuel burning leading to atmospheric co2 increase climatic warming followed by polar ice melting and global sea level rise are predicted due to the greenhouse effect of increasing co2 in the atmosphere houghton et al 1995 the ocean plays a major role in neutralizing the excess co2 because the amount of inorganic carbon available for exchange with the atmosphere in the ocean is approximately 50 60 times larger than in the atmosphere e g siegenthaler and sarmiento 1993 the bulk of the atmospheric co2 excess will eventually be neutralized by caco3 dissolution in the deep marine environment this is however is a relatively slow process that operates on the time scale of ocean circulation 1000 yrs and is therefore causing an accumulation of co2 in the atmosphere this phenomenon will result in potentially severe consequences to the well being of global ecological systems obviously the scientific attention of many biogeochemists is focused on processes controlling the response of the marine system to changes in atmospheric co2 concentrations e g archer and maier reimer 1994 broecker 1997 sigman and boyle 2000 berger 2002 foraminifera corals and coccolithophores in the global carbon cycle there are four dominant processes involved in neutralizing the excess atmospheric co2 in the ocean these are 1 gas exchange at the air sea interface and reaction with the carbonate ion to form bicarbonate 2 net primary productivity 3 caco3 production and dissolution and 4 ocean circulation most of these processes are biologically mediated and may have special importance in shallow tropical environments where the exchange with the atmosphere is more direct in this review we address the mechanism of biomineralization in one of the major groups that precipitates caco3 in the ocean the foraminifera as we will show this group

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

modulation and daily banding of mg ca in orbulina universa tests by symbiont photosynthesis and respiration a complication for seawater thermometry the mg ca composition of calcium carbonate tests shells secreted by planktonic foraminifera is increasingly being employed to estimate past seawater temperatures and reconstruct paleocean and climate records spanning hundreds of thousands of years we show using two high resolution microanalysis techniques that the final chamber of the planktonic foraminifera orbulina universa typically comprises between three and six paired low and high mg growth bands the number and spacing of these bands is consistent with a diurnal origin modulated by changing ph within the foraminiferal microenvironment due to the day night photosynthesis respiration cycle of algal symbionts the amplitude of mg ca variation within individual tests and across many daily growth bands cannot be accounted for by seawater temperature in the shallow euphotic zone habitat of o universa our results indicate the mg ca composition of calcite precipitated by o universa in nature is strongly influenced by diurnal changes in the biological activity of algal symbionts and the host foraminifer this brings into question the fundamental premise often made in applying mg ca palaeoseawater thermometry that the mg ca composition of foraminiferal calcite is determined by seawater temperature and whether the mg ca composition of other planktonic species that are more widely used for palaeoseawater thermometry are subject to similar influences 2004 elsevier b v all rights reserved

mg ca in the planktonic foraminifera globorotalia inflata and globigerinoides bulloides from western mediterranean plankton tow and core top samples abstract due to its strong gradient in salinity and small temperature gradient the mediterranean provides an ideal setting to study the impact of salinity on the incorporation of mg into foraminiferal tests we have investigated tests of globorotalia inflata and globigerina bulloides in plankton tow and core top samples from the western mediterranean using icp oes for bulk analyses and la icp ms for analyses of individual chambers in single specimens mg ca observed in g inflata are consistent with existing calibrations whereas g bulloides had significantly higher mg ca than predicted particularly in core top samples from the easterly stations scanning electron microscopy and laser ablation icp ms revealed secondary overgrowths on some tests which could explain the observed high core top mg ca we suggest that the mediterranean intermediate and deep water supersaturated with respect to calcite cause these overgrowths and therefore increased bulk mg ca however the different species are influenced by diagenesis to different degrees probably due to different test morphologies our results provide new perspectives on reported anomalously high mg ca in sedimentary foraminifera and the applicability of the mg ca paleothermometry in high salinity settings by showing that 1 part of the signal is generated by precipitation of inorganic calcite on the foraminifer test due to increased calcite saturation state of the water and 2 species with high surface to volume shell surfaces are potentially more affected by secondary mg rich calcite encrustation

