Changes in bottom water corrosiveness and carbonate ion concentrations in the sub-Antarctic Atlantic during the last glacial period

The glacial climate system transitioned rapidly between cold (stadial) and warm (interstadial) conditions in the Northern Hemisphere. This variability, referred to as Dansgaard-Oeschger variability, is widely believed to arise from perturbations of the Atlantic Meridional Overturning Circulation. Evidence for such changes during the longer Heinrich stadials has been identified, but direct evidence for overturning circulation changes during Dansgaard-Oeschger events has proven elusive. Here we reconstruct bottom water [CO3]2- variability from B/Ca ratios of benthic foraminifera and indicators of sedimentary dissolution, and use these reconstructions to infer the flow of northern-sourced deep water to the deep central sub-Antarctic Atlantic Ocean. We find that nearly every Dansgaard-Oeschger interstadial is accompanied by a rapid incursion of North Atlantic Deep Water into the deep South Atlantic. Based on these results and transient climate model simulations, we conclude that North Atlantic stadial-interstadial climate variability was associated with significant Atlantic overturning circulation changes that were rapidly transmitted across the Atlantic. However, by demonstrating the persistent role of Atlantic overturning circulation changes in past abrupt climate variability, our reconstructions of carbonate chemistry further indicate that the carbon cycle response to abrupt climate change was not a simple function of North Atlantic overturning.

Age models and stable isotope ratios from the Mid-Miocene

Mid-Miocene pelagic sedimentary sections can be correlated using intermediate and high resolution oxygen and carbon isotopic records of benthic foraminifera. Precision of a few tens of thousands of years is readily achievable at sites with high sedimentation rates, for example, Deep Sea Drilling Project sites 289 and 574. The mid-Miocene carbon isotope records are characterized by an interval of high d13C values between 17 and 13.5 Ma (the Monterey Excursion of Vincent and Berger 1985) upon which are superimposed a series of periodic or quasi-periodic fluctuations in d13C values. These fluctuations have a period of approximately 440 kyr, suggestive of the 413 kyr cycle predicted by Milankovitch theory. Vincent and Berger proposed that the Monterey Excursion was the result of increased organic carbon burial in continental margins sediments. The increased d13C values (called 13C maxima) superimposed on the generally high mid-Miocene signal coincide with increases in d18O values suggesting that periods of cooling and/or ice buildup were associated with exceptionally rapid burial of organic carbon and lowered atmospheric CO2 levels. It is likely that during the Monterey Excursion the ocean/atmosphere system became progressively more sensitive to small changes in insolation, ultimately leading to major cooling of deep water and expansion of continental ice. We have assigned an absolute chronology, based on biostratigraphic and magneto-biostratigraphic datum levels, to the isotope stratigraphy and have used that chronology to correlate unconformities, seismic reflectors, carbonate minima, and dissolution intervals. Intervals of sediment containing 13C maxima are usually better preserved than the overlying and underlying sediments, indicating that the d13C values of TCO2 in deep water and the corrosiveness of seawater are inversely correlated. This again suggests that the 13C maxima were associated with rapid burial of organic carbon and reduced levels of atmospheric CO2. The absolute chronology we have assigned to the isotopic record indicates that the major mid-Miocene deepwater cooling/ice volume expansion took 2 m.y. and was not abrupt as had been reported previously. The cooling appears abrupt at many sites because the interval is characterized by a number of dissolution intervals. The cooling was not monotonic, and the 2 m.y. interval included an episode of especially rapid cooling as well as a brief return to warmer conditions before the final phase of the cooling period. The increase in d18O values of benthic foraminifera between 14.9 and 12.9 Ma was greatest at deeper water sites and at sites closest to Antarctica. The data suggest that the d18O value of seawater increased by no more than about 1.1 per mil during this interval and that the remainder of the change in benthic d18O values resulted from cooling in Antarctic regions of deepwater formation. Equatorial planktonic foraminifera from sites 237 and 289 exhibit a series of 0.4 per mil steplike increases in d13C values. Only one of these increases in planktonic d13C is correlated with any of the features in the mid-Miocene benthic carbon isotope record.

