Stable isotope and Cd/Ca ratios of Neogloboquadrina pachyderma in high-latitude sediments

Recent studies have stressed the role of high latitude nutrient levels and productivity in controlling the carbon isotopic composition of the deep sea and the CO2 content of the atmosphere. We undertook a study of the chemical composition of the polar planktonic foraminifer Neogloboquadrina pachyderma (s., sinistral coiling) from 30 late Holocene samples and 49 down core records from the high-latitude North and South Atlantic Oceans to evaluate the history of sea surface chemical change from glacial to interglacial time. Stable isotopic analysis of coretop samples from the Atlantic, Pacific and Southern Oceans shows no significant correlation between the delta13C of N. pachyderma and either delta13C or PO4 in seawater. Conversely, Cd/Ca ratios in planktonic foraminifera are consistent with the PO4 content of surface waters. The level of maximum glaciation (18,000 yr B.P.), identified by CLIMAP and delta18O, was chosen for mapping. Isopleths of delta18O on N. pachyderma (s.) in the North Atlantic reveal a pattern largely influenced by sea surface temperature (S.S.T.) and generally support the S.S.T. reconstruction of CLIMAP. Differences between the two suggest significantly lower salinity in North Atlantic surface waters at high latitudes than in lower latitudes. Down core delta13C records of N. pachyderma confirm that low delta13C values occurred in the northeast Atlantic during the latest glacial maximum (Labeyrie and Duplessy, 1985, doi:10.1016/0031-0182(85)90069-0). However, a map of delta13C for the 18,000 yr B.P. level for a much larger region in the North Atlantic shows that minimum N. pachyderma delta13C occurred in temperate waters. N. pachyderma delta13C decreased toward the southwest, reaching a minimum of -1 per mil at 37°N. Despite the variability seen in delta13C records of N. pachyderma, none of our cores show significant temporal variability in Cd/Ca. From the combined Cd/Ca and delta13C data we can see no evidence for an upwelling gyre in the eastern North Atlantic during the latest glacial maximum, nor evidence that the southern and northern oceans had significantly different levels of preformed nutrients than today.

Multi-proxy record of planktonic and benthic foraminiferal d18O, and Mg/Ca-derived surface and lower thermocline temperatures in sediment core SO18471 (GIK18471), Timor Sea

Paleostudies of the Indonesian Throughflow (ITF) are largely based on temperature and salinity reconstructions of its near surface component, whereas the variability of its lower thermocline flow has rarely been investigated. We present a multi-proxy record of planktonic and benthic foraminiferal d18O, Mg/Ca-derived surface and lower thermocline temperatures, X-ray fluorescence (XRF)-derived runoff and sediment winnowing for the past 130 ka in marine sediment core SO18471. Core SO18471, retrieved from a water depth of 485 m at the southern edge of the Timor Strait close to the Sahul Shelf, sits in a strategic position to reconstruct variations in both the ITF surface and lower thermocline flow as well as to investigate hydrological changes related to monsoon variability and shelf dynamics over time. Sediment winnowing demonstrates that the ITF thermocline flow intensified during MIS 5d-a and MIS 1. In contrast during MIS 5e, winnowing was reduced and terrigenous input increased suggesting intensification of the local wet monsoon and a weaker ITF. Lower thermocline warming during globally cold periods (MIS 4 - MIS 2) appears to be related to a weaker and contracted thermocline ITF and advection of warm and salty Indian Ocean waters.

Stable isotope and Mg/Ca ratios of Globigerinoides ruber from core-top sediment samples

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 d18O and Mg/Ca was then compared to established modern seasonal changes in temperature and salinity for both regions. The results show that (1) average d18O-derived temperatures correlate with modern annual average temperatures for most sites, (2) the range in d18O- 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 d18O-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.

(Appendix) Stable carbon and oxygen isotopes, and Mg/Ca ratios of foraminifera from ODP Hole 154-925A