trace element proxies for surface ocean conditions a synthesis of culture calibrations with planktic foraminifera abstract the trace element composition of planktic foraminiferal calcite provides a useful means of determining past surface ocean conditions we have assembled the results of culture experiments for three species of symbiont bearing planktic foraminifera globigerinoides ruber globigerinoides sacculifer and orbulina universa and one symbiont barren species globigerina bulloides to evaluate their responses to temperature salinity ph carbonate ion and dissolved inorganic carbon dic growth conditions trace element ratios li ca b ca mg ca sr ca mn ca cd ca ba ca na ca and u ca were measured simultaneously on samples grown with the same culture techniques which provides robust relatable calibrations that may be used together in multi proxy paleoceanographic studies our data confirm that temperature is the dominant control on foraminiferal mg ca under the ranges of conditions studied and that the potential effects of salinity and co32 on mg ca of these tropical species across late pleistocene glacial cycles are relatively small carbonate system experiments suggest that sr ca may be useful for reconstructing large dic changes na ca increases with salinity in g ruber pink but not in g sacculifer as these emerging proxy relationships become more firmly established the synthesis of multiple trace element ratios may help paleoceanographers isolate the effects of different environmental parameters in paleo records calcification rates g day vary among species and do not respond consistently to any experimental parameter comparison of our calcification rates with those observed in inorganic calcite precipitation experiments suggest that foraminifera calcify 100 more slowly than inorganic calcites grown in similar solutions we suggest that calcification rate does not typically exert a dominant control on trace element partitioning in planktic foraminiferal calcite though it may play a role for some elements under certain circumstances differences in average growth rate cannot explain composition differences among species pointing to alternative controls that may be biological in origin

uncertainties in seawater thermometry deriving from intratest and intertest mg ca variability in globigerinoides ruber intertest mg ca variability within these deep sea core top samples is a source of significant uncertainty in mg ca seawater temperature estimates and is notable for being site specific our results indicate that widely assumed uncertainties in mg ca thermometry may be underestimated we show that statistical power analysis can be used to evaluate the number of tests needed to achieve a target level of uncertainty on a sample by sample case a varying bias also arises from the presence and varying mix of two morphotypes g ruber ruber and g ruber pyramidalis which have different mean mg ca values estimated calcification temperature differences between these morphotypes range up to 5c and are notable for correlating with the seasonal range in seawater temperature at different sites

opening the carbon isotope vital effect black box 1 seasonal temperatures in the euphotic zone recent laboratory experiments with orbulina universa show that the carbon and oxygen isotope signals from this symbiont bearing planktonic foraminifera record distinct environmental parameters irradiance and temperature since light levels are correlated with depth in the marine environment the carbon isotopic composition of o universa can be utilized to differentiate individuals from different depth habitats by combining 18o and 13c data from individuals in an assemblage estimates of seasonal temperature ranges are possible for the upper and lower euphotic zone of the ocean reconstruction of seasonal temperatures using individual holocene o universa from western equatorial pacific ocean boxcore erdc 83 yields ranges of 23 5 to 29 9 c and 20 1 to 24 5 c for the shallow and deep euphotic zone respectively these values are in excellent agreement with recent temperature measurements from this region analyses of individual late glacial 12 000 13 000 years b p o universa from this site suggest the seasonal upper euphotic zone temperature range was approximately 2 5 c lower than it is today a function of cooler summers

