Ground truthing the Cd/Ca-carbon isotope relationship in foraminifera of the Greenland-Iceland-Norwegian Seas

In order to examine whether the paleoceanographic nutrient proxies, d13C and cadmium/calcium in foraminiferal calcite, are well coupled to nutrients in the region of North Atlantic Deep Water formation, we present da ta from two transects of the Greenland-Iceland-Norwegian Seas. Along Transect A (74.3°N, 18.3°E to 75.0°N, 12.5°W, 15 stations), we measured phosphate and Cd concentrations of modern surface sea water. Along Transect B (64.5°N, 0.7°W to 70.4°N, 18.2°W, 14 stations) we measured Cd/Ca ratios and d13C of the planktonic foraminifera Neogloboquadrina pachyderma sinistral in core top sediments. Our results indicate that Cd and phosphate both vary with surface water mass and are well correlated along Transect A. Our planktonic foraminiferal d13C data indicate similar nutrient variation with water mass along Transect B. Our Cd/Ca data hint at the same type of nutrient variability, but interpretations are hampered by low values close to the detection limit of this technique and therefore relatively large error bars. We also measured Cd and phosphate concentrations in water depth profiles at three sites along Transect A and the d13C of the benthic foraminifera Cibicidoides wuellerstorfi along Transect B. Modern sea water depth profiles along Transect A have nutrient depletions at the surface and then constant values at depths greater than 100 meters. The d13C of planktonic and benthic foraminifera from Transect B plotted versus depth also reflect surface nutrient depletion and deep nutrient enrichment as seen at Transect A, with a small difference between intermediate and deep waters. Overall we see no evidence for decoupling of Cd/Ca ratio and d13C in foraminiferal calcite from water column nutrient concentrations along these transects in a region of North Atlantic Deep Water formation.

Strontium isotope ratios of pore waters and planktonic foraminifera from DSDP holes

A detailed record of the strontium-87 to strontium-86 ratio in seawater during the last 100 million years was determined by measuring this ratio in 137 well-preserved and well-dated fossil foraminifera samples. Sample preservation was evaluated from scanning electron microscopy studies, measured strontium-calcium ratios, and pore water strontium isotope ratios. The evolution of the strontium isotopic ratio in seawater offers a means to evaluate long-term changes in the global strontium isotope mass balance. Results show that the marine strontium isotope composition can be used for correlating and dating well-preserved authigenic marine sediments throughout much of the Cenozoic to a precision of +/- 1 million years. The strontium-87 to strontium-86 ratio in seawater increased sharply across the Cretaceous/Tertiary boundary, but this feature is not readily explained as strontium input from a bolide impact on land.

Sediment and pore water geochemistry of sediment cores, Potter Cove, King George Island

Redox-sensitive trace metals (Mn, Fe, U, Mo, Re), nutrients and terminal metabolic products (NO3-, NH4+, PO43-, total alkalinity) were for the first time investigated in pore waters of Antarctic coastal sediments. The results of this study reveal a high spatial variability in redox conditions in surface sediments from Potter Cove, King George Island, western Antarctic Peninsula. Particularly in the shallower areas of the bay the significant correlation between sulphate depletion and total alkalinity, the inorganic product of terminal metabolism, indicates sulphate reduction to be the major pathway of organic matter mineralisation. In contrast, dissimilatory metal oxide reduction seems to be prevailing in the newly ice-free areas and the deeper troughs, where concentrations of dissolved iron of up to 700 µM were found. We suggest that the increased accumulation of fine-grained material with high amounts of reducible metal oxides in combination with the reduced availability of metabolisable organic matter and enhanced physical and biological disturbance by bottom water currents, ice scouring and burrowing organisms favours metal oxide reduction over sulphate reduction in these areas. Based on modelled iron fluxes we calculate the contribution of the Antarctic shelf to the pool of potentially bioavailable iron (Feb) to be 6.9x10**3 to 790x10**3 t/yr. Consequently, these shelf sediments would provide an Feb flux of 0.35-39.5/mg/m**2/yr (median: 3.8 mg/m**2/yr) to the Southern Ocean. This contribution is in the same order of magnitude as the flux provided by icebergs and significantly higher than the input by aeolian dust. For this reason suboxic shelf sediments form a key source of iron for the high nutrient-low chlorophyll (HNLC) areas of the Southern Ocean. This source may become even more important in the future due to rising temperatures at the WAP accompanied by enhanced glacier retreat and the accumulation of melt water derived iron-rich material on the shelf.