Miocene benthic foraminifer oxygen and carbon isotope record of ODP Site 115-709

The benthic isotopic record of Miocene Cibicidoides from Site 709 provides a record of conditions in the Indian Ocean at a depth of about 3200 mbsf. As expected, the record qualitatively resembles those of other Deep Sea Drilling Project and Ocean Drilling Program sites. The data are consistent with the scenario for the evolution of thermohaline circulation in the Miocene Indian Ocean proposed by Woodruff and Savin (1989, doi:10.1029/PA004i001p00087). Further testing of that scenario, however, requires isotopic data for Cibicidoides from other Indian Ocean sites. There is a correlation between d13C values of Cibicidoides and planktonic:benthic (P:B)ratios of Site 709 sediments, implying a causal relationship between the corrosiveness of deep waters and concentration of CO2 derived from oxidation of organic matter.

Age model and grain size distribution of the fine fraction of ODP Site 114-704

The physical properties of sediments beneath an upwelling area in the southern part of the Atlantic Ocean (ODP Hole 704A) were investigated. Highly significant correlations characterize the relationship of carbonate content to bulk density (R = 0.85), carbonate content to porosity (R = 0.84), and carbonate content to impedance (R = 0.84). No relationship exists between carbonate content and compressional-wave velocity (R = 0.24), indicating that amplitude variations in impedance are primarily controlled by variations in bulk density, which, in turn, are controlled by climatically driven biogenic opal and carbonate deposition. In general, maxima in impedance correspond to maxima in carbonate content (minima in opal content). The impedance record exhibits its most drastic change at about 2.4 Ma, marking dramatic increases in the average content of biogenic opal and the beginning of large-amplitude fluctuations. Between 0.7 and 0.4 Ma carbonate content, bulk density, and grain density decrease while opal content drastically increases. Similar changes have been observed in sediments beneath an upwelling cell off northwest Africa, indicating an oceanwide enhancement in upwelling or in the calcite corrosiveness of bottom water that appears to be isochronous.

Aragonite distribution and preservation of sediment cores from the Brazilian Continental Slope

We present late Quaternary records of aragonite preservation determined for sediment cores recovered on the Brazilian Continental Slope (1790-2585 m water depth) where North Atlantic Deep Water (NADW) dominates at present. We have used various indirect dissolution proxies (carbonate content, aragonite/calcite contents, and sand percentages) as well as gastropodal abundances and fragmentation of Limacina inflata to determine the state of aragonite preservation. In addition, microscopic investigations of the dissolution susceptibility of three Limacina species yielded the Limacina Dissolution Index which correlates well with most of the other proxies. Excellent preservation of aragonite was found in the Holocene section, whereas aragonite dissolution gradually increases downcore. This general pattern is attributed to an overall increase in aragonite corrosiveness of pore waters. Overprinted on this early diagenetic trend are high-frequency fluctuations of aragonite preservation, which may be related to climatically induced variations of intermediate water masses.

Stable oxygen isotope record and Calcium concentrations of sediment core GeoB3910-2

There is increasing evidence that the preceding Holocene climate was as unstable as the last glacial period, although variations occurred at much lower amplitudes. However, low-latitude climate records that confirm this variability are sparse. Here we present a radiocarbon-dated Holocene marine record from the tropical western Atlantic. Aragonite dissolution derived from the degree of preservation of the pteropod Limacina inflata records changes in the corrosiveness of the bottom water at the core site due to the changing influence of northern versus southern water masses. The delta18O difference between the shallow-living planktonic foraminifera Globigerinoides sacculifer and the deep-living Globorotalia tumida is used as proxy for changes in the vertical stratification of the surface water, hence the trade wind strength at this latitude. We compared our data to high-latitude records of the North Atlantic region. A good agreement is found between the aragonite dissolution and the strength in the Island-Scotland Overflow Water, which contributes significantly to the North Atlantic Deep Water. This suggests that large-scale variations in the Atlantic thermohaline circulation occurred throughout the Holocene. Concurrently, the comparison of our Delta delta18O with the GISP2 glaciochemical records points to global Holocene atmospheric reorganizations seen in both the tropics and high northern latitudes.

