Carbonate properties and oxygen concentrations at time series station DYFAMED

Monthly measurements of pH, alkalinity and oxygen over two years (February 1998-February 2000) at the Dyfamed site in the central zone of the Ligurian-Provençal Basin of the Mediterranean made it possible to assess the vertical distributions (5-2000 m) and the seasonal variations of these properties. Alkalinity varies linearly with salinity between surface water and the Levantine Intermediate Water (marked by a maximum of temperature and salinity). In deep water, total alkalinity is also correlated linearly to salinity, but the slope of the regression line is 15% less. In surface water, the pH at 25°C varies between 7.91 and 8.06 on the total proton scale depending upon the season. The lowest values are observed in winter, the highest in spring and in summer. These variations are primarily due to biological production. The pH goes through a minimum around 150-200 m and a small maximum below the intermediate water. The total dissolved inorganic carbon content (deduced from pH and alkalinity) is variable in surface water (2205-2310 ?mol/kg) and has a maximum in intermediate water, which is related to the salinity maximum. Normalized total inorganic carbon at a constant salinity is strongly negatively correlated with pH at 25°C. The fugacity of CO2, (fCO2) varies between 320 and 430 ?atm in surface water, according to the season. Below the seasonal thermocline, the maximum fCO2 (about 410 ?atm) is located around 150-200 m. The presence of a minimum of oxygen in the intermediate water of this area has been observed for several years, but our measurements made it possible to specify the relationship between oxygen and salinity in deep water. Data from the intense vertical mixing during the winters of 1999 and 2000 were used to calculate the oxygen quantity exchanged with the atmosphere during these periods. The estimated quantity of oxygen entering the Mediterranean Sea exceeds that deduced from exchange coefficients calculated with the formula of Wanninkhof and McGillis. During the vertical mixing in the 1999 winter, fCO2 in surface water was on average below equilibrium with atmospheric fCO2, thus implying that CO2 was entering the sea. However, on this time scale, even with high exchange coefficients, the estimated CO2 uptake had no significant influence on the inorganic carbon content in the water column.

Iodine speciation at time series station DYFAMED

Iodine speciation analysis was carried out upon seawater samples collected in July 1993 at the DYFAMED station (43 °25?N, 7 °52?E) located in the northwestern Mediterranean Sea. Dissolved iodate and iodide were directly determined by differential pulse polarography and cathodic stripping square wave voltammetry, respectively, and organically bound iodine was estimated by wet-chemical oxidation with sodium hypochlorite. Iodate is the predominant species ranging from 416 nM in surface waters to 480 nM in bottom waters. Iodide is present in significant concentrations up to 60 nM in surface waters, undetectable between 500 and 1000 m depth and present in very low but measurable concentrations (about 6 nM) in deep waters. The vertical profile of total free iodine demonstrates observable removal from surface waters, slight enrichment at about 200 m depth and constant there below. Up to 40 nM of organically bound iodine has been estimated between 20 to 30 m. Factorial analysis of different iodine species with biologically relevant parameters provided strong evidence for iodine biophilic features.

Alkenones in the northwestern Mediterranean Sea

C37 alkenone fluxes were measured with sediment traps at 200 m depth over the years 1989/1990 and 1993/1994 to assess the interannual variability of the alkenone flux from the surface waters of the Mediterranean Sea. Fall and spring were identified as the high flux periods. SST estimates derived from the UK'37 index indicated 50 m and 30 m as major production depths in spring and fall, respectively. Althought interannual variation of alkenone fluxes was notable, the seasonality and depth of production appeared to be recurrent features of the coccolithophorid cycle of production. Alkenone fluxes at 1000 m measured over the year 1993/1994 were about 5 times lower than at 200 m and show no evidence of preferential preservation relative to the organic carbon between these depths. SST predicted at 200 m and 1000 m indicated a remarkably good transfer of the surface temperature signal to deeper layers.

