Mg/Ca and Sr/Ca ratios of planktonic foraminifera from North Atlantic surface sediments

Reliable temperature estimates from both surface and subsurface ocean waters are needed to reconstruct past upper water column temperature gradients and past oceanic heat content. This work examines the relationships between trace element ratios in fossil shells and seawater temperature for surface-dwelling foraminifera species, Globigerinoides ruber (white) and Globigerina bulloides, and deep-dwelling species, Globorotalia inflata, Globorotalia truncatulinoides (dextral and sinistral) and Pulleniatina obliquiloculata. Mg/Ca and Sr/Ca ratios in shells picked in 29 modern core tops from the North Atlantic Ocean are calibrated using calculated isotopic temperatures. Mg/Ca ratios on G. ruber and G. bulloides agree with published data and relationships. For deep-dwelling species, Mg/Ca calibration follows the equation Mg/Ca = 0.78 (±0.04) * exp (0.051 (±0.003) * T) with a significant correlation coefficient of R**2 = 0.74. Moreover, there is no significant difference between the different deep-dwellers analyzed. For the Sr/Ca ratio, the surface dwellers and P. obliquiloculata do not record any temperature dependence. For the Globorotalia species, the thermo dependence of Sr/Ca ratio can be described by a single linear relationship: Sr/Ca = (0.0182 (±0.001) * T) + 1.097 (±0.018), R**2 = 0.85. Temperature estimates with a 1 sigma error of ±2.0°C and ±1.3°C can be derived from the Mg/Ca and Sr/Ca ratios, respectively, as long as the Sr geochemistry in the ocean has been constant through time.

(Table 1) Temperature and foraminiferal Mg/Ca ratios of samples off Japan

We studied Mg/Ca in high-Mg, shallow-water benthic foraminifera in culture and in samples from natural environments, in order to evaluate the expression of latitudinal and seasonal temperature variability in Mg/Ca in their tests. We cultured Planoglabratella opercularis (d'Orbigny) and Quinqueloculina yabei Asano under controlled temperature (10°-25°C) and salinity (30-38) conditions. Both species show a linear correlation between Mg/Ca and temperature, but they differ in temperature sensitivity. Salinity does not significantly influence Mg/Ca. In the samples collected in nature, Mg/Ca and seawater temperatures are positively correlated, but there are more complexities than in the records for cultured specimens due to such factors as seasonal fluctuations in temperature. We conclude that Mg/Ca ratios in monospecific benthic foraminiferal samples may be used as a reliable temperature proxy, if the lifetime of the species is taken into account.

(Table 1) Radiocarbon dating of a lake sediment core, southern West Greenland

The dominant processes determining biological structure in lakes at millennial timescales are complex. In this study, we used a multi-proxy approach to determine the relative importance of in-lake versus indirect processes on the Holocene development of an oligotrophic lake in SW Greenland (66.99°N, 50.97°W). A 14C and 210Pb-dated sediment core covering approximately 8500 years BP was analyzed for organic-inorganic carbon content, pigments, diatoms, chironomids, cladocerans, and stable isotopes (d13C, d18O). Relationships among the different proxies and a number of independent controlling variables (Holocene temperature, an isotope-inferred cooling period, and immigration of Betula nana into the catchment) were explored using redundancy analysis (RDA) independent of time. The main ecological trajectories in the lake biota were captured by ordination first axis sample scores (18-32% variance explained). The importance of the arrival of Betula (ca. 6500 years BP) into the catchment was indicated by a series of partial-constrained ordinations, uniquely explaining 12-17% of the variance in chironomids and up to 9% in pigments. Climate influences on lake biota were strongest during a short-lived cooling period (identified by altered stable isotopes) early in the development of the lake when all proxies changed rapidly, although only chironomids had a unique component (8% in a partial-RDA) explained by the cooling event. Holocene climate explained less variance than either catchment changes or biotic relationships. The sediment record at this site indicates the importance of catchment factors for lake development, the complexity of community trends even in relatively simple systems (invertebrates are the top predators in the lake) and the challenges of deriving palaeoclimate inferences from sediment records in low-Arctic freshwater lakes.