Silt grain-size analysis of ODP holes from the western equatorial Atlantic

Grain-size records of the terrigenous and calcareous silt fraction, preservation of planktic foraminifera, and benthic foraminiferal stable-isotope data (delta13C, delta18O values of C. wuellerstorfi) at ODP Site 927 on the Ceará Rise (5°27.7'N, 44°28.8'W), are used to reconstruct variations in the history of bottom current strength, ventilation, and carbonate corrosiveness of deep waters during the time interval from 0.8 to 0.3 Ma. Glacial periods are characterized by generally smaller mean sizes of the terrigenous sortable silt fraction (mean(SS)), lower delta13C values, and poorer preservation of planktic foraminifera compared to interglacials. This indicates lower bottom current speeds, larger nutrient contents and more corrosive deep water. By contrast, larger mean(SS) sizes, higher delta13C values, and well preserved planktic foraminifera indicate strong circulation and a well ventilated deep-water mass during interglacials. The observed changes are most likely related to the weakening and strengthening of circulation of Lower North Atlantic Deep Water (LNADW). Cross-spectral analysis between the mean(SS) and benthic delta18O records reveals that minima in mean(SS) occur about 7.6 k.y. after the maximum in ice volume. This indicates a considerable lag time between ice-shield induced changes in LNADW production and subsequent changes in the velocity of LNADW flow in the western equatorial Atlantic. Striking changes in bottom current speed occur regularly during glacial to interglacial transitions. Extremely fine mean(SS) minima point to an almost complete shutdown of bottom current vigor in response to a cessation of LNADW production caused by an enhanced melt water release during the initial phases of deglaciation. However, each of the fine minima extremes is followed by a rapid shift to very high mean(SS) values that indicate strong bottom currents, and hence, vigorous LNADW flow during the early interglacials. After the onset of glacial Stage 12, generally poorer carbonate preservation and higher variability is registered. This coincides with a global decrease in carbonate preservation during the mid-Brunhes (mid-Brunhes dissolution event). Detailed grain-size analysis of the calcareous fine fraction (<63 µm) revealed a considerable reduction of particles in the fraction from 7 to 63 µm during periods of enhanced dissolution. This indicates a preferential dissolution of larger planktic foraminiferal fragments which leads to an enrichment of coccoliths in the calcareous fine fraction.

Planktonic foraminiferal preservation in Plio/Pleistocene sediments from the western equatorial Atlantic and Caribbean

Records of mean sortable silt and planktonic foraminiferal preservation from the Ceará Rise (western equatorial Atlantic) and from the Caribbean are presented to analyze the Pliocene (3.5-2.2 Ma) to Pleistocene (1.6-0.3 Ma) evolution of near-bottom current strength and the carbonate corrosiveness of deep water. During the mid-Pleistocene climate transition (~1 Ma) a drastic decrease in glacial bottom current strength and an increase in carbonate corrosiveness is registered, demonstrating a substantial decrease in the glacial contribution of the Lower North Atlantic Deep Water (LNADW) to the Atlantic Ocean. Also, an increased sensitivity to eccentricity orbital forcing is registered after the MPT. By contrast, carbonate preservation increases considerably in the deep Caribbean in response to a strong and persistent stable contribution of Upper North Atlantic Deep Water (UNADW). We found evidence for the strongest and most stable circulation within the LNADW cell during the Northern Hemisphere cooling period between ~3.2 and 2.75 Ma. This is in agreement with the 'superconveyor model' which postulates that the highest NADW production took place prior to ~2.7 Ma. A considerable decrease in bottom current strength and planktonic foraminiferal preservation is observed synchronous with the first occurrence of large-scale continental ice sheets in the Northern Hemisphere. This documents the final termination of the 'superconveyor' at ca. 2.75 Ma. However, our data do not support a 'superconveyor' in the interval between 3.5 and 3.2 Ma when high-amplitude fluctuations in bottom current flow and preservation in planktonic foraminifera are observed. Because of the great sensitivity of NADW production to changes in surface water salinity, we assume that the high-amplitude fluctuations of LNADW circulation prior to ~3.2 Ma are linked to changes in the Atlantic salinity budget. After 2.75 Ma they are primarily controlled by ice-sheet forcing. In contrast to the stepwise deterioration of planktonic foraminiferal preservation in the western deep Atlantic, a trend toward better preservation from the Pliocene to Pleistocene is observed in the deep Caribbean. This indicates a long-term increase in the contribution of UNADW to the Atlantic Ocean.