To better understand the links between the carbon cycle and changes in past climate over tectonic timescales we need new geochemical proxy records of secular change in silicate weathering rates. A number of proxies are under development, but some of the most promising (e.g. palaeoseawater records of Li and Nd isotope change) can only be employed on such large samples of mono-specific foraminifera that application to the deep sea sediment core archive becomes highly problematic. "Dentoglobigerina" venezuelana presents a potentially attractive target for circumventing this problem because it is a typically large (> 355 ?m diameter), abundant and cosmopolitan planktic foraminifer that ranges from the early Oligocene to early Pliocene. Yet considerable taxonomic and ecological uncertainties associated with this taxon must first be addressed. Here, we assess the taxonomy, palaeoecology, and ontogeny of "D." venezuelana using stable isotope (oxygen and carbon) and Mg/Ca data measured in tests of late Oligocene to early Miocene age from Ocean Drilling Program (ODP) Site 925, on Ceara Rise, in the western equatorial Atlantic. To help constrain the depth habitat of "D." venezuelana relative to other species we report the stable isotope composition of selected planktic foraminifera species within Globigerina, Globigerinoides, Paragloborotalia and Catapsydrax. We define three morphotypes of "D." venezuelana based on the morphology of the final chamber and aperture architecture. We determine the trace element and stable isotope composition of each morphotype for different size fractions, to test the validity of pooling these morphotypes for the purposes of generating geochemical proxy datasets and to assess any ontogenetic variations in depth habitat. Our data indicate that "D." venezuelana maintains a lower thermocline depth habitat at Ceara Rise between 24 and 21 Ma. Comparing our results to published datasets we conclude that this lower thermocline depth ecology for the Oligo-Miocene is part of an Eocene-to-Pliocene evolution of depth habitat from surface to sub-thermocline for "D." venezuelana. Our size fraction data advocate the absence of photosymbionts in "D." venezuelana and suggest that juveniles calcify higher in the water column, descending into slightly deeper water during the later stages of its life cycle. Our morphotype data show that d18O and d13C variation between morphotypes is no greater than within-morphotype variability. This finding will permit future pooling of morphotypes in the generation of the "sample hungry" palaeoceanographic records.

Stable carbon and oxygen isotopes and Mg/Ca ratios of foraminifers from ODP Site 202-1241 sediments

A combination of stable isotope records and Mg/Ca temperature estimates of four different planktonic foraminiferal species from Ocean Drilling Program Site 1241 allows differentiation between temperature and salinity changes in the tropical east Pacific (TEP) upper water column during the Pliocene (~5.7-2.1 Ma). The deviation of d18O records and Mg/Ca temperature estimates from thermocline-dwelling planktonic foraminifers suggests that local changes in salinity exerted a much stronger control on Pliocene TEP upper ocean water mass signatures than previously assumed. The most pronounced Pliocene change in TEP upper ocean stratification was the shoaling of the thermocline from ~4.8 to 4.0 Ma that was possibly triggered by changes in the configuration of low-latitude ocean gateways. During this time interval, mixed-layer temperatures and salinities remained relatively constant in contrast to a pronounced temperature (~6°C) and salinity decrease at the bottom of the photic zone. This change led to a new state in the thermal structure of the TEP, as the thermocline remained relatively shallow until ~2.1 Ma.

(Table 2) Mg/Ca and Sr/Ca composition of planktonic foraminifera from ODP Hole 143-865B

To understand the climate dynamics of hypothesized past greenhouse intervals, it is essential to constrain tropical sea-surface temperatures (SST), yet existing proxy records give conflicting results. Here we present the first Mg/Ca-based study of pre-Quaternary SST and investigate early Paleogene (late Paleocene through late middle Eocene; 58.6-39.8 Ma) tropical temperatures, using planktonic foraminifera belonging to the genus Morozovella from Ocean Drilling Program Site 865 on Allison Guyot (western central equatorial Pacific Ocean). Calcification temperatures similar to or warmer than modern tropical SST are calculated using a range of assumptions regarding diagenesis, temperature calibration, and seawater Mg/Ca. Long-term warming is observed into the early Eocene (54.8-49.0 Ma), with peak SST between 51 and 48 Ma and rapid cooling of 4°C beginning at 48 Ma. These findings are inconsistent with the d18O-based SST previously estimated for this site.

Delta 44/40 Ca, Mg/Ca and Sr/Ca record of Globigerinoides sacculifer and calculated temperatures and salinity changes of ODP Hole 165-999A

