Southwest Pacific deep-water carbonate chemistry during the Mid-Pleistocene Transition

After more than 40 years of research, there is still wide disagreement in defining when the Mid-Pleistocene Transition (MPT) occurred, with climate reconstructions ranging from an abrupt versus gradual transition that began as early as 1500 ka and ended as late as 600 ka. Our recent work in the Southwest Pacific (Ocean Drilling Program Site 1123) has provided some evidence for a rapid transition, suggesting that the MPT was initiated by an abrupt increase in global ice volume 900 thousand years ago [1]. This study uses shallow-infaunal benthic foraminifera Uvigerina spp. to disentangle the contributions of deep-water temperature (using Mg/Ca ratios) and ice volume to the oxygen isotopic composition of foraminiferal calcite over the last 1.5 Ma. The resulting sea-level reconstruction across the MPT shows that the critical step in ice-volume variation was associated with the suppression of melting in Marine Isotope Stage (MIS) 23, followed by renewed ice growth in MIS 22 to yield a very large ice sheet with 120 m of sea level lowering. Here, we built on this work with the aim to investigate further the abrupt event centered on MIS 24 to 22 (the ‘900-ka event’) and try to shed some light on the processes and mechanisms that caused the MPT. Different hypotheses account for the origin of the MPT as a response to long-term ocean cooling, perhaps because of lowering CO2. To better quantify the role of the carbon system during the MPT, we reconstruct past changes in bottom water inorganic carbon chemistry from the trace element (B/Ca) and stable isotopic composition of calcite shells of the infaunal benthic foraminifera Uvigerina spp. from 1100 ka to 350 ka at ODP Site 1123. This site was retrieved from Chatham Rise, east of New Zealand in the Southwest Pacific Ocean (41º47.2’S, 171º 29.9’ W, 3290 m water depth) and lies under the Deep Western Boundary Current (DWBC) that flows into the Pacific Ocean, and is responsible for most of the deep water in that ocean; DWBC strength is directly related to processes occurring around Antarctica. The ratio of boron to calcium (B/Ca) in benthic foraminifer shells has proven to be a reliable indicator of the calcite saturation state of ocean bottom waters. The comparison between benthic foraminifera δ18O and δ13C shows a similar trend at ODP Site 1123, implying a close relationship between these climate and carbon cycle signals, and we use our B/Ca record reconstructed from the same samples to explore the potential processes behind this tight coupling. These results permit preliminary discussion on the deep-water carbonate saturation state during glacial/interglacial cycles. Deep-water temperatures estimates using Mg/Ca and oxygen isotopic composition of seawater (δ18Osw) are available from Site 1123 for the last 1.5 million years [1] and the phase relationship between the different signals is tentatively assessed for the early/middle Pleistocene, when different patterns of climate variability have been inferred from marine and ice cores records. [1] Elderfield et al. (2012). Evolution of ocean temperature and ice volume through the Mid Pleistocene Climate Transition. Science, vol. 337, 6095, 704-70

Antarctic Intermediate Water properties since 400 ka recorded in infaunal (Uvigerina peregrina) and epifaunal (Planulina wuellerstorfi) benthic foraminifera

Reconstruction of intermediate water properties is important for understanding feedbacks within the ocean-climate system, particularly since these water masses are capable of driving high–low latitude teleconnections. Nevertheless, information about intermediate water mass evolution through the late Pleistocene remains limited. This paper examines changes in Antarctic Intermediate Water (AAIW), the most extensive intermediate water mass in the modern ocean through the last 400 kyr using the stable isotopic composition (δ18O and δ13C) and trace element concentration (Mg/Ca and B/Ca) of two benthic foraminiferal species from the same samples: epifaunal Planulina wuellerstorfi and infaunal Uvigerina peregrina. Our results confirm that the most reasonable estimates of AAIW temperature and Δ[CO2−3] are generated by Mg/CaU. peregrina and B/CaP. wuellerstorfi, respectively. We present a 400 kyr record of intermediate water temperature and Δ[CO2−3] from a sediment core from the Southwest Pacific (DSDP site 593; 40°30′S, 167°41′E, 1068 m water depth), which lies within the core of modern AAIW. Our results suggest that a combination of geochemical analyses on both infaunal and epifaunal benthic foraminiferal species yields important information about this critical water mass through the late Pleistocene. When combined with two nearby records of water properties from deeper depths, our data demonstrate that during interglacial stages of the late Pleistocene, AAIW and Circumpolar Deep Water (CPDW) have more similar water mass properties (temperature and δ13C), while glacial stages are typified by dissimilar properties between AAIW and CPDW in the Southwest Pacific. Our new Δ[CO2−3] record shows short time-scale variations, but a lack of coherent glacial–interglacial variability indicating that large quantities of carbon were not stored in intermediate waters during recent glacial periods