Mg/Ca and stable oxygen isotope ratios of Uvigerina spp. from the Southern Ocean

The sensitivity to temperature of Mg/Ca ratios in the shallow-infaunal benthic foraminifera Uvigerina spp. has been assessed. Core-top calibrations over ~1-20 °C show a range in sensitivity of 0.065-0.084 mmol/mol/°C but few data are available spanning the temperature range anticipated in deep-sea records over glacial-interglacial cycles. In contrast to epibenthic foraminiferal species, carbonate ion saturation appears not to affect Mg/Ca significantly. A method based on estimating the ratio of the temperature sensitivity of foraminiferal Mg/Ca to that of d18Ocalcite shows that sensitivity for Mg/Ca at the high end of the observed core-top range (~0.1 mmol/mol/°C) is required for consistency with LGM-Holocene differences in each property as constrained by independent proxy data. This is supported by a Mg/Ca record for Uvigerina spp. generated for the Southern Ocean over the past 440,000 years from Ocean Drilling Program Site 1123 (Chatham Rise, New Zealand). The record shows variability that correlates with climate oscillations. The LGM deep ocean temperature derived from the Mg/Ca record is -1.1 ± 0.3 °C. Transformation to temperature allows estimates to be made of changes in bottom water temperature and seawater d18O and comparison made with literature records. Analysis reveals a ~2.5-kyr lead in the record of temperature over calcite d18O and a longer lead over seawater d18O. This is a reflection of larger phase offsets at eccentricity periods; phase offsets at tilt and precession are within error zero.

Mg/Ca ratio of Globorotalia tumida and subsurface temperature reconstruction for ODP Site 130-806

The tropical Pacific thermocline strength, depth, and tilt are critical to tropical mean state and variability. During the early Pliocene (~3.5 to 4.5 Ma), the Eastern Equatorial Pacific (EEP) thermocline was deeper and the cold tongue was warmer than today, which resulted in an mean state with a reduced zonal sea surface temperature gradient, or El Padre. However, it is unclear whether the deep thermocline was a local feature of the EEP or a basin-wide condition with global implications. Our measurements of Mg/Ca of Globorotalia tumida in a western equatorial Pacific site indicate Pliocene subsurface temperatures warmer than today; thus, El Padre included a basin-wide thermocline that was relatively warm, deep, and weakly tilted. At ~4 Ma, thermocline steepening was coupled to cooling of the cold tongue. Since ~4 Ma, the basin-wide thermocline cooled/shoaled gradually, with implications for thermocline feedbacks in tropical dynamics and the interpretation of TEX86-derived temperatures.

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.

Great Barrier Reef coral element/Ca and stable isotope data and U-Th ages from IODP Expedition 325

Tropical south-western Pacific temperatures are of vital importance to the Great Barrier Reef (GBR), but the role of sea surface temperatures (SSTs) in the growth of the GBR since the Last Glacial Maximum remains largely unknown. Here we present records of Sr/Ca and d18O for Last Glacial Maximum and deglacial corals that show a considerably steeper meridional SST gradient than the present day in the central GBR. We find a 1-2 °C larger temperature decrease between 17° and 20°S about 20,000 to 13,000 years ago. The result is best explained by the northward expansion of cooler subtropical waters due to a weakening of the South Pacific gyre and East Australian Current. Our findings indicate that the GBR experienced substantial meridional temperature change during the last deglaciation, and serve to explain anomalous deglacial drying of northeastern Australia. Overall, the GBR developed through significant SST change and may be more resilient than previously thought.