timing and mechanism for intratest mg ca variability in a living planktic foraminifer abstract geochemical observations indicate that planktic foraminifer test mg ca is heterogeneous in many species thereby challenging its use as a paleotemperature proxy for paleoceanographic reconstructions we present mg ca and ba ca data collected by laser ablation icp ms from the shells of orbulina universa cultured in controlled laboratory experiments test calcite was labeled with ba spiked seawater for 12 h day or night calcification periods to quantify the timing of intratest mg banding across multiple diurnal cycles results demonstrate that high mg bands are precipitated during the night whereas low mg bands are precipitated during the day data obtained from specimens growing at 20 c and 25 c show that mg ca ratios in both high and low mg bands increase with temperature and average test mg ca ratios are in excellent agreement with previously published empirical calibrations based on bulk solution icp ms analyses in general mg band concentrations decrease with increasing ph and or co2 3 but this effect decreases as experimental temperatures increase from 20 c to 25 c we suggest that mitochondrial uptake of mg2 from the thin calcifying fluid beneath streaming rhizopodial filaments may provide the primary locus for mg2 removal during test calcification and that diurnal variations in either mitochondrial density or activity produce mg banding these results demonstrate that mg banding is an inherent component of test biomineralization in o universa and show that the mg ca paleothermometer remains a fundamental tool for reconstructing past ocean temperatures from fossil foraminifers

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

determination of intratest variability of trace elements in foraminifera by laser ablation inductively coupled plasma mass spectrometry 1 we have developed a technique to determine the variability of trace elements including li b na mg mn cu zn sr and ba within foraminifera tests using laser ablation inductively coupled plasma mass spectrometry la icp ms this technique has a high spatial resolution width 40 80 m depth 0 5 m is reproducible 8 external reproducibility and has low detection limits generally 0 05 g g 1 we demonstrate that normalization of data to a calcite standard usually gives results that are more consistent with solution icp ms data than normalization to nist 612 rastering into the wall of the final chamber of globigerinoides sacculifer shows that the outermost 1 5 m of the test is enriched in trace elements including mn relative to the interior indicating the presence of a contaminant surface phase pustule calcite close to the aperture of globorotalia tumida has different sr ca and ba ca compared to other parts of the test sr ca and ba ca partition coefficients suggest that the pustule calcite is diagenetic and or formed in a more open system multiple analyses of orbulina universa tests recovered from a latitudinal transect in the north atlantic give a relationship between mg ca and sea surface temperature similar to that reported elsewhere in the literature these initial data demonstrate the validity of this technique and show that it is potentially an extremely powerful microanalytical tool for palaeoceanographic and palaeontological studies

comparison of δ18o analyses on individual planktic foraminifer orbulina universa shells by sims and gas source mass spectrometry author s wycech jb kelly dc kozdon r orland ij spero hj valley jw abstract 2018 elsevier b v the oxygen isotope 18o compositions of final chamber fragments of individual shells of the planktic foraminifer orbulina universa were measured in situ via secondary ion mass spectrometry sims and by traditional gas source mass spectrometry gsms entailing acid digestion of sampled calcite the paired sims gsms analyses were performed on final chamber fragments of fossil shells taken from the top of a sediment core holocene as well as shells grown in laboratory culture multiple iterations of sims gsms analyses were conducted on final chamber fragments treated with a variety of cleaning protocols the series of paired analyses yielded an average sims gsms 18o offset 18osims gsms of 0 9 0 1 2 se the volume of material analyzed in 10 m sims spots is 105 times smaller than that analyzed by gsms hence the extent to which these 18osims gsms values represent real differences in analyte vs instrumental factors remains unclear possible contributing factors to the sims gsms 18o difference include sample standard mismatch by sims differences in standardization of sims and gsms and non calcite contaminants in samples although the two datasets are consistently offset sims values reproduce inter shell 18o variability delineated by shell fragment gsms values this strong positive covariance proved useful for bringing the two datasets into agreement i e 18osims gsms 0 and confirms that sims based foraminifer 18o values record changes in calcification temperature and or 18o of seawater whether shells of foraminifer taxa with differing microcrystalline structures chemical composition and or preservation histories register a similar 18osims gsms value is a subject of ongoing testing