Li Partitioning Into Coccoliths of Emiliania huxleyi : Evaluating the General Role of “Vital Effects” in Explaining Element Partitioning in Biogenic Carbonates

Emiliania huxleyi cells were grown in artificial seawater of different Li and Ca concentrations and coccolith Li/Ca ratios determined. Coccolith Li/Ca ratios were positively correlated to seawater Li/Ca ratios only if the seawater Li concentration was changed, not if the seawater Ca concentration was changed. This Li partitioning pattern of E. huxleyi was previously also observed in the benthic foraminifer Amphistegina lessonii and inorganically precipitated calcite. We argue that Li partitioning in both E. huxleyi and A. lessonii is dominated by a coupled transmembrane transport of Li and Ca from seawater to the site of calcification. We present a refined version of a recently proposed transmembrane transport model for Li and Ca. The model assumes that Li and Ca enter the cell via Ca channels, the Li flux being dependent on the Ca flux. While the original model features a linear function to describe the experimental data, our refined version uses a power function, changing the stoichiometry of Li and Ca. The version presented here accurately predicts the observed dependence of DLi on seawater Li/Ca ratios. Our data demonstrate that minor element partitioning in calcifying organisms is partly mediated by biological processes even if the partitioning behavior of the calcifying organism is indistinguishable from that of inorganically precipitated calcium carbonate

Coupled Mg/Ca and clumped isotope analyses of foraminifera provide consistent water temperatures

The reliable determination of past seawater temperature is fundamental to paleoclimate studies. We test the robustness of two paleotemperature proxies by combining Mg/Ca and clumped isotopes (Δ47) on the same specimens of core top planktonic foraminifera. The strength of this approach is that Mg/Ca and Δ47 are measured on the same specimens of foraminifera, thereby providing two independent estimates of temperature. This replication constitutes a rigorous test of individual methods with the advantage that the same approach can be applied to fossil specimens. Aliquots for Mg/Ca and clumped analyses are treated in the same manner following a modified cleaning procedure of foraminifera for trace element and isotopic analyses. We analysed eight species of planktonic foraminifera from coretop samples over a wide range of temperatures from 2 to 29°C. We provide a new clumped isotope temperature calibrations using subaqueous cave carbonates, which is consistent with recent studies. Tandem Mg/Ca–Δ47 results follow an exponential curve as predicted by temperature calibration equations. Observed deviations from the predicted Mg/Ca-Δ47 relationship are attributed to the effects of Fe-Mn oxide coatings, contamination, or dissolution of foraminiferal tests. This coupled approach provides a high degree of confidence in temperature estimates when Mg/Ca and Δ47 yield concordant results, and can be used to infer the past δ18O of seawater (δ18Osw) for paleoclimate studies

Mg/Ca-Temperature Calibration of Polar Benthic foraminifera species for reconstruction of bottom water temperatures on the Antarctic shelf