The delta18O values of planktonic foraminifera increased in the Caribbean by about 0.5? relative to the equatorial East Pacific values between 4.6 and 4.2 Ma as a consequence of the closure of the Central American Gateway (CAG). This increase in delta18O can be interpreted either as an increase in Caribbean sea surface (mixed layer) salinity (SSS) or as a decrease in sea surface temperatures (SST). This problem represents an ideal situation to apply the recently developed paleotemperature proxy delta44/40Ca together with Mg/Ca and d18O on the planktic foraminifer Globigerinoides sacculifer from ODP Site 999. Although differences in absolute temperature calibration of delta44/40Ca and Mg/Ca exist, the general pattern is similar indicating a SST decrease of about 2-3 8C between 4.4 and 4.3 Ma followed by an increase in the same order of magnitude between 4.3 and 4.0 Ma. Correcting the delta18O record for this temperature change and assuming that changes in global ice volume are negligible, the salinity-induced planktonic delta18O signal decreased by about 0.4? between 4.4 and 4.3 Ma and increased by about 0.9? between 4.3 and 4.0 Ma in the Caribbean. The observed temperature and salinity trends are interpreted to reflect the restricted exchange of surface water between the Caribbean and the Pacific in response to the shoaling of the Panamanian Seaway, possibly accompanied by a southward shift of the Intertropical Convergence Zone (ITCZ) between 4.4 and 4.3 Ma. Differences in Mg/Ca- and delta44/40Ca-derived temperatures can be reconciled by corrections for secular variations of the marine Mg/Ca[sw] and delta44/40Ca, a salinity effect on the Mg/Ca ratio and a constant temperature offset of ~2.5 °C between both SST proxy calibrations.

In situ d18O and Mg/Ca analyses of ODP Site 143-865 samples

We report d18O and minor element (Mg/Ca, Sr/Ca) data acquired by high-resolution, in situ secondary ion mass spectrometry (SIMS) from planktic foraminiferal shells and 100-500 µm sized diagenetic crystallites recovered from a deep-sea record (ODP Site 865) of the Paleocene-Eocene thermal maximum (PETM). The d18O of crystallites (~1.2 per mil Pee Dee Belemnite (PDB)) is ~4.8 per mil higher than that of planktic foraminiferal calcite (-3.6 per mil PDB), while crystallite Mg/Ca and Sr/Ca ratios are slightly higher and substantially lower than in planktic foraminiferal calcite, respectively. The focused stratigraphic distribution of the crystallites signals an association with PETM conditions; hence, we attribute their formation to early diagenesis initially sourced by seafloor dissolution (burndown) ensued by reprecipitation at higher carbonate saturation. The Mg/Ca ratios of the crystallites are an order of magnitude lower than those predicted by inorganic precipitation experiments, which may reflect a degree of inheritance from "donor" phases of biogenic calcite that underwent solution in the sediment column. In addition, SIMS d18O and electron microprobe Mg/Ca analyses that were taken within a planktic foraminiferal shell yield parallel increases along traverses that coincide with muricae blades on the chamber wall. The parallel d18O and Mg/Ca increases indicate a diagenetic origin for the blades, but their d18O value (-0.5 per mil PDB) is lower than that of crystallites suggesting that these two phases of diagenetic carbonate formed at different times. Finally, we posit that elevated levels of early diagenesis acted in concert with sediment mixing and carbonate dissolution to attenuate the d18O decrease signaling PETM warming in "whole-shell" records published for Site 865.

Stable isotope and Mg/Ca record of IODP Site 339-U1385

Although millennial-scale climate variability (<10 ka) has been well studied during the last glacial cycles, little is known about this important aspect of climate in the early Pleistocene, prior to the Middle Pleistocene Transition. Here we present an early Pleistocene climate record at centennial resolution for two representative glacials (marine isotope stages (MIS) 37-41 from approximately 1235 to 1320 ka) during the "41 ka world" at Integrated Ocean Drilling Program Site U1385 (the "Shackleton Site") on the southwest Iberian margin. Millennial-scale climate variability was suppressed during interglacial periods (MIS 37, MIS 39, and MIS 41) and activated during glacial inceptions when benthic d18O exceeded 3.2 per mil. Millennial variability during glacials MIS 38 and MIS 40 closely resembled Dansgaard-Oeschger events from the last glacial (MIS 3) in amplitude, shape, and pacing. The phasing of oxygen and carbon isotope variability is consistent with an active oceanic thermal bipolar see-saw between the Northern and Southern Hemispheres during most of the prominent stadials. Surface cooling was associated with systematic decreases in benthic carbon isotopes, indicating concomitant changes in the meridional overturning circulation. A comparison to other North Atlantic records of ice rafting during the early Pleistocene suggests that freshwater forcing, as proposed for the late Pleistocene, was involved in triggering or amplifying perturbations of the North Atlantic circulation that elicited a bipolar see-saw response. Our findings support similarities in the operation of the climate system occurring on millennial time scales before and after the Middle Pleistocene Transition despite the increases in global ice volume and duration of the glacial cycles.