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).

(Table 1) Trace element/Ca ratios of Orbulina universa shells from late Neogene Mediterranean samples

A Mediterranean composite sedimentary record was analyzed for Ba/Ca ratios on carbonate shells of Orbulina universa planktonic foraminifer (Ba/Ca)carb providing the opportunity to study and assess the extent of freshwater inputs on the basin and possible impacts on its dynamics during the Tortonian to Recent period. A number of scanning electron microscope analyses and auxiliary trace element measurements (Mn, Sr, and Mg), obtained from the same samples, exclude important diagenetic effects on the studied biogenic carbonates and corroborate the reliability of (Ba/Ca)carb ratios in foraminifera calcite as indicators of seawater source components during the studied interval. A long-term trend with (Ba/Ca)carb values shifting from ~7 to 3 µmol/mol from the base of the Tortonian to the top of the Messinian is observed. The interval of the late Messinian salinity crisis, where biogenic carbonates are missing or strongly diagenized, represents a crucial passage not monitored in our record. At the base of the Pliocene, up to about 4.7 Ma, the (Ba/Ca)carb record shows a decreasing trend from ~4 µmol/mol stabilizing itself to an about constant value of 0.9 ± 0.3 µmol/mol for the whole Plio-Pleistocene interval. These results suggest a dramatic change in the continental runoff values, up to ~3-16 times higher during part of the late Neogene (Tortonian-early Pliocene), with a possible profound modification in the physical dynamics of the Mediterranean basin. First-order mass balance equations used to estimate barium and salinity budgets in the Mediterranean Sea during the late Miocene-early Pliocene interval support the hypothesis of an active connection of the basin with the Paratethys region and of a definitive restriction at the base of the Pliocene after about 0.7 Ma from the well-known Messinian Lagomare phase. They also open intriguing scenarios on possible circulation shifts during the Neogene.

Stable isotope and Mg/Ca record of Globigerinoides ruger morphotypes

Tests of the planktonic foraminifer Globigerinoides ruber (white; d'Orbigny) have become a standard tool for reconstructing past oceanic environments. Paleoceanographers often utilize the Mg/Ca ratios of the foraminiferal tests for reconstructing low-latitude ocean glacial-interglacial changes in sea surface temperatures (SST). We report herein a comparison of Mg/Ca measurements on sample pairs (n = 20) of two G. ruber (white) morphotypes (G. ruber sensu stricto (s.s.) and G. ruber sensu lato (s.l.)) from surface and downcore samples of the western Pacific and Indian Oceans. G. ruber s.s. refers to specimens with spherical chambers sitting symmetrically over previous sutures with a wide, high arched aperture, whereas G. ruber s.l. refers to a more compact test with a diminutive final chamber and small aperture. The G. ruber s.s. specimens generally show significantly higher Mg/Ca ratios compared to G. ruber s.l. Our results from the Mg/Ca ratio analysis suggest that G. ruber s.l. specimens precipitated their shells in slightly colder surface waters than G. ruber s.s. specimens. This conclusion is supported by the differences in delta18O and delta13C values between the two morphotypes. Although it is still unclear if these two morphotypes represent phenotypic variants or sibling species, our findings seem to support the hypothesis of depth and/or seasonal allopatry within a single morphospecies.

B/Ca ratios of benthic foraminifera

We present modern B/Ca core-top calibrations for the epifaunal benthic foraminifer Nuttallides umbonifera and the infaunal Oridorsalis umbonatus to test whether B/Ca values in these species can be used for the reconstruction of paleo-D[[CO3]2-]. O. umbonatus originated in the Late Cretaceous and remains extant, whereas N. umbonifera originated in the Eocene and is the closest extant relative to Nuttallides truempyi, which ranges from the Late Cretaceous through the Eocene. We measured B/Ca in both species in 35 Holocene sediment samples from the Atlantic, Pacific and Southern Oceans. B/Ca values in epifaunal N. umbonifera (~ 85-175 µmol/mol) are consistently lower than values reported for epifaunal Cibicidoides (Cibicides) wuellerstorfi (130-250 µmol/mol), though the sensitivity of D[[CO3]2-] on B/Ca in N. umbonifera (1.23 ± 0.15) is similar to that in C. wuellerstorfi (1.14 ± 0.048). In addition, we show that B/Ca values of paired N. umbonifera and its extinct ancestor, N. truempyi, from Eocene cores are indistinguishable within error. In contrast, both the B/Ca (35-85 µmol/mol) and sensitivity to D[[CO3]2-] (0.29 ± 0.20) of core-top O. umbonatus are considerably lower (as in other infaunal species), and this offset extends into the Paleocene. Thus the B/Ca of N. umbonifera and its ancestor can be used to reconstruct bottom water D[[CO3]2?], whereas O. umbonatus B/Ca appears to be buffered by porewater [[CO3]2-] and suited for constraining long-term drift in seawater B/Ca.