Rare earth and other element contents and speciations in samples from Core AKO26-35, Pacific Ocean, Southwest Basin

Ferromanganese micro- and macronodules in eupelagic clays at Site AKO26-35 in the Southwest Pacific Basin were studied in order to check REE distribution during ferromanganese ore formation in non-productive zones of the Pacific Ocean. Host sediments and their labile fraction, ferromanganese micronodules (in size fractions 50-100, 100-250, 250-500, and >500 ?m) from eupelagic clays (horizons 37-10, 105-110, 165-175, and 189-190 cm), and buried ferromanganese micronodules (horizons 64-68, 158-159, and 165-166 cm) were under study. Based on partition analysis data anomalous REE enrichment in eupelagic clays from Site AKO26-35 is related to accumulation of rare earth elements in iron hydroxophosphates. Concentration of Ce generally bound with manganese oxyhydroxides is governed by oxidation of Mn and Ce in ocean surface waters. Micronodules (with Mn/Fe from 0.7 to 1.6) inherit compositional features of the labile fraction of bottom sediments. Concentrations of Ce, Co, and Th depend on micronodule sizes. Enrichment of micronodules in hydrogenic or hydrothermal matter is governed by their sizes and by a dominant source of suspended oxyhydroxide material. The study of buried ferromanganese micronodules revealed general regularities in compositional evolution of oxyhydroxide matrices of ferromanganese micro- and macronodules. Compositional variation of micro- and macronodules relative to the labile fraction of sediments in the Pacific non-productive zone dramatically differs from the pattern in bioproductive zones where micronodule compositions in coarser fractions are similar to those in associated macronodules and labile fractions of host sediments due to more intense suboxidative diagenesis.

Stable isotope record of sediment cores from the North Atlantic

Abrupt and short climate changes, such as the Younger Dryas, punctuated the last glacial-to-interglacial transition (Ruddiman and McIntyre, 1981 doi:10.1016/0031-0182(81)90097-3; Duplessy et al., 1981 doi:10.1016/0031-0182(81)90096-1; Oeschger et al. 1984; Broecker et al., 1985 doi:10.1038/315021a0). Broecker et al. (1988 doi:10.1029/PA003i001p00001) proposed that these may have been caused by an interruption of thermohaline circulation as inputs of glacial meltwater freshened the surface waters of the North Atlantic. The finding (Fairbanks, 1989 doi:10.1038/342637a0) that meltwater discharge was minimal during the Younger Dryas, however, led to the suggestion that the surface-water salinity drop might have been caused instead by changes in the freshwater budget (the difference between precipitation and evaporation), accompanied by a reduction in poleward advection of saline subtropical water. Here we use micropalaeontological and stable-isotope records from foraminifera in two cores from the North Atlantic to generate two continuous, high-resolution records of sea surface temperature and salinity changes over the past 18,000 years. Despite the injection of glacial meltwater during warm episodes, we find that sea surface salinity and temperature remain positively correlated during deglaciation. Cold, low-salinity events occurred during the early stages of deglaciation (14,500-13,000 years ago) and the Younger Dryas, but the minor injections of meltwater at high latitudes during these events are insufficient to account for the observed salinity changes. We conclude that an additional feedback from changes in the hydrological cycle and in advection was necessary to trigger changes in thermohaline circulation and thus in climate. This feedback did not act when the meltwater injection occurred at low latitude.

Oxygen and carbon isotope stratigraphy of ODP Holes 107-653A and 107-654A

Stable isotope analysis of two species (or groups of species) of planktonic foraminifers: Globigerinoides ruber (or G. obliquus and G. obliquus extremus) and Globigerina bulloides (or G. falconensis and G. obesa) from ODP Hole 653A and Site 654 in the Tyrrhenian basin, records the Pliocene-Pleistocene glacial history of the Northern Hemisphere. The overall increase in mean d18O values through the interval 4.6-0.08 Ma is 1.7 per mil for G. bulloides and 1.5 per mil for G. ruber. The time interval 3.1-2.5 Ma corresponds to an important phase of 18O enrichment for planktonic foraminifers. In this interval, glacial d18O values of both species G. bulloides and G. ruber increase by about l per mil, this increase being more progressive for G. ruber than for G. bulloides. The increase of interglacial d18O values is higher for G. bulloides (1.5 per mil) than for the Gruber group (1 per mil). These data suggest a more pronounced seasonal stratification of the water masses during interglacial phases. Large positive d18O fluctuations of increasing magnitude are also recorded at 2.25 and 2.15 Ma by G bulloides and appear to be diachronous with those of Site 606 in the Atlantic Ocean. Other events of increasing d18O values are recorded between 1.55 and 1.3 Ma, at 0.9 Ma, 0.8 Ma, and near 0.34 Ma. In the early Pliocene the d18O variability recorded by the planktonic species G. bulloides was higher in the Mediterranean than in the Atlantic at the same latitude. This suggests that important cyclic variations in the water budget of the Mediterranean occurred since that time. Step increases in the d18O variability are synchronous with those of the open ocean at 0.9 and 0.34 Ma. The higher variability as well as the higher amplitude of the peaks of 18O enrichment may be partly accounted for by increase of dryness over the Mediterranean area. In particular the high amplitude d18O fluctuations recorded between 3.1 and 2.1 Ma are correlated with the onset of a marked seasonal contrast and a summer dryness, revealed by pollen analyses. Strong fluctuations towards d13C values higher than modern ones are recorded by the G. ruber group species before 1.7 Ma and suggest a high production of phytoplankton. When such episodes of high primary production are correlated with episodes of decreasing 13C content of G. bulloides, they are interpreted as the consequence of a higher stratification of the upper water masses resulting itself from a marked seasonality. Such episodes occur between 4.6 and 4.05 Ma, 3.9 and 3.6 Ma, and 3.25 and 2.66 Ma. The interval 2.66-1.65 Ma corresponds to a weakening of the stratification of the upper water layers. This may be related to episodes of cooling and increasing dryness induced by the Northern Hemisphere Glaciations. The Pleistocene may have been a less productive period. The transition from highly productive to less productive surface waters also coincides with a new step increase in dryness and cooling, between 1.5 and 1.3 Ma. The comparison of the 13C records of G ruber and G. bulloides in fact suggests that a high vertical convection became a dominant feature after 2.6 Ma. Increases in the nutrient input and the stratification of the upper water masses may be suspected, however, during short episodes near 0.86 Ma (isotopic stage 25), 0.57-0.59 Ma (isotopic stage 16), 0.49 Ma (isotopic stage 13), 0.4-0.43 Ma (isotopic stage 11), and 0.22 and 0.26 Ma (part of isotopic stage 7 and transition 7/8). In fact, changes in the C02 balance within the different water masses of the Tyrrhenian basin as well as in the local primary production did not follow the general patterns of the open ocean.

Middle Miocene stable carbon and oxygen isotope record of foraminifera of ODP Hole 120-747A

Paleoceanographic variability at southern high latitude Ocean Drilling Program (ODP) Site 747 was investigated in this study through the interval which spans the Middle Miocene Climate Transition (MMCT). Between 15.0 and 12.2 million years ago (Ma), foraminiferal d18O records derived from both benthic (Cibicidoides spp.) and planktonic taxa (Globorotalia praescitula and Globigerina bulloides) reveal a history of changes in water column thermal and salinity structure and a strong imprint of seasonality. Prior to the MMCT, in the interval between 14.35 and 13.9 Ma, G. bulloides displays relatively high d18O values similar to those of G. praescitula, interpreted to indicate weakening of the thermocline and/or increased seasonality with cooler early-spring and/or late-fall temperatures. Following this interval, G. bulloidesd18O values diverge significantly from benthic and G. praescitula values, with G. bulloides values remaining relatively low for at least 600 kyr following the benthic foraminiferal d18O shift during the MMCT at ~13.9 Ma. This divergence in d18O records occurs in direct association with the Mi3 cooling and glaciation event and may suggest: (1) a strengthening of the vertical temperature gradient, with greater cooling of deep waters than surface waters, (2) changes in the depth habitat of G. bulloides, (3) changes in the dominant season of G. bulloides calcification, (4) modification of surface-water d18O values in association with enhanced sea-ice formation, (5) increased surface-water carbonate ion concentration, and/or (6) a significant decrease in surface-water salinity across the MMCT. The first of these possible scenarios is not likely, particularly in light of recent Mg/Ca evidence for significant surface-water cooling in the Southern Ocean associated with the MMCT. Of the remaining possibilities, we favor a change in surface salinity to explain the observed trends in d18O values and hypothesize that surface salinity may have decreased by up to 2 salinity units at ~13.9 Ma. In this scenario, the development of a lower-salinity Antarctic surface layer coincided with regional cooling of both surface and deep waters of the Southern Ocean during the Mi3 glaciation of East Antarctica, and contributed into the dominance of Neogloboquadrina spp. between 13.8 and 13.2 Ma. Additionally, the distinct patterns observed in planktonic foraminiferal d18O records spanning the MMCT correspond with changes in the vertical d13C gradient between planktonic and benthic foraminiferal records and major changes in planktonic foraminiferal assemblages at Site 747, providing further evidence of the environmental significance of this climatic transition.

Stable carbon and oxygen isotope ratios of benthic foraminifera from Paleocene to Oligocene sediments

Benthic oxygen and carbon isotopic results from a depth transect on Maud Rise, Antarctica, provide the first evidence for Warm Saline Deep Water (WSDW) in the Paleogene oceans. Distinct reversals occur in the oxygen isotopic gradient between the shallower Hole 689B (Eocene depth ~1400 m; present-day depth 2080 m) and the deeper Hole 690B (Eocene depth ~2250 m; present-day depth 2914 m). The isotopic reversals, well developed by at least 46 Ma (middle middle Eocene), existed for much of the remaining Paleogene. We do not consider these reversals to be artifacts of differential diagenesis between the two sites or to have resulted from other potentially complicating factors. This being so, the results show that deep waters at Hole 690B were significantly warmer than deep waters at the shallower Hole 689B. A progressive decrease and eventual reversal in benthic to planktonic delta18O gradients in Hole 690B, demonstrate that the deeper waters became warmer relative to Antarctic surface waters during the Eocene. The warmer deep waters of the Paleogene are inferred to have been produced at middle to low latitudes, probably in the Tethyan region which contained extensive shallow-water platforms, ideal sites for the formation of high salinity water through evaporative processes. The ocean during the Eocene, and perhaps the Paleocene, is inferred to have been two-layered, consisting of warm, saline deep waters formed at low latitudes and overlain by cooler waters formed at high latitudes. This thermospheric ocean, dominated by halothermal circulation we name Proteus. The Neogene and modern psychrospheric ocean Oceanus is dominated by thermohaline circulation of deep waters largely formed at high latitudes. An intermediate condition existed during the Oligocene, with a three-layered ocean that consisted of cold, dense deep waters formed in the Antarctic (Proto-AABW), overlain by warm, saline deep waters from low latitudes, and in turn overlain by cool waters formed in the polar regions. This we name Proto-oceanus which combined both halothermal and thermohaline processes. The sequence of high latitude, major, climatic change inferred from the oxygen isotopic records is as follows: generally cooler earlier Paleocene; warming during the late Paleocene; climax of Cenozoic warmth during the early Eocene and continuing into the early middle Eocene; cooling mainly in a series of steps during the remainder of the Paleogene. Superimposed upon this Paleogene pattern, the Paleocene/Eocene boundary is marked by a brief but distinct warming that involved deep to surface waters and a reduction in surface to deep carbon and oxygen isotopic gradients. This event coincided with major extinctions among the deep-sea benthic foraminifers as shown by Thomas (1990 doi:10.2973/odp.proc.sr.113.123.1990). Salinity has played a major role in deep ocean circulation, and thus paleotemperatures cannot be inferred directly from the oxygen isotopic composition of Paleogene benthic foraminifers without first accounting for the salinity effect.

Geochemistry of planktonic foraminifera of sediment core MD97-2121

In situ measurements of Mg/Ca, Zn/Ca, Mn/Ca, and Ba/Ca in Globigerinoides bulloides and Globigerina ruber from southwest Pacific core top sites and plankton tow are reported and their potential as paleoproxies is explored. The modern samples cover 20° of latitude from 34°S to 54°S, 7-19°C water temperature, and variable influence of subantarctic (SAW) and subtropical (STW) surface waters. Trace element signatures recorded in core top and plankton tow planktic foraminifera are examined in the context of the chemistry and nutrient profiles of their modern water masses. Our observations suggest that Zn/Ca and Mn/Ca may have the potential to trace SAW and STW. Intraspecies and interspecies offsets identified by in situ measurements of Mg/Ca and Zn/Ca indicate that these ratios may also record changes in thermal and nutrient stratification in the upper ocean. We apply these potential proxies to fossilized foraminifera from the high-resolution core MD97 2121. At the Last Glacial Maximum, surface water Mg/Ca temperature estimates indicate that temperatures were approximately 6-7°C lower than those of the present, accompanied by low levels of Mn/Ca and Zn/Ca and minimal thermal and nutrient stratification. This is consistent with regional dominance of SAW and reduced STW inflow associated with a reduced South Pacific Gyre (SPG). Upper ocean thermal and nutrient stratification collapsed during the Antarctic Cold Reversal, before poleward migration of the zonal winds and ocean fronts invigorated the SPG and increased STW inflow in the early Holocene. Together with reduced winds, this favored a stratified upper ocean from circa 10 ka to the present.

Production of biogenic silica during the EBENE cruise, Equatorial Pacific

During the EBENE cruise (November 1996), distributions of biogenic silica concentration and production rates were investigated in the surface waters of the equatorial Pacific (180°W, from 8°S to 8°N), with particular emphasis on the limitation of the biogenic silica production by ambient silicic acid concentrations. Integrated over the depth of the euphotic layer, concentrations of biogenic silica and production rates were maximum at the Equator (8.0 and 2.6 mmol/m**2/d) and decreased more or less symmetrically polewards. Contribution of diatoms to the new production was estimated indirectly, comparing biogenic silica production rates and available data of new and export production in the same area. This comparison shows that new production in the equatorial area could mostly be sustained by diatoms, accounting for the major part of the exported flux of organic carbon. Kinetics experiments of silicic acid enrichment were performed. Half saturation constants were 1.57 µM at 3°S and 2.42 µM at the Equator close to the ambient concentrations. The corresponding Vmax values for Si uptake were 0.028/h at 3°S and 0.052/h at the equator. Experiments also show that in situ rates were restricted to 13-78% of Vmax, depending on ambient silicic acid concentrations. This work provides the first direct evidence that the rate of Si uptake by diatom populations of the equatorial Pacific is limited by the ambient concentration of silicic acid. However, such Si limitation might not be sufficient in itself to explain the low diatom growth rates observed, and additional limitation is suggested. One hypothesis that is consistent with the results of Fe limitation studies is that Fe and Si limitations may interact, rather than just being a mutually exclusive explanation for the HNLC character of the system.

Planktonic foraminiferal and stable oxygen isotope record of Holocene sediments from the Norwegian Sea

High-resolution records from IMAGES core MD95-2011 in the eastern Norwegian Sea provide evidence for relatively large- and small-scale high-latitude climate variability throughout the Holocene. During the early and mid-Holocene a situation possibly driven by consistent stronger westerlies increased the eastward influence of Arctic intermediate and near-surface waters. For the late Holocene a relaxation of the atmospheric forcing resulted in increased influence of Atlantic water. The main changes in Holocene climate show no obvious connection to changing solar irradiance, and spectral analysis reveals no consistent signature for any periodic behavior of Holocene climate at millennial or centennial timescales. There are, however, indications of consistent multidecadal variability.