the influence of salinity on mg ca in planktic foraminifers evidence from cultures core top sediments and complementary δ18o the mg ca ratio in foraminiferal calcite is one of the principal proxies used for paleoceanographic temperature reconstructions but recent core top sediment observations suggest that salinity may exert a significant secondary control on planktic foraminifers this study compiles new and published laboratory culture experiment data from the planktic foraminifers orbulina universa globigerinoides sacculifer and globigerinoides ruber in which salinity was varied but temperature ph and light were held constant combining new data with results from previous culture studies yields a mg ca sensitivity to salinity of 4 4 2 3 4 7 1 2 and 3 3 1 7 per salinity unit 95 confidence respectively for the three foraminifer species studied here comparison of these sensitivities with core top data suggests that the much larger sensitivity 27 4 per salinity unit derived from atlantic core top sediments in previous studies is not a direct effect of salinity rather we suggest that the dissolution correction often applied to mg ca data can lead to significant overestimation of temperatures we are able to reconcile culture calibrations with core top observations by combining evidence for seasonal occurrence and latitude specific habitat depth preferences with corresponding variations in physico chemical environmental parameters although both mg ca and 18o yield temperature estimates that fall within the bounds of hydrographic observations discrepancies between the two proxies highlight unresolved challenges with the use of paired mg ca and 18o analyses to reconstruct paleo salinity patterns across ocean basins the first step towards resolving these challenges requires a better spatially and seasonally resolved 18osw archive than is currently available nonetheless site specific reconstructions of salinity change through time may be valid

reconciling discrepancies between uk37 and mg ca reconstructions of holocene marine temperature variability significant discrepancies exist between the detrended variability of late holocene marine temperatures inferred from mg ca and uk37 proxies with the former showing substantially more centennial scale variation than the latter discrepancies exceed that attributable to differences in location and persist across various calibrations indicating that they are intrinsic to the proxy measurement we demonstrate that these discrepancies can be reconciled using a statistical model that accounts for the effects of bioturbation sampling and measurement noise and aliasing of seasonal variability the smaller number of individual samples incorporated into mg ca measurements relative to uk37 measurements leads to greater aliasing and generally accounts for the differences in the magnitude and distribution of variability an inverse application of the statistical model is also developed and applied in order to estimate the spectrum of marine temperature variability after correcting for proxy distortions the correction method is tested on surrogate data and shown to reliably estimate the spectrum of temperature variance when using high resolution records applying this inverse method to the actual mg ca and uk37 data results in estimates of the spectrum of temperature variance that are consistent this approach provides a basis by which to accurately estimate the distribution of intrinsic marine temperature variability from marine proxy records

micromapping of mg ca values in cultured specimens of the high magnesium benthic foraminifera 1 this study measured mg ca values in cross sections of the benthic foraminifer planoglabratella opercularis d orbigny using an electron probe microanalyzer epma spot size 2 m 1000 analyses we cultured clonal juveniles of this species under controlled temperatures this species precipitates high magnesium calcite as its test material mean mg ca values increased linearly with the culture temperature therefore mg ca values in walls of subsequently formed chambers reflected changes in temperature during the experiment foraminiferal specimens yielded variable mg ca values within their test walls which resulted from the pattern of chamber formation and from minor variations of mg ca within one chamber wall