Primary composition, alteration, and origin of Cretaceous volcaniclastic rocks at DSDP Site 89-585

An upper Aptian to middle Albian series of volcaniclastic rocks more than 300 m thick was drilled at Site 585 in the East Mariana Basin. On the basis of textural and compositional (bulk-rock chemistry, primary and secondary mineral phases) evidence, the volcaniclastic unit is subdivided into a lower (below 830 m sub-bottom) and an upper (about 670-760 m) sequence; the boundary in the interval between is uncertain owing to lack of samples. The rocks are dominantly former vitric basaltic tuffs and minor lapillistones with lesser amounts of crystals and basaltic lithic clasts. They are mixed with shallow-water carbonate debris (ooids, skeletal debris), and were transported by mass flows to their site of deposition. The lower sequence is mostly plagioclase- and olivine-phyric with lesser amounts of Ti-poor clinopyroxene. Mineralogical and bulk-rock chemical data indicate a tholeiitic composition slightly more enriched than N-MORB (normal mid-ocean ridge basalt). Transport was by debris flows from shallow-water sites, as indicated by admixed ooids. Volcanogenic particles are chiefly moderately vesicular to nonvesicular blocky shards (former sideromelane) and less angular tachylite with quench plagioclase and pyroxene, indicating generation of volcanic clasts predominantly by spalling and breakage of submarine pillow and/or sheet-flow lavas. The upper sequence is mainly clinopyroxene- and olivine-phyric with minor plagioclase. The more Ti-rich clinopyroxene and the bulk-rock analyses show that the moderately alkali basaltic composition throughout is more mafic than the basal tholeiitic sequence. Transport was by turbidity currents. Rounded epiclasts of crystalline basalts are more common than in the lower sequence, and, together with the occurrence of oxidized olivine pseudomorphs and vesicular tachylite, are taken as evidence of derivation from eroded subaerially exposed volcanics. Former sideromelane shards are more vesicular than in the lower sequence; vesicularity exceeds 60 vol.% in some clasts. The dominant clastic process is interpreted to be by shallow-water explosive eruptions. All rocks have undergone low-temperature alteration; the dominant secondary phases are "palagonite," chlorite/smectite mixed minerals, analcite, and chabazite. Smectite, chlorite, and natrolite occur in minor amounts. Phillipsite is recognized as an early alteration product, now replaced by other zeolites. During alteration, the rocks have lost up to 50% of their Ca, compared with a fresh shard and fresh glass inclusions in primary minerals, but have gained much less K, Rb, and Ba than expected, indicating rapid deposition prior to significant seafloor weathering.

Oxygen isotope and Mg/Ca record of planktonic foraminifera of sediment core MD01-2390

Changes in the local freshwater budget over the last 22,000 years have been estimated from a sediment core located in the southern South China Sea (SCS) using a combined approach of Mg/Ca and oxygen isotopes on the planktonic foraminifera Globigerinoides ruber (white) sensu stricto (s.s.). Core MD01-2390 (06°28,12N, 113°24,56E; water depth 1591 m) is located near the glacial paleo-river mouths of the Baram, Rajang and North Sunda/Molengraaff Rivers that drained the exposed Sunda Shelf. The delta18Oseawater record reveals lower average values (-0.96±0.18 per mil) during the Last Glacial Maximum (LGM) when compared with modern values (-0.54±0.18 per mil). Low salinity during the LGM is interpreted to reflect a higher freshwater contribution due to a greater proximity of the core site to the mouths of the Baram, Rajang and North Sunda/Molengraaff Rivers at that time. A general deglacial increasing trend in salinity due to the progressive landward displacement of the coastline during deglacial shelf flooding is punctuated by several short-term shifts towards higher and lower salinity that are likely related to abrupt changes in the intensity of the East Asian summer monsoon. Thus, the deglacial delta18Oseawater changes reflect the combined effects of sea-level-induced environmental changes on the shelf (e.g. phases of retreat and breakdown of the shelf drainage systems) and East Asian monsoon climate change. Lower salinity than at present during the Early Holocene may be attributed to an increase in summer monsoonal precipitation that is corroborated by previous marine and terrestrial studies that report a Preboreal-Early Holocene monsoon optimum in the Asian monsoon region.