Potassium and argon concentrations and age determination of ODP Site 125-782 and 125-786

K-Ar whole-rock ages have been obtained for 30 samples from Sites 782 and 786, Ocean Drilling Program Leg 125 in the Izu-Bonin (Ogasawara) forearc region. They form a trimodal spread of ages between 9 Ma and 44 Ma and are, with a few exceptions, consistent with the inferred lithostratigraphy. The ages have been interpreted in terms of at least two distinct episodes of magmatic and/or hydrothermal activity. A group of ten samples, including the lava flows, gave an isochron age of 41.3 ± 0.5 Ma (middle-late Eocene). This is thought to represent the age of the principal magmatic development of the volcanic forearc basement, and is comparable to published ages on equivalent rocks from other parts of the forearc basement high (e.g., the Ogasawara Islands). It may be significant that this age is slightly younger than the timing of major plate reorganization in the Western Pacific at about 43 Ma. This was followed by a minor episode of intrusive magmatism at 34.6 ± 0.7 Ma (early Oligocene) which appears to have reset the ages of some of the earlier units. This event probably corresponds to the initiation of rifting of the "proto-arc" to form the Parece Vela Basin. Boninitic samples were erupted during both episodes of magmatism, the earlier being of low-Ca boninite type and the later being of medium- and high-Ca types. It is also possible that a third episode of intrusive magmatism affected the Izu-Bonin forearc region at both Sites 782 and 786 at about 17 Ma. This would be consistent with magmatic activity elsewhere in the region during the Miocene, associated with the end of active spreading in the Parece Vela Basin and the start of arc activity in the West Mariana Ridge.

Planktonic foraminiferal Cd/Ca ratios

Records of Cd/Ca in planktonic foraminiferal calcite of Globigerinoides bulloides in cores from the Subantarctic region of the Southern Ocean show large glacial-interglacial variations with lower Cd/Ca (by 0.06-0.10 µmol/mol) at glacial times. Interpretation of these records in terms of lower dissolved phosphate and inferred higher glacial nutrient utilization has significant implications for glacial atmospheric carbon dioxide (pCO2) draw-down. However, box core-top data for G. bulloides in the North Atlantic suggest that the incorporation of Cd into planktonic foraminifera relative to seawater (DCd) is temperature sensitive (DCd=0.637 exp 0.15T). When the Subantarctic planktonic Cd/Ca records are corrected for this temperature dependence, they show little or no glacial-interglacial diferences. If, as seems likely, this observation can be interpreted to indicate a minimal change (< 0.5 µmol/kg) in surface water phosphate concentrations, then the explanation for lowered glacial pCO2 must be looked for elsewhere.

Chemical composition of interstitial waters from sediments of brine-bearing deeps of the Red Sea

Data on concentrations of the major ions (Cl, SO4, Alk, Na, K, Ca, Mg, NH4) in interstitial waters from sediments of three brine-bearing deeps of the Red Sea rift zone are reported. Interstitial waters of the Atlantis-II Deep have the highest salinity (310.1 g/l), of the Discovery Deep - slightly lower (298.8 g/l), and of the Suakin Deep - the lowest (159.9 g/l). Interstitial waters of all three deeps are characterized by low, compared with sea water, absolute and relative concentrations of Mg and SO4 ions and have extremely low alkaline reserve (0.15-0.64 meq/l). Concentrations of K, Ca and especially Na and Cl ions, as compared with sea water, are highly increased. Interstitial waters from the deeps in study have high, compared with sea water, concentrations of NH4 (12-62 mg/l).

Quaternary oxygen isotope record of planktonic foraminifera from ODP Site 805 on the Ontong Java Plateau

