Coccoliths and carbonate grain-size compositions in sediment samples from the Mid-Atlantic Ridge

This study presents a differentiated carbonate budget for marine surface sediments from the Mid-Atlantic Ridge of the South Atlantic, with results based on carbonate grain-size composition. Upon separation into sand, silt, and clay sub-fractions, the silt grain-size distribution was measured using a SediGraph 5100. We found regionally characteristic grain-size distributions with an overall minimum at 8 µm equivalent spherical diameter (ESD). SEM observations reveal that the coarse particles (>8 µm ESD) are attributed to planktic foraminifers and their fragments, and the fine particles (<8 µm ESD) to coccoliths. On the basis of this division, the regional variation of the contribution of foraminifers and coccoliths to the carbonate budget of the sediments are calculated. Foraminifer carbonate dominates the sediments in mesotropic regions whereas coccoliths contribute most carbonate in oligotrophic regions. The grain size of the coccolith share is constant over water depth, indicating a lower susceptibility for carbonate dissolution compared to foraminifers. Finally, the characteristic grain-size distribution in fine silt (<8 µm ESD) is set into context with the coccolith assemblage counted and biometrically measured using a SEM. The coccoliths present in the silt fraction are predominantly large species (length > 4 µm). Smaller species (length < 4 µm) belong to the clay fraction (<2 µm ESD). The average length of most frequent coccolith species is connected to prominent peaks in grain-size distributions (ESD) with a shape factor. The area below Gaussian distributions fitted to these peaks is suggested as a way to quantitatively estimate the carbonate contribution of single coccolith species more precisely compared to conventional volume estimates. The quantitative division of carbonate into the fraction produced by coccoliths and that secreted by foraminifers enables a more precise estimate for source/sink relations of consumed and released CO2 in the carbon cycle. The allocation of coccolith length and grain size (ESD) suggests size windows for the separation or accumulation of distinct coccolith species in investigations that depend on non to slightly-mixed signals (e.g., isotopic studies).

Chemical and physical oceanography on 131 CTD casts from METEOR cruise M59/2

The oceans absorb and store a significant portion of anthropogenic CO2 emissions, but large uncertainties remain in the quantification of this sink. An improved assessment of the present and future oceanic carbon sink is therefore necessary to provide recommendations for long-term global carbon cycle and climate policies. The formation of North Atlantic Deep Water (NADW) is a unique fast track for transporting anthropogenic CO2 into the ocean's interior, making the deep waters rich in anthropogenic carbon. Thus the Atlantic is presently estimated to hold 38% of the oceanic anthropogenic CO2 inventory, although its volume makes up only 25% of the world ocean. Here we analyze the inventory change of anthropogenic CO2 in the Atlantic between 1997 and 2003 and its relationship to NADW formation. For the whole region between 20°S and 65°N the inventory amounts to 32.5 ± 9.5 Petagram carbon (Pg C) in 1997 and increases up to 36.0 ± 10.5 Pg C in 2003. This result is quite similar to earlier studies. Moreover, the overall increase of anthropogenic carbon is in close agreement with the expected change due to rising atmospheric CO2 levels of 1.69% a?1. On the other hand, when considering the subpolar region only, the results demonstrate that the recent weakening in the formation of Labrador Sea Water, a component of NADW, has already led to a decrease of the anthropogenic carbon inventory in this water mass. As a consequence, the overall inventory for the total water column in the western subpolar North Atlantic increased only by 2% between 1997 and 2003, much less than the 11% that would be expected from the increase in atmospheric CO2 levels.