Mg/Ca, Sr/Ca and Ca isotope ratios in benthonic foraminifers of surface sediment samples

We analysed Mg/Ca, Sr/Ca and Ca isotope ratios of benthonic foraminifers from sediment core tops retrieved during several research cruises in the Atlantic Ocean, in order to improve the understanding of isotope fractionation and element partitioning resulting from biomineralisation processes and changes in ambient conditions. Species include foraminifers secreting tests composed of hyaline low magnesium calcite, porcelaneous high magnesium calcite as well as aragonite. Our results demonstrate systematic isotope fractionation and element partitioning patterns specific for these foraminiferal groups. Calcium isotope fractionation is similar in porcelaneous and hyaline calcite tests and both groups demonstrate the previously described anomaly with enrichment of heavy isotopes around 3 - 4 °C (Gussone and Filipsson, 2010). Calcium isotope ratios of the aragonitic species Hoeglundina elegans, on the other hand, are about 0.4 per mil lighter compared to the calcitic species, which is in general agreement with stronger fractionation in inorganic aragonite compared to calcite. However, the low and strongly variable Sr content suggests additional processes during test formation, and we propose that transmembrane ion transport or a precursor phase to aragonite may be involved. Porcelaneous tests, composed of high Mg calcite, incorporate higher amounts of Sr compared to hyaline low Mg calcite, in agreement with inorganic calcite systematics, but also porcelaneous tests with reduced Mg/Ca show high Sr/Ca. While calcium isotopes, Sr/Ca and Mg/Ca in benthonic foraminifers primarily appear to fractionate and partition with a dominant inorganic control, d44/40Ca temperature and growth rate dependencies of benthonic foraminifer tests favour a dominant contribution of light Ca by transmembrane transport relative to unfractionated seawater Ca to the calcifying fluid, thus controlling the formation of foraminiferal d44/40Ca and Sr/Ca proxy signals.

Mg/Ca ratios of Neogloboquadrina pachyderma (s) and Globigerina bulloides in Irminger Sea sediment trap time series

iven the importance of high-latitude areas in the ocean-climate system, there is need for a paleothermometer that is reliable at low temperatures. Here we assess the applicability of the Mg/Ca-temperature proxy in colder waters (5-10?°C) by comparing for the first time the seasonal Mg/Ca and d18O cycles of N. pachyderma (s) and G. bulloides using a sediment trap time-series from the northern North Atlantic. While both species show indistinguishable seasonal d18O patterns that clearly track the near surface temperature cycle, their Mg/Ca are very different. G. bulloides Mg/Ca is high (2.0-3.1 mmol/mol), but varies in concert with the seasonal temperature cycle. The Mg/Ca of N. pachyderma (s), on the other hand, is low (1.1-1.5 mmol/mol) and shows only a very weak seasonal cycle. The d18O patterns indicate that both species calcify in the same depth zone. Consequently, depth habitat differences cannot explain the contrasting Mg/Ca patterns. The elevated Mg/Ca in pristine G. bulloides might be due to the presence of high Mg phases that are not preserved in fossil shells. The contrasting absence of a seasonal trend in the Mg/Ca of N. pachyderma (s) confirms other studies where calcification temperatures were less well constrained. The reason for this absence is not fully known, but may include species-specific vital effects. The very different seasonal patterns of both species' Mg/Ca underscore the importance of parameters other than temperature in controlling planktonic foraminiferal Mg/Ca. Our results therefore lend further caution in the interpretation of Mg/Ca-temperature reconstructions from high northern latitudes.

Mg/Ca and d18O measurements of planktonic foraminifera from Sargasso Sea

Paired Mg/Ca and d18O 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 d18O 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.