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

impact of biomineralization processes on the mg content of foraminiferal shells a biological perspective the mg ca ratio in foraminiferal shells is widely used as a proxy for paleotemperatures nevertheless it seems that the basic mg content of foraminifera is determined by biological factors as can be concluded from the large inter species and intrashell variability and the frequent deviations from inorganic behavior this paper discusses three possible ways by which foraminifera can control or modify the mg content in their shell 1 involvement of organic matrix in the precipitation process that may alter the partition coefficient of mg in biogenic calcite 2 controlled conversion of transient amorphous phases to calcite and 3 modification of the mg concentration in the parent solution from which the crystals precipitate the first two mechanisms are probably responsible for the precipitation of high mg calcite phases whole shell or sublayers while the third mechanism leads to the formation of low mg calcite phases we propose a model adapted from epithelial cells that allows massive mg2 removal from the biomineralization site this model is especially relevant to the planktonic and deep benthic low mg foraminifera that are frequently used for paleotemperature reconstructions we discuss the possible biological roles of mg in the shell in terms of the calcite polymorph conservation the in vivo chemical stability of the shell the functions of mg as a stabilizer of transient phases and as a controlling agent of the precipitation process several temperature sensitive biological processes that may influence the mg ca ratio of the shell are suggested and a model that combines biogenic and inorganic considerations is presented the model uses mg heterogeneity in the shell together with temperature response biologic and inorganic of biomineralization processes to account for the deviation of planktonic foraminifera from inorganic calcite at equilibrium with seawater

effects of seafloor and laboratory dissolution on the mg ca composition of globigerinoides sacculifer and orbulina universa tests a laser ablation icpms microanalysis perspective article i nfo partial or selective dissolution of planktonic foraminiferal tests on the seafloor has been shown to alter original test mg ca compositions and thus may limit the accuracy of mg ca based thermometry for reconstructions of past sea surface temperatures we have employed laser ablation icpms to determine the extent of dissolution caused changes in mg ca distribution across individual chamber walls of the planktonic foraminifera globigerinoides sacculifer and orbulina universa g sacculifer samples collected from a core top depth transect in the ne indian ocean and laboratory dissolution experiments show little if any evidence of preferential removal of mg rich calcite layers by progressive dissolution of the tests we attribute the absence of selective dissolution to the banded distribution of mg across the chamber walls of these foraminiferal species and to the minimal presence of calcite crusts with relatively low mg composition on the outer surfaces of tests mg ca microanalyses of g sacculifer from core top samples further indicate that for samples collected above the calcite lysocline the effect of postdepositional dissolution on mg ca sample mean values is minimal and within the uncertainty of mg ca thermometry i e 0 4 mmol mol 0 8 c at 28 c comparison with previously published results for g sacculifer supports these observations simple modelling of g sacculifer test dissolution indicates that selective removal of calcite with high mg ca values from within the final chamber of g sacculifer test appears insufficient to cause the 10 decrease in mg ca values observed above calcite lysocline these changes in test composition might be related to development removal as a function of co3 2 of a thin diagenetic surface coating which has a relatively high mg ca

mapping of an ophiolite complex by high resolution visible infrared spectrometry the sumail massif of the oman peridotite has been surveyed by the high spectral resolution imager hymap the field measurements have been taken simultaneously to the hymap campaign with a ger 3700 spectrometer to compare the two data sets further calibration and atmospheric correction are made through empirical line corrections a continuum removal by a modified gaussian model on reflectance is then performed for each pixel to minimize atmospheric scattering and shadowing effects classification from spectral distance is established using field observations and comparisons at full spectral resolution to identify peridotite subunits harzburgites and dunites and to distinguish plagioclase wehrlites from gabbros detections of hydrothermal transformations of olivine in serpentines and their alteration in carbonates along fracture networks characterized by narrow spectral signatures validate the classification this demonstrates the utility of the high spectral resolution and the development of appropriate processing methods for geological identifications