(Table S1) Stable oxygen isotopic values and Mg/Ca ratios of Globigerinoides ruber w from sediment core AAS9_21

Variations in sea surface temperature (SST), d18O of sea water (?18Ow), and salinity were reconstructed for the past 68 ka using a sediment core (AAS9/21) from the eastern Arabian Sea (EAS) in order to understand the changes in evaporation and precipitation associated with the monsoon system. The Mg/Ca-derived SST record varies by ~4°C; it shows that marine isotope stage (MIS) 4 was warmer than MIS 3, that the Last Glacial Maximum was 4°C cooler than the present, and that there was a 2°C increase within the Holocene. MIS 4 records higher d18Ow and salinity values than MIS 2, suggesting variable flow of low-salinity Bay of Bengal flow into the EAS during glacial periods. The transition from MIS 4 to MIS 3 was marked with a conspicuous shift from higher to lower d18Ow values, which reflects a decrease in the evaporation-precipitation budget in the EAS, perhaps due to the strengthening of southwest monsoon. Monsoon reconstructions based on d18Ow reveal that monsoon-driven precipitation was higher during MIS 3 and MIS 1 and was lower during MIS 2 and MIS 4. This is consistent with earlier monsoon reconstructions based on upwelling indices from the western Arabian Sea. However, the amplitude of monsoon fluctuations derived through upwelling indices and d18Ow varies significantly, which may indicate spatial variability of monsoon rainfall.

Sr/Ca and Cd/Ca ratios of benthic foraminifera in surface deep-sea sediments

Measurements of Sr/Ca 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 Cd/Ca 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 (alpha), such that D = (1 - f**alpha)/(l - 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 D[Sr], D[Ba], and D[Cd] 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 D[Cd] 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 [Sr], or D[Ba] may be because of dissolution or a calcification response to a lower carbonate saturation state.

Measurement results of d18O, Mg/Ca, and Ti/Ca of sediment cores GeoB10042-1 and GeoB10043-3

The advection of relatively fresh Java Sea water through the Sunda Strait is presently responsible for the low-salinity "tongue" in the eastern tropical Indian Ocean with salinities as low as 32 per mil. The evolution of the hydrologic conditions in the eastern tropical Indian Ocean since the last glacial period, when the Sunda shelf was exposed and any advection via the Sunda Strait was cutoff, and the degree to which these conditions were affected by the Sunda Strait opening are not known. Here we have analyzed two sediment cores (GeoB 10042-1 and GeoB 10043-3) collected from the eastern tropical Indian Ocean off the Sunda Strait that cover the past ~40,000?years. We investigate the magnitude of terrigenous supply, sea surface temperature (SST), and seawater d18O (d18Osw) changes related to the sea level-driven opening of the Sunda Strait. Our new spliced records off the Sunda Strait show that during the last glacial, average SST was cooler and d18Osw was higher than elsewhere in the eastern tropical Indian Ocean. Seawater d18O decreased ~0.5 per mil after the opening of the Sunda Strait at ~10 kyr B.P. accompanied by an SST increase of 1.7°C. We suggest that fresher sea surface conditions have persisted ever since due to a continuous transport of low-salinity Java Sea water into the eastern tropical Indian Ocean via the Sunda Strait that additionally increased marine productivity through the concomitant increase in terrigenous supply.

(Table T1) Geochemical composition of tochilinite and related minerals of ODP Hole 173-1068A

Tochilinite (approximately FeS(Mg,Fe)(OH)2) is locally abundant in Hole 1068A serpentinites from Cores 173-1068A-21R and 22R. It occurs in veins, as fillings in void space, and in intergrowths with serpentine and andradite. An apparently related mineral, but with Ca and Al largely replacing Mg, occurs in association with, and possibly as a replacement of, pyrrhotite in serpentinite breccias from the bottom of Core 173-1068A-20R. The transition from Mg-Fe-rich brucite tochilinites to Ca- and S-rich carbonate tochilinites is consistent with increasing sulfur and oxygen activity upsection. Tochilinite has been reported at other sites on the Iberia Abyssal Plain and is abundant to the point of being a rock-forming mineral in several samples from Site 1068. Rather than being a mineralogical curiosity, tochilinite appears to be common and a major sink for sulfur in the upper serpentinites of the Iberia Abyssal Plain.