Benthic foraminifera Mg/Ca is a well-established bottom water temperature (BWT) proxy used in paleoclimate studies. The relationship between Mg/Ca and BWT for numerous species has been determined using core-top and culturing studies. However, the scarcity of calcareous microfossils in Antarctic shelf sediments and poorly defined calibrations at low temperatures has limited the use of the foraminiferal Mg/Ca paleothermometer in ice proximal Antarctic sediments. Here we present paired ocean temperature and modern benthic foraminifera Mg/Ca data for three species, Trifarina angulosa, Bulimina aculeata, and Globocassidulina subglobosa, but with a particular focus on Trifarina angulosa. The core-top data from several Antarctic sectors span a BWT range of −1.7 to +1.2 °C and constrain the relationship between Mg/Ca and cold temperatures. We compare our results to published lower-latitude core-top data for species in the same or related genera, and in the case of Trifarina angulosa, produce a regional calibration. The resulting regional equation for Trifarina angulosa is Temperature (°C) = (Mg/Ca −1.14 ± 0.035)/0.069 ± 0.033). Addition of our Trifarina angulosa data to the previously published Uvigerina spp. dataset provides an alternative global calibration, although some data points appear to be offset from this relationship and are discussed. Mg-temperature relationships for Bulimina aculeata and Globocassidulina subglobosa are also combined with previously published data to produce calibration equations of Temperature (°C) = (Mg/Ca-1.04 ± 0.07)/0.099 ± 0.01 and Temperature (°C) = (Mg/Ca-0.99 ± 0.03)/0.087 ± 0.01, respectively. These refined calibrations highlight the potential utility of benthic foraminifera Mg/Ca-paleothermometry for reconstructing past BWT in Antarctic margin settings

The Carbon-Sulfur Link in the Remineralization of Organic Carbon in Surface Sediments

Here we present the carbon isotopic composition of dissolved inorganic carbon (DIC) and the sulfur isotopic composition of sulfate, along with changes in sulfate concentrations, of the pore fluid collected from a series of sediment cores located along a depth transect on the Iberian Margin. We use these data to explore the coupling of microbial sulfate reduction (MSR) to organic carbon oxidation in the uppermost (up to nine meters) sediment. We argue that the combined use of the carbon and sulfur isotopic composition, of DIC and sulfate respectively, in sedimentary pore fluids, viewed through a δ13CDIC vs. δ34SSO4 cross plot, reveals significant insight into the nature of carbon-sulfur coupling in marine sedimentary pore fluids on continental margins. Our data show systemic changes in the carbon and sulfur isotopic composition of DIC and sulfate (respectively) where, at all sites, the carbon isotopic composition of the DIC decreases before the sulfur isotopic composition of sulfate increases. We compare our results to global data and show that this behavior persists over a range of sediment types, locations and water depths. We use a reactive-transport model to show how changes in the amount of DIC in seawater, the carbon isotopic composition of organic matter, the amount of organic carbon oxidation by early diagenetic reactions, and the presence and source of methane influence the carbon and sulfur isotopic composition of sedimentary pore fluids and the shape of the δ13CDIC vs. δ34SSO4 cross plot. The δ13C of the DIC released during sulfate reduction and sulfate-driven anaerobic oxidation of methane is a major control on the minimum δ13CDIC value in the δ13CDIC vs. δ34SSO4 cross plot, with the δ13C of the organic carbon being important during both MSR and combined sulfate reduction, sulfate-driven AOM and methanogenesis

Assessing Sedimentary Boundary Layer Calcium Carbonate Precipitation and Dissolution Using the Calcium Isotopic Composition of Pore Fluids

We present pore fluid geochemistry, including major ion and trace metal concentrations and the isotopic composition of pore fluid calcium and sulfate, from the uppermost meter of sediments from the Gulf of Aqaba (Northeast Red Sea) and the Iberian Margin (North Atlantic Ocean). In both the locations, we observe strong correlations among calcium, magnesium, strontium, and sulfate concentrations as well as the sulfur isotopic composition of sulfate and alkalinity, suggestive of active changes in the redox state and pH that should lead to carbonate mineral precipitation and dissolution. The calcium isotope composition of pore fluid calcium (δ44Ca) is, however, relatively invariant in our measured profiles, suggesting that carbonate mineral precipitation is not occurring within the boundary layer at these sites. We explore several reasons why the pore fluid δ44Ca might not be changing in the studied profiles, despite changes in other major ions and their isotopic composition, including mixing between the surface and deep precipitation of carbonate minerals below the boundary layer, the possibility that active iron and manganese cycling inhibits carbonate mineral precipitation, and that mineral precipitation may be slow enough to preclude calcium isotope fractionation during carbonate mineral precipitation. Our results suggest that active carbonate dissolution and precipitation, particularly in the diffusive boundary layer, may elicit a more complex response in the pore fluid δ44Ca than previously thought