daily growth and tidal rhythms in miocene and modern giant clams revealed via ultra high resolution la icpms analysis a novel methodological approach towards improved sclerochemistry abstract we present a novel approach for ultra high resolution laser ablation inductively coupled plasma mass spectrometry la icpms analysis which not only allows us to clearly resolve tridacna giant clam shells daily element ca variability preserved within microscopically visible growth increments is resolved by utilizing the combined capabilities of a rotating rectangular aperture spot size on target 4 50 m the rapid signal washout of a laurin two volume laser ablation cell and slow compositional profiling 1 5 m s striking co variation between oscillating cycles in b ca mg ca sr ca and ba ca is discernible yet also tantalizingly sub daily shifts between these element ca ratios can be observed in comparison to a lower resolution seasonally resolved 18 o mg ca record warter et al 2015 the 10 20 m element ca cycles are determined to be daily in origin and a further 14 15 day cyclicity is superimposed on the daily cycles the latter is interpreted to reflect miocene tidal periodicity changes in pixel intensity during thin section observation associated with micro and macroscopically visible low and high density bands have been quantified via image processing analysis this reveals close correspondence to the measured trace elemental cyclicity indicating a coupling between the geochemical composition of the shell and the incremental growth pattern a comparison between the elemental and image processing results reveals that ultra high resolution la icpms analysis surpasses the latter in detecting environmental rhythms including daily and tidal cycles highly resolved la icpms analysis is a viable alternative to nanosims and opens up routine investigation of long term deep time paleoenvironmental records at daily resolution

mg ca of globorotalia inflata as a recorder of permanent thermocline temperatures in the south atlantic 1 we present a species specific mg ca calcification temperature calibration for globorotalia inflata from a suite of 38 core top samples from the south atlantic from 8 s to 49 s g inflata is a deep dwelling planktonic foraminifer commonly occurring in subtropical to subpolar conditions which qualifies it for reconstructions of the permanent thermocline apparent calcification depths and calcification temperatures were determined by comparing measured 18o with equilibrium 18o of calcite based on water column properties based on our core top samples g inflata apparent calcification depth is constant throughout the south atlantic midlatitudes with a depth of 350 400 m within the permanent thermocline the resulting mg ca calcification temperature calibration is mg ca 0 72 0 045 0 042 exp 0 076 0 006 calcification temperature r2 0 81 and covers the temperature range 3 1 c 16 5 c we applied our mg ca calibration to gravity core ps2495 3 from the mid atlantic ridge at 41 s to test its validity by reconstructing a low resolution record covering the last two glacial interglacial cycles our paleotemperature record reveals large changes in temperature for terminations i and ii when permanent thermocline temperature increased by as much as 8 c the g inflata paleotemperature record suggests that oceanic fronts repeatedly migrated over the location of core ps2495 3 during the last 160 kyr this study shows the potential of g inflata mg ca to reconstruct paleotemperatures in the permanent thermocline

a biomineralization model for the incorporation of trace elements into foraminiferal calcium carbonate measurements of srca of benthic foraminifera show a linear decrease with water depth which is superimposed upon significant variability identified by analyses of individual foraminifera new data for cdca support previous work in defining a contrast between waters shallower and deeper than 2500 m measured element partition coefficients in foraminiferal calcium carbonate relative to sea water d have been described by means of a one box model in which elements are extracted by rayleigh distillation from a biomineralization reservoir that serves for calcification with a constant fractionation factor such that d 1 f 1 f where f is the proportion of ca remaining after precipitation a modification to the model recognises differences in element speciation the model is consistent with differences between dsr dba and dcd in benthic but not planktonic foraminifera depth variations in d for sr and ba are consistent with the model as are differences in depth variation of dcd in calcitic and aragonitic benthic foraminifera the shallower depth variations may reflect increasing calcification rates with increasing water depth to an optimum of about 2500 m observations of unusually lower dcd for some deep waters not accompanied by similar dsr or dba may be because of dissolution or a calcification response to a lower carbonate saturation state