Mid-Pliocene deep-sea bottom water temperatures based on ostracode Mg/Ca ratios

We studied magnesium:calcium (Mg/Ca) ratios in shells of the deep-sea ostracode genus Krithe from a short interval in the middle Pliocene between 3.29 and 2.97 Ma using deep-sea drilling sites in the North and South Atlantic in order to estimate bottom water temperatures (BWT) during a period of climatic warmth. Results from DSDP and ODP Sites 552A, 610A, 607, 658A, 659A, 661A and 704 for the period Ma reveal both depth and latitudinal gradients of mean Mg/Ca values. Shallower sites (552A, 610A and 607) have higher mean Mg/Ca ratios (10.3, 9.7, 10.1 mmol/mol) than deeper sites (661A, 6.3 mmol/mol), and high latitude North Atlantic sites (552A, 610 and 607) have higher Mg/Ca ratios than low latitude (658A: 9.8 mmol/mol, 659A: 7.7 mmol/mol, 661A: 6.3 mmol/mol) and Southern Ocean (704: 8.0 mmol/mol) sites. Converting Mg/Ca ratios into estimated temperatures using the calibration of Dwyer et al. (1995) [Dwyer, G.S., Cronin, T.M., Baker, P.A., Raymo, M.E., Buzas, J.S., Corrège, T., 1995. North Atlantic deepwater temperature change during late Pliocene and late Quaternary climatic cycles. Science 270, 1347-1351] suggests that mean middle Pliocene bottom water temperatures at the study sites in the deep Atlantic were about the same as modern temperatures. However, brief pulses of elevated BWT occurred several times between 3.29 and 2.97 Ma in both the North and South Atlantic Ocean suggesting short-term changes in deep ocean circulation.

Pore water (SO4, CH4, alkalinity, HS-, Ca, Sr, Mg, Ba) and solid phase (Ca, Sr, Mg, Ba) data measured in pockmark sediments of the Northern Congo Fan

This study focuses on the vertical distribution of authigenic carbonates (aragonite and high Mg-calcite) in the form of finely disseminated precipitates as well as massive carbonate concretions present in and above gas hydrate bearing sediments of the Northern Congo Fan. Analyses of Ca, Mg, Sr and Ba in pore water, bulk sediments and authigenic carbonates were carried out on gravity cores taken from three pockmark structures (Hydrate Hole, Black Hole and Worm Hole). In addition, a background core was retrieved from an area not influenced by fluid seepage. Pore water Sr/Ca and Mg/Ca ratios are used to reveal the current depths of carbonate formation as well as the mineralogy of the authigenic precipitates. The Sr/Ca and Mg/Ca ratios of bulk sediments and massive carbonate concretions were applied to infer the presence and depth distribution of authigenic aragonite and high Mg-calcite, based on the approach presented by Bayon et al. [Bayon et al. (2007). Sr/Ca and Mg/Ca ratios in Niger Delta sediments: Implications for authigenic carbonate genesis in cold seep environments. Marine Geology 241(1-4), 93-109, doi:10.1016/j.margeo.2007.03.007]. We show that the approach developed by Bayon et al. (2007) for sediments of cold seeps of the Niger Delta is also suitable to identify the mineralogy of authigenic carbonates in pockmark sediments of the Congo Deep-Sea Fan. We expand this approach by combining interstitial with solid phase Sr/Ca and Mg/Ca ratios, which demonstrate that high Mg-calcite is the predominant authigenic carbonate that currently forms at the sulfate/methane reaction zone (SMRZ). This is the first study which investigates both solid phase and pore water signatures typical for either aragonite or high Mg-calcite precipitation for the same sediment cores and thus is able to identify active and fossil carbonate precipitation events. At all investigated pockmark sites fossil horizons of the SMRZ were deduced from high Mg-calcite located above and below the current depths of the SMRZ. Additionally, aragonite enrichments typical for high seepage rates were detected close to the sediment surface at these sites. However, active precipitation of aragonite as indicated by pore water characteristics only occurs at the Black Hole site. Dissolved and solid phase Ba concentrations were used to estimate the time the SMRZ was fixed at the current depths of the diagenetic barite fronts. The combined pore water and solid phase elemental ratios (Mg/Ca, Sr/Ca) and Ba concentrations allow the reconstruction of past changes in methane seepage at the investigated pockmark sites. At the Hydrate Hole and Worm Hole sites the time of high methane seepage was estimated to have ceased at least 600 yr BP. In contrast, a more recent change from a high flux to a more dormant stage must have occurred at the Black Hole site as evidenced by active aragonite precipitation at the sediment surface and a lack of diagenetic Ba enrichments.