The oxygen isotope records of G. sacculifer and Pulleniatina in the uppermost three cores at Ocean Drilling Program Hole 805C span the last 1.6 m.y., an estimate based on Fourier stratigraphy. The last 700,000 yr are dominated by both eccentricity and obliquity-related orbital fluctuations. The range of variation of delta18O values is about 1.5?, of which ca. 75% may be assigned to global ice-volume effect. The remainder of the range is shared by the effects of surface temperature variation, thermocline depth change (in the case of Pulleniatina, especially), and differential dissolution. Before 1 Ma, obliquity-related fluctuations dominate. The transition between obliquity- and eccentricity-dominated time occurs between ca. 1 and 0.7 Ma. It is marked by irregularities in phase relationships, the source of which is not clear. The age of the Brunhes/Matuyama boundary is determined as 794,000 yr by obliquity counting. However, an age of 830,000 yr also is compatible with the counts of both eccentricity and obliquity cycles. In the first case, Stage 19 (which contains the boundary) is coincident with the crest of the 19th obliquity cycle, setting the first crest downcore equal to zero, and counting backward (o19). In the second, Stage 19 coincides with o20. No evidence was found for fluctuations related to precession (23 and 19 k.y.) rising above the noise level, using plain Fourier expansion on the age model of the entire series. Detailed stratigraphic comparison with the Quaternary record of Hole 806B allows the recognition of major dissolution events (which increase the difference in delta18O values of G. sacculifer at the two sites). These occur at Stages 11-13, 16-17, and near 1.5 Ma (below o33).

Geochemistry of igneous rock samples of ODP Site 125-786

A morphologically complex igneous basement was penetrated at Leg 125 Site 786 beneath approximately 100 m of Eocene-Pleistocene sediments at 31°52.45 'N, 141°13.59'E in a 3082-m water depth. The site is located on the forearc basement high (FBH) of the Izu-Bonin (Ogasawara) Arc. In the broadest terms, the sequence in Hole 786B consists of a basal sheeted dike complex, heavily mineralized in places, with overlying pillow lavas giving way to a complex and repeated sequence of interlayered volcanic breccias and lava flows with some thin sedimentary intervals. The sequence has been further cut by dikes or sills, particularly of high-Ca and intermediate-Ca boninite, and is locally strongly sheared by faulting. The whole basement has been covered with middle Eocene-early Pleistocene sediments. A monomict breccia forms the shallowest portion of Hole 786B and a polymict breccia having Mn-oxide-rich clast coatings and matrix forms the deepest part of Hole 786A (-100-160 mbsf). The basement is tectonized in some places, and a mineralized stockwork is present in the deepest part of Hole 786B. A wide variety of rock types form this basement, ranging from mafic to silicic in character and including high-, intermediate-, and low-Ca boninites, intermediate- and low-Ca bronzite andesites, andesite, dacite, and rhyolite groups. Intragroup and intergroup relationships are complicated in detail, and several different upper mantle source(s) probably were involved. A significant role for orthopyroxene-clinopyroxene-plagioclase fractionation is indicated in the mafic-intermediate groups, and the most probable complementary cumulates should be noritic gabbros. Many overall similarities but some subtle differences are noted between the igneous basement at Site 786 and the subaerial outcrops of the FBH to the south in the type boninite locality of Chichijima. Both suites were derived by hydrous melting of a relatively shallow, refractory (harzburgitic) upper mantle source. These Bonin forearc basement rocks are similar in many respects to those of Eocene-Oligocene age now forming the forearc of the Marianas at Leg 60 Site 458 and on Guam. In sharp distinction, the geochemistry of the Eocene-Pleistocene ash sequences overlying the Bonin FBH must have been derived from a very different upper mantle source, implying considerable across-strike differences in sub-arc mantle composition.

Isotope ratios of osmiun, carbon and oxygen of Miocene sediments and benthic foraminifera