micron scale intrashell oxygen isotope variation in cultured planktic foraminifers abstract in this study we show that the rate of shell precipitation in the extant planktic foraminifer orbulina universa is sufficiently rapid that 12 h calcification periods in 18 o labeled seawater can be resolved and accurately measured using secondary ion mass spectrometry sims for in situ 18 o analyses calcifying o universa held at constant temperature 22 c were transferred every 12 h between ambient seawater 18 o w 0 4 vsmow and seawater with enriched barium and 18 o w 18 6 vsmow to produce geochemically distinct layers of calcite separated by calcite precipitated with an ambient geochemical signature we quantify the position of the ba labeled calcite in the shell wall of o universa via laser ablation icp ms depth profiling of trace element ratios and then measure intrashell 18 o calcite in the same shells using sims with a 3 m spot and an average precision of 0 6 2 sd measured 18 o calcite values in o universa shell layers are within 1 1 of predicted 18 o calcite values elemental and oxygen isotope data show that la icp ms and sims measurements can be cross correlated within the spatial resolution of the two analytical techniques and that 18 o calcite and elemental tracers appear to be precipitated synchronously with no measurable spatial offsets these results demonstrate the capability of sims to resolve daily growth increments in foraminifer shells and highlight its potential for paleoceanographic and biomineralization applications on microfossils

environmental versus biomineralization controls on the intratest variation in the trace element composition of the planktonic foraminifera g inflata and g scitula the intratest variation in the chemical composition of globorotalia scitula and g inflata recovered from a sediment trap sample collected at 3000 m in the north atlantic in early spring has been investigated using laser ablation inductively coupled plasma mass spectrometry and electron microprobe mg ca li ca b ca mn ca and ba ca vary by up to a factor of 10 through the test walls water column properties including temperature and salinity are well documented at the trap site and the observed variations are too large to be explained by vertical migration of the foraminifera however changes in calcite precipitation rate crystal structure or the chemical composition of the internal calcification reservoir also cannot by themselves fully account for the pattern of intratest variability nevertheless the average mg ca for each chamber generally produces a mg ca temperature that matches that measured in the water column the exception is small morphologically distinct g inflata tests that have anomalously high mg ca

approaches to unravel seasonality in sea surface temperatures using paired single specimen foraminiferal δ18o and mg ca analyses 1 seasonal changes in surface ocean temperature are increasingly recognized as an important parameter of the climate system here we assess the potential of analyzing single specimen planktonic foraminifera as proxy for the seasonal temperature contrast seasonality oxygen isotopes and mg ca ratios were measured on single specimens of globigerinoides ruber extracted from surface sediment samples of the mediterranean sea and the adjacent atlantic ocean variability in 18o and mg ca was then compared to established modern seasonal changes in temperature and salinity for both regions the results show that 1 average 18o derived temperatures correlate with modern annual average temperatures for most sites 2 the range in 18o and mg ca derived temperature estimates from single specimen analysis resembles the range in seasonal temperature values at the sea surface 0 50 m in the mediterranean sea and the atlantic ocean and 3 there is no strong correlation between mg ca and 18o derived temperatures from the same specimens in the current data set indicating that other parameters salinity carbonate ion concentration symbiont activity ontogenesis and natural variability potentially affect these proxies

characterization of mg ca distributions in planktonic foraminifera species by electron microprobe mapping 1 the distribution of mg ca within the tests of eight modern planktonic foraminifer species has been characterized using electron microprobe mapping species include several that are commonly used for estimation of past seawater temperatures globigerinoides ruber g sacculifer neogloboquadrina incompta synonym of n pachyderma dex n dutertrei and g truncatulinoides each of the investigated species displays large variations in mg ca composition within individual tests however the pattern of mg ca variation is notably different between symbiont bearing and symbiont free species in symbiotic species cyclic mg ca compositional banding occurs that is characterized by narrow 1 3 m high mg ca typically 8 11 mmol mol bands intercalated between broader low mg ca typically 1 5 mmol mol bands this factor of 2 3 difference equates to an apparent calcification temperature change of 10 c or more such temperature changes are considered highly improbable and suggest vital effects significantly modify the incorporation of mg ca into the tests of symbiont bearing species these vital effects remain poorly understood and demand further careful evaluation as they may need to be accounted for when making reliable reconstructions of past oceanic temperatures symbiont free species typically have fewer and broader compositional bands that may reflect more closely changes in calcification temperature as these species migrate within a water column