Mg/Ca of planktonic foraminifera from tropical Pacific surface sediments

Mg/Ca in planktonic foraminifers carries two main signals: calcification temperature and postdepositional test dissolution. Shell dissolution thus distorts water temperature reconstructions made with Mg/Ca in foraminifers. This problem could be resolved by quantifying the impact of carbonate dissolution on Mg/Ca with an independent, temperature-insensitive deep-sea calcite dissolution proxy, such as the Globorotalia menardii fragmentation index (MFI). To test the validity of this approach, we measured Mg/Ca in the tests of several planktonic foraminifers and MFI in core tops collected over a wide geographic region of the tropical Pacific and covering a wide range of deep-sea calcite dissolution and seawater temperature. We confirm that Mg/Ca from different species have different susceptibility to temperature and dissolution. Mg/Ca in surface-dwelling Globigerina bulloides is controlled by calcification temperature and is largely unaffected by carbonate dissolution estimated from MFI. In contrast, Mg/Ca in deeper dwelling G. menardii is minimally sensitive to temperature and dominantly affected by dissolution. Mg/Ca in Neogloboquadrina dutertrei and Pulleniatina obliquiloculata are significantly affected by both temperature and dissolution, and MFI can be effectively used to correct temperature estimates from these species for calcite dissolution. Additional variables besides temperature and dissolution appear to control Mg/Ca in Globorotalia tumida, and their identification is a prerequisite for interpreting elemental shell composition in this species. Combining down-core measurements of Mg/Ca in multiple foraminifer species with MFI provides a powerful tool for reconstructing past changes in the upper water column temperature structure in the tropical Pacific.

High resolution stable isotope and Mg/Ca record of sediment core MD02-2550C2

An early Holocene record from the Gulf of Mexico (GOM) reveals climatic and hydrologic changes during the interval from 10.5 to 7 thousand calendar years before present from paired analyses of Mg/Ca and d18O on foraminiferal calcite. The sea surface temperature record based on foraminiferal Mg/Ca contains six oscillations and an overall ~1.5°C warming that appears to be similar to the September-March insolation difference. The d18O of seawater in the GOM (d18OGOM) record contains six oscillations, including a -0.8 per mil excursion that may be associated with the "8.2 ka climate event" or a broader climate anomaly. Faunal census records from three GOM cores exhibit similar changes, suggesting subcentennial-scale variability in the incursions of Caribbean waters into the GOM. Overall, our results provide evidence that the subtropics were characterized by decadal- to centennial-scale climatic and hydrologic variability during the early Holocene.

Seawater carbonate chemistry and physiological response of the Mediterranean crustose coralline alga Lithophyllum cabiochae to elevated pCO2 and temperature

The response of respiration, photosynthesis, and calcification to elevated pCO2 and temperature was investigated in isolation and in combination in the Mediterranean crustose coralline alga Lithophyllum cabiochae. Algae were maintained in aquaria during 1 year at near-ambient conditions of irradiance, at ambient or elevated temperature (+3 °C), and at ambient (ca. 400 µatm) or elevated pCO2 (ca. 700 µatm). Respiration, photosynthesis, and net calcification showed a strong seasonal pattern following the seasonal variations of temperature and irradiance, with higher rates in summer than in winter. Respiration was unaffected by pCO2 but showed a general trend of increase at elevated temperature at all seasons, except in summer under elevated pCO2. Conversely, photosynthesis was strongly affected by pCO2 with a decline under elevated pCO2 in summer, autumn, and winter. In particular, photosynthetic efficiency was reduced under elevated pCO2. Net calcification showed different responses depending on the season. In summer, net calcification increased with rising temperature under ambient pCO2 but decreased with rising temperature under elevated pCO2. Surprisingly, the highest rates in summer were found under elevated pCO2 and ambient temperature. In autumn, winter, and spring, net calcification exhibited a positive or no response at elevated temperature but was unaffected by pCO2. The rate of calcification of L. cabiochae was thus maintained or even enhanced under increased pCO2. However, there is likely a trade-off with other physiological processes. For example, photosynthesis declines in response to increased pCO2 under ambient irradiance. The present study reports only on the physiological response of healthy specimens to ocean warming and acidification, however, these environmental changes may affect the vulnerability of coralline algae to other stresses such as pathogens and necroses that can cause major dissolution, which would have critical consequence for the sustainability of coralligenous habitats and the budgets of carbon and calcium carbonate in coastal Mediterranean ecosystems.