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.

Element ratio (Sr/Ca, Ba/Ca, B/Ca, and Mg/Ca) profiles throughout the larval life stage of Mytilus edulis, 2011

Rising anthropogenic CO2 in the surface ocean has raised serious concerns for the ability of calcifying organisms to secrete their shells and skeletons. Previous mollusc carbonate perturbation experiments report deleterious effects at lowered pH (7.8-7.4 pH units), including reduced shell length and thickness and deformed shell morphology. It is not clear whether the reduced shell growth results from a decrease in calcification rate due to lowered aragonite saturation or from an indirect effect on mollusc metabolism. We take a novel approach to discerning between these two processes by examining the impact of lowered pH on the 'vital-effect' associated with element ratios. Reported herein are the first element ratio (Sr/Ca, Ba/Ca, B/Ca, Mg/Ca and Mn/Ca) profiles throughout the larval life stage of Mytilus edulis. Element ratio data for individuals reared in ambient conditions provide new insights into biomineralization during larval development. Sr/Ca ratios are consistent with Sr incorporation in the mineral phase. Mg and Mn are likely hosted in an organic phase. The Ba partition coefficient of early larval shells is one of the highest reported in biogenic aragonite. The reason for the high Ba concentrations is unknown, but may reflect the assimilation of Ba from food and/or Ba concentration in an organic or amorphous carbonate phase. There is no observable difference in the way the studied elements are incorporated into the shells of individuals reared in ambient and lowered pH conditions. The reduced growth rate at lower pH may be a consequence of a disruption to the larval mollusc metabolism.

Foraminiferal Mg/Ca and Mn/Ca ratios across the Eocene-Oligocene transition

Constraining the magnitude of high-latitude temperature change across the Eocene-Oligocene transition (EOT) is essential for quantifying the magnitude of Antarctic ice-sheet expansion and understanding regional climate response to this event. To this end, we constructed high-resolution stable oxygen isotope (d18O) and magnesium/calcium (Mg/Ca) records from planktic and benthic foraminifera at four Ocean Drilling Program (ODP) sites in the Southern Ocean. Planktic foraminiferal Mg/Ca records from the Kerguelen Plateau (ODP Sites 738, 744, and 748) show a consistent pattern of temperature change, indicating 2-3 °C cooling in direct conjunction with the first step of a two-step increase in benthic and planktic foraminiferal d18O values across the EOT. In contrast, benthic Mg/Ca records from Maud Rise (ODP Site 689) and the Kerguelen Plateau (ODP Site 748) do not exhibit significant temperature change. The contrasting temperature histories derived from the planktic and benthic Mg/Ca records are not reconcilable, since vertical d18O gradients remained nearly constant at all sites between 35.0 and 32.5 Ma. Based on the coherency of the planktic Mg/Ca records from the Kerguelen Plateau sites and complications with benthic Mg/Ca paleothermometry at low temperatures, the planktic Mg/Ca records are deemed the most reliable measure of Southern Ocean temperature change. We therefore interpret a uniform cooling of 2-3 °C in both deep surface (thermocline) waters and intermediate deep waters of the Southern Ocean across the EOT. Cooling of Southern Ocean surface waters across the EOT was likely propagated to the deep ocean, since deep waters were primarily sourced on the Antarctic margin throughout this time interval. Removal of the temperature component from the observed foraminiferal d18O shift indicates that seawater d18O values increased by 0.6 ± 0.15 per mil across the EOT interval, corresponding to an increase in global ice volume to a level equivalent with 60-130% modern East Antarctic ice sheet volume.