Effect of Carbonate Chemistry Alteration on the Early Embryonic Development of the Pacific Oyster (Crassostrea gigas)

Ocean acidification, due to anthropogenic CO2 absorption by the ocean, may have profound impacts on marine biota. Calcareous organisms are expected to be particularly sensitive due to the decreasing availability of carbonate ions driven by decreasing pH levels. Recently, some studies focused on the early life stages of mollusks that are supposedly more sensitive to environmental disturbances than adult stages. Although these studies have shown decreased growth rates and increased proportions of abnormal development under low pH conditions, they did not allow attribution to pH induced changes in physiology or changes due to a decrease in aragonite saturation state. This study aims to assess the impact of several carbonate-system perturbations on the growth of Pacific oyster (Crassostrea gigas) larvae during the first 3 days of development (until shelled D-veliger larvae). Seawater with five different chemistries was obtained by separately manipulating pH, total alkalinity and aragonite saturation state (calcium addition). Results showed that the developmental success and growth rates were not directly affected by changes in pH or aragonite saturation state but were highly correlated with the availability of carbonate ions. In contrast to previous studies, both developmental success into viable D-shaped larvae and growth rates were not significantly altered as long as carbonate ion concentrations were above aragonite saturation levels, but they strongly decreased below saturation levels. These results suggest that the mechanisms used by these organisms to regulate calcification rates are not efficient enough to compensate for the low availability of carbonate ions under corrosive conditions

Responses of the emiliania huxleyi proteome to ocean acidification

Ocean acidification due to rising atmospheric CO2 is expected to affect the physiology of important calcifying marine organisms, but the nature and magnitude of change is yet to be established. In coccolithophores, different species and strains display varying calcification responses to ocean acidification, but the underlying biochemical properties remain unknown. We employed an approach combining tandem mass-spectrometry with isobaric tagging (iTRAQ) and multiple database searching to identify proteins that were differentially expressed in cells of the marine coccolithophore species Emiliania huxleyi (strain NZEH) between two CO2 conditions: 395 (~current day) and ~1340 p.p.m.v. CO2. Cells exposed to the higher CO2 condition contained more cellular particulate inorganic carbon (CaCO3) and particulate organic nitrogen and carbon than those maintained in present-day conditions. These results are linked with the observation that cells grew slower under elevated CO2, indicating cell cycle disruption. Under high CO2 conditions, coccospheres were larger and cells possessed bigger coccoliths that did not show any signs of malformation compared to those from cells grown under present-day CO2 levels. No differences in calcification rate, particulate organic carbon production or cellular organic carbon: nitrogen ratios were observed. Results were not related to nutrient limitation or acclimation status of cells. At least 46 homologous protein groups from a variety of functional processes were quantified in these experiments, of which four (histones H2A, H3, H4 and a chloroplastic 30S ribosomal protein S7) showed down-regulation in all replicates exposed to high CO2, perhaps reflecting the decrease in growth rate. We present evidence of cellular stress responses but proteins associated with many key metabolic processes remained unaltered. Our results therefore suggest that this E. huxleyi strain possesses some acclimation mechanisms to tolerate future CO2 scenarios, although the observed decline in growth rate may be an overriding factor affecting the success of this ecotype in future oceans

Chemical concentration of major metal and rare reath elements (REE) in manganese nodules

Oceanic manganese nodules samples were obtained from the Scripps Institution of Oceanography. They were subsamples of the powdered material used for studies of the major and minor element geochemistry of the deposits by Clavert and Price, 1977 (see Related to: reference). The powdered samples were leached with 0.1 M HCl at a ratio of 1:4 by weight at room temperature for 140 days after which the leachate and the residue were separately analyzed. The determinations of Fe, Mn, (atomic absorption spectrophotometry) and P (colorimetry) were made on the leachate. The REE were analysed by mixed-solvent ion exchange and mass spectrometric isotope dilution. Isotope analyses were performed on an A.E.I. MS5 mass spectrometer. RMS precision were generally 2% (and often 1%). except for La (5%). Eight replicate analyses of USGS standard rock BCR-1 wre used for comparison