High-precision determination of lithium and magnesium isotopes utilising single column separation and multi-collector inductively coupled plasma mass spectrometry.

RATIONALE: Li and Mg isotopes are increasingly used as a combined tool within the geosciences. However, established methods require separate sample purification protocols utilising several column separation procedures. This study presents a single-step cation-exchange method for quantitative separation of trace levels of Li and Mg from multiple sample matrices. METHODS: The column method utilises the macro-porous AGMP-50 resin and a high-aspect ratio column, allowing quantitative separation of Li and Mg from natural waters, sediments, rocks and carbonate matrices following the same elution protocol. High-precision isotope determination was conducted by multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) on the Thermo Scientific™ NEPTUNE Plus™ fitted with 1013  Ω amplifiers which allow accurate and precise measurements at ion beams ≤0.51 V. RESULTS: Sub-nanogram Li samples (0.3-0.5 ng) were regularly separated (yielding Mg masses of 1-70 µg) using the presented column method. The total sample consumption during isotopic analysis is <0.5 ng Li and <115 ng Mg with long-term external 2σ precisions of ±0.39‰ for δ7 Li and ±0.07‰ for δ26 Mg. The results for geological reference standards and seawater analysed by our method are in excellent agreement with published values despite the order of magnitude lower sample consumption. CONCLUSIONS: The possibility of eluting small sample masses and the low analytical sample consumption make this method ideal for samples of limited mass or low Li concentration, such as foraminifera, mineral separates or dilute river waters.

West Antarctic Ice Sheet retreat driven by Holocene warm water incursions.

Glaciological and oceanographic observations coupled with numerical models show that warm Circumpolar Deep Water (CDW) incursions onto the West Antarctic continental shelf cause melting of the undersides of floating ice shelves. Because these ice shelves buttress glaciers feeding into them, their ocean-induced thinning is driving Antarctic ice-sheet retreat today. Here we present a multi-proxy data based reconstruction of variability in CDW inflow to the Amundsen Sea sector, the most vulnerable part of the West Antarctic Ice Sheet, during the Holocene epoch (from 11.7 thousand years ago to the present). The chemical compositions of foraminifer shells and benthic foraminifer assemblages in marine sediments indicate that enhanced CDW upwelling, controlled by the latitudinal position of the Southern Hemisphere westerly winds, forced deglaciation of this sector from at least 10,400 years ago until 7,500 years ago-when an ice-shelf collapse may have caused rapid ice-sheet thinning further upstream-and since the 1940s. These results increase confidence in the predictive capability of current ice-sheet models.

Pliocene-Pleistocene evolution of sea surface and intermediate water temperatures from the southwest Pacific.

Over the last 5 million years, the global climate system has evolved toward a colder mean state, marked by large-amplitude oscillations in continental ice volume. Equatorward expansion of polar waters and strengthening temperature gradients have been detected. However, the response of the mid latitudes and high latitudes of the Southern Hemisphere is not well documented, despite the potential importance for climate feedbacks including sea ice distribution and low-high latitude heat transport. Here we reconstruct the Pliocene-Pleistocene history of both sea surface and Antarctic Intermediate Water (AAIW) temperatures on orbital time scales from Deep Sea Drilling Project Site 593 in the Tasman Sea, southwest Pacific. We confirm overall Pliocene-Pleistocene cooling trends in both the surface ocean and AAIW, although the patterns are complex. The Pliocene is warmer than modern, but our data suggest an equatorward displacement of the subtropical front relative to present and a poleward displacement of the subantarctic front of the Antarctic Circumpolar Current (ACC). Two main intervals of cooling, from ~3 Ma and ~1.5 Ma, are coeval with cooling and ice sheet expansion noted elsewhere and suggest that equatorward expansion of polar water masses also characterized the southwest Pacific through the Pliocene-Pleistocene. However, the observed trends in sea surface temperature and AAIW temperature are not identical despite an underlying link to the ACC, and intervals of unusual surface ocean warmth (~2 Ma) and large-amplitude variability in AAIW temperatures (from ~1 Ma) highlight complex interactions between equatorward displacements of fronts associated with the ACC and/or varying poleward heat transport from the subtropics.

Mid Pleistocene foraminiferal mass extinction coupled with phytoplankton evolution.

Understanding the interaction between climate and biotic evolution is crucial for deciphering the sensitivity of life. An enigmatic mass extinction occurred in the deep oceans during the Mid Pleistocene, with a loss of over 100 species (20%) of sea floor calcareous foraminifera. An evolutionarily conservative group, benthic foraminifera often comprise >50% of eukaryote biomass on the deep-ocean floor. Here we test extinction hypotheses (temperature, corrosiveness and productivity) in the Tasman Sea, using geochemistry and micropalaeontology, and find evidence from several globally distributed sites that the extinction was caused by a change in phytoplankton food source. Coccolithophore evolution may have enhanced the seasonal 'bloom' nature of primary productivity and fundamentally shifted it towards a more intra-annually variable state at ∼0.8 Ma. Our results highlight intra-annual variability as a potential new consideration for Mid Pleistocene global biogeochemical climate models, and imply that deep-sea biota may be sensitive to future changes in productivity.

Evolution of South Atlantic density and chemical stratification across the last deglaciation.

Explanations of the glacial-interglacial variations in atmospheric pCO2 invoke a significant role for the deep ocean in the storage of CO2. Deep-ocean density stratification has been proposed as a mechanism to promote the storage of CO2 in the deep ocean during glacial times. A wealth of proxy data supports the presence of a "chemical divide" between intermediate and deep water in the glacial Atlantic Ocean, which indirectly points to an increase in deep-ocean density stratification. However, direct observational evidence of changes in the primary controls of ocean density stratification, i.e., temperature and salinity, remain scarce. Here, we use Mg/Ca-derived seawater temperature and salinity estimates determined from temperature-corrected δ(18)O measurements on the benthic foraminifer Uvigerina spp. from deep and intermediate water-depth marine sediment cores to reconstruct the changes in density of sub-Antarctic South Atlantic water masses over the last deglaciation (i.e., 22-2 ka before present). We find that a major breakdown in the physical density stratification significantly lags the breakdown of the deep-intermediate chemical divide, as indicated by the chemical tracers of benthic foraminifer δ(13)C and foraminifer/coral (14)C. Our results indicate that chemical destratification likely resulted in the first rise in atmospheric pCO2, whereas the density destratification of the deep South Atlantic lags the second rise in atmospheric pCO2 during the late deglacial period. Our findings emphasize that the physical and chemical destratification of the ocean are not as tightly coupled as generally assumed.

Obliquity pacing of the western Pacific Intertropical Convergence Zone over the past 282,000 years.

The Intertropical Convergence Zone (ITCZ) encompasses the heaviest rain belt on the Earth. Few direct long-term records, especially in the Pacific, limit our understanding of long-term natural variability for predicting future ITCZ migration. Here we present a tropical precipitation record from the Southern Hemisphere covering the past 282,000 years, inferred from a marine sedimentary sequence collected off the eastern coast of Papua New Guinea. Unlike the precession paradigm expressed in its East Asian counterpart, our record shows that the western Pacific ITCZ migration was influenced by combined precession and obliquity changes. The obliquity forcing could be primarily delivered by a cross-hemispherical thermal/pressure contrast, resulting from the asymmetric continental configuration between Asia and Australia in a coupled East Asian-Australian circulation system. Our finding suggests that the obliquity forcing may play a more important role in global hydroclimate cycles than previously thought.

Palaeoclimate reconstructions reveal a strong link between El Niño-Southern Oscillation and Tropical Pacific mean state.

The El Niño-Southern Oscillation (ENSO) is one of the most important components of the global climate system, but its potential response to an anthropogenic increase in atmospheric CO2 remains largely unknown. One of the major limitations in ENSO prediction is our poor understanding of the relationship between ENSO variability and long-term changes in Tropical Pacific oceanography. Here we investigate this relationship using palaeorecords derived from the geochemistry of planktonic foraminifera. Our results indicate a strong negative correlation between ENSO variability and zonal gradient of sea-surface temperatures across the Tropical Pacific during the last 22 ky. This strong correlation implies a mechanistic link that tightly couples zonal sea-surface temperature gradient and ENSO variability during large climate changes and provides a unique insight into potential ENSO evolution in the future by suggesting enhanced ENSO variability under a global warming scenario.

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.

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.

The deglacial evolution of North Atlantic deep convection.

Deepwater formation in the North Atlantic by open-ocean convection is an essential component of the overturning circulation of the Atlantic Ocean, which helps regulate global climate. We use water-column radiocarbon reconstructions to examine changes in northeast Atlantic convection since the Last Glacial Maximum. During cold intervals, we infer a reduction in open-ocean convection and an associated incursion of an extremely radiocarbon ((14)C)-depleted water mass, interpreted to be Antarctic Intermediate Water. Comparing the timing of deep convection changes in the northeast and northwest Atlantic, we suggest that, despite a strong control on Greenland temperature by northeast Atlantic convection, reduced open-ocean convection in both the northwest and northeast Atlantic is necessary to account for contemporaneous perturbations in atmospheric circulation.

Eocene bipolar glaciation associated with global carbon cycle changes.

The transition from the extreme global warmth of the early Eocene 'greenhouse' climate approximately 55 million years ago to the present glaciated state is one of the most prominent changes in Earth's climatic evolution. It is widely accepted that large ice sheets first appeared on Antarctica approximately 34 million years ago, coincident with decreasing atmospheric carbon dioxide concentrations and a deepening of the calcite compensation depth in the world's oceans, and that glaciation in the Northern Hemisphere began much