Seawater 187Os/188Os ratios for the Middle Miocene were reconstructed by measuring the 187Os/188Os ratios of metalliferous carbonates from the Pacific (DSDP 598) and Atlantic (DSDP 521) oceans. Atlantic and Pacific 187Os/188Os measurements are nearly indistinguishable and are consistent with previously published Os isotope records from Pacific cores. The Atlantic data reported here provide the first direct evidence that the long-term sedimentary 187Os/188Os record reflects whole-ocean changes in the Os isotopic composition of seawater. The Pacific and the Atlantic Os measurements confirm a long-term 0.01/Myr increase in marine 187Os/188Os ratios that began no later than 16 Ma. The beginning of the Os isotopic increase coincided with a decrease in the rate of increase of marine 87Sr/86Sr ratios at 16 Ma. A large increase of 1? in benthic foraminiferal delta18O values, interpreted to reflect global cooling and ice sheet growth, began approximately 1 million years later at 14.8 Ma, and the long-term shift toward lower bulk carbonate delta13C values began more than 2 Myr later around 13.6 Ma. The post-16 Ma increase in marine 187Os/188Os ratios was most likely forced by weathering of radiogenic materials, either old sediments or sialic crust with a sedimentary protolith. We consider two possible Miocene-specific geologic events that can account for both this increase in marine 187Os/188Os ratios and also nearly constant 87Sr/86Sr ratios: (1) the first glacial erosion of sediment-covered cratons in the Northern Hemisphere; (2) the exhumation of the Australian passive margin-New Guinea arc system. The latter event offers a mechanism, via enhanced availability of soluble Ca and Mg silicates in the arc terrane, for the maintenance of assumed low CO2 levels after 15 Ma. The temporal resolution (three samples/Myr) of the 187Os/188Os record from Site 598, for which a stable isotope stratigraphy was also constructed, is significantly higher than that of previously published records. These high resolution data suggest oscillations with amplitudes of 0.01 to 0.02 and periods of around 1 Myr. Although variations in the 187Os/188Os record of this magnitude can be easily resolved analytically, this higher frequency signal must be verified at other sites before it can be safely interpreted as global in extent. However, the short-term 187Os/188Os variations may correlate inversely with short-term benthic foraminiferal delta18O and bulk carbonate delta13C variations that reflect glacioeustatic events.

Geochemistry of a coral from Bermuda

We present a 55-year-long record (1928-1982) of Sr/Ca in a Bermuda coral (Diploria strigosa), which we use to reconstruct local twentieth century climate features. The clearest climate signal emerges for the late-year Sr/Ca. Although the coral was collected in shallow water (12 m), the correlation with station data is highest for temperatures at 50 m depth (r = -0.70), suggesting that local temperatures at the collection site are not representative for the sea surface temperatures in the adjacent open ocean. The most striking feature of the coral record is the persistent and significant correlation (r = -0.50) with the North Atlantic Oscillation (NAO) index. Field correlations of fall Sr/Ca with the winter sea level pressure (SLP) show the typical spatial NAO pattern. The stable relationship with the NAO shows that Sr/Ca in Bermuda corals is a suitable tool for the reconstruction of North Atlantic climate variability.

Magnetic properties of ODP Site 175-1075

We present sediment magnetic and chemical analysis of cyclic ocean sediments of the upwelling region of the Lower Congo Basin (equatorial Atlantic). We investigated two >100-k.y. intervals from Ocean Drilling Program Site 1075 to analyze the hysteresis properties, sources of magnetic susceptibility, anhysteretic remanent magnetizations, thermomagnetic behavior, and element concentrations of Fe, Ca, Ti, Mn, and K using an X-ray fluorescence (XRF) core scanner. The upper interval was sampled between 14 and 32 meters composite depth (mcd; 0.09-0.21 Ma) and the lower between 141 and 163 mcd (1.31-1.54 Ma) at a resolution of 20 cm, which represents a temporal resolution of 2.0 and 1.3 k.y., respectively. XRF core-scanner data were acquired at 5-cm intervals. The measurements show that ferri(o)magnetic minerals have no significant influence on the cyclicity of the magnetic susceptibility, which is dominated by paramagnetic and diamagnetic minerals and reflects changes of sediment input from the Congo River. The Fe, Ti, K, and Mn concentrations covary with the magnetic susceptibility where high concentrations of these elements correlate with intervals of high susceptibility and low concentrations with intervals of low susceptibility. The Ca counts correlate well with the calcium carbonate concentration but do not show the same cyclicity as the other elements or the susceptibility. With the exception of the Ca concentration, which is significantly higher in the upper interval, and the magnetic grain size, which indicates that less fine grained magnetite is present in the lower interval, no significant differences in the properties of the upper and the lower intervals were detected.