Shell preservation of Limacina inflata in surface sediments of the Central and South Atlantic

Over 300 surface sediment samples from the Central and South Atlantic Ocean and the Caribbean Sea were investigated for the preservation state of the aragonitic test of Limacina inflata. Results are displayed in spatial distribution maps and are plotted against cross-sections of vertical water mass configurations, illustrating the relationship between preservation state, saturation state of the overlying waters, and overall water mass distribution. The microscopic investigation of L. inflata (adults) yielded the Limacina dissolution index (LDX), and revealed three regional dissolution patterns. In the western Atlantic Ocean, sedimentary preservation states correspond to saturation states in the overlying waters. Poor preservation is found within intermediate water masses of southern origin (i.e. Antarctic intermediate water (AAIW), upper circumpolar water (UCDW)), which are distinctly aragonite-corrosive, whereas good preservation is observed within the surface waters above and within the upper North Atlantic deep water (UNADW) beneath the AAIW. In the eastern Atlantic Ocean, in particular along the African continental margin, the LDX fails in most cases (i.e. less than 10 tests of L. inflata per sample were found). This is most probably due to extensive "metabolic" aragonite dissolution at the sediment-water interface combined with a reduced abundance of L. inflata in the surface waters. In the Caribbean Sea, a more complex preservation pattern is observed because of the interaction between different water masses, which invade the Caribbean basins through several channels, and varying input of bank-derived fine aragonite and magnesian calcite material. The solubility of aragonite increases with increasing pressure, but aragonite dissolution in the sediments does not simply increase with water depth. Worse preservation is found in intermediate water depths following an S-shaped curve. As a result, two aragonite lysoclines are observed, one above the other. In four depth transects, we show that the western Atlantic and Caribbean LDX records resemble surficial calcium carbonate data and delta13C and carbonate ion concentration profiles in the water column. Moreover, preservation of L. inflata within AAIW and UCDW improves significantly to the north, whereas carbonate corrosiveness diminishes due to increased mixing of AAIW and UNADW. The close relationship between LDX values and aragonite contents in the sediments shows much promise for the quantification of the aragonite loss under the influence of different water masses. LDX failure and uncertainties may be attributed to (1) aragonite dissolution due to bottom water corrosiveness, (2) aragonite dissolution due to additional CO2 release into the bottom water by the degradation of organic matter based on an enhanced supply of organic matter into the sediment, (3) variations in the distribution of L. inflata and hence a lack of supply into the sediment, (4) dilution of the sediments and hence a lack of tests of L. inflata, or (5) redeposition of sediment particles.

Dissolution index of Globigerina bulloides in recent and Last Glacial Maximum sediments

The modern Atlantic Ocean, dominated by the interactions of North Atlantic Deep Water (NADW) and Antarctic Bottom Water (AABW), plays a key role in redistributing heat from the Southern to the Northern Hemisphere. In order to reconstruct the evolution of the relative importance of these two water masses, the NADW/AABW transition, reflected by the calcite lysocline, was investigated by the Globigerina bulloides dissolution index (BDX?). The depth level of the Late Glacial Maximum (LGM) calcite lysocline was elevated by several hundred metres, indicating a more corrosive water mass present at modern NADW level. Overall, the small range of BDX? data and the gradual decrease in preservation below the calcite lysocline point to a less stratified Atlantic Ocean during the LGM. Similar preservation patterns in the West and East Atlantic demonstrate that the modern west-east asymmetry did not exist due to an expansion of southern deep waters compensating for the decrease in NADW formation.

G. bulloides dissolution index of surface sediments

The Atlantic is regarded as a huge carbonate depocenter due to an on average deep calcite lysocline. However, calculations and models that attribute the calcite lysocline to the critical undersaturation depth (hydrographic or chemical lysocline) and not to the depth at which significant calcium carbonate dissolution is observed (sedimentary calcite lysocline) strongly overestimate the preservation potential of calcareous deep-sea sediments. Significant calcium carbonate dissolution is expected to begin firstly below 5000 m in the deep Guinea and Angola Basin and below 4400 m in the Cape Basin. Our study that is based on different calcium carbonate dissolution stages of the planktic foraminifera Globigerina bulloides clearly shows that it starts between 400 and 1600 m shallower depending on the different hydrographic settings of the South Atlantic Ocean. In particular, coastal areas are severely affected by increased supply of organic matter and the resultant production of metabolic CO2 which seems to create microenvironments favorable for dissolution of calcite well above the hydrographic lysocline.

Benthic foraminifera in surface sediments, South Atlantic

Sixty surface sediment samples from the eastern South Atlantic Ocean including the Walvis Ridge, the Angola and Cape basins, and the Southwest African continental margin were analysed for their benthic foraminiferal content to unravel faunal distribution patterns and ecological preferences. Live (stained with Rose Bengal) and dead faunas were counted separately and then each grouped by Q-mode principal component analysis into seven principal faunal end-members. Then, multiple regression technique was used to correlate Recent assemblages with available environmental variables and to finally differentiate between four principal groups of environmental agents acting upon the generation of benthic foraminiferal assemblages: (1) seasonality of food supply and organic carbon flux rates, together with oxygen content in the pore and bottom waters; (2) lateral advection of deep-water masses; (3) bottom water carbonate corrosiveness; and (4) energetic state at the benthic boundary layer and grain size composition of the substrate. Food supply and corresponding dissolved oxygen contents in the pore and bottom waters turned out to be the most important factors which control the distribution pattern of the Recent benthic foraminifera. At the continental margin, in the zone of coastal upwelling and its mixing area, benthic foraminiferal assemblages are dominated by stenobathic high-productivity faunas, characterized by elevated standing stocks, low diversities and a large number of endobenthic living species. At the continental shelf and upper continental slope the live assemblages are characterized by Rectuvigerina cylindrica, Uvigerina peregrina s.1., Uvigerina auberiana and Rhizammina spp. while the dead assemblages are characterized by Cassidulina laevigata, Bolivina dilatata, Bulimina costata and B. mexicana. At the lower continental slope strong influence of high organic matter fluxes on the species composition is restricted to the area off the Cunene river mouth, where the live assemblage is dominated by Uvigerina peregrina s.1., the corresponding dead assemblage by Melonis barleeanum and M. zaandamae. In the adjacent areas of the lower continental slope the biocoenosis is characterized by Reophax bilocularis, and Epistominella exigua which becomes dominant in the corresponding dead assemblage. At the Walvis Ridge and in the abyssal Angola and Cape basins, where organic matter fluxes are low and highly seasonal, benthic foraminiferal assemblages reflect both the oligotrophic situation and the deep and bottom water mass configuration. The top and flanks of the Walvis Ridge are inhabited by the Rhizammina, Psammosphaera and R. bilocularis live assemblages, the corresponding dead assemblages are dominated by G. subglobosa on the ridge top and E. exigua on the flanks. Within the highly diverse E. exigua dead assemblage several associated epibenthic species coincide with the core of NADW between about 1600 and 3700 m water depth. These species include Osangularia culter, Cibicidoides kullenbergi, Melonis pompilioides, Bolivinita pseudothalmanni and Bulimina alazanensis. The assemblages of the abyssal Cape and Angola basins are characterized by Nuttallides umbonifer and a high proportion of agglutinated species. These species are adapted to very low organic matter fluxes and a carbonate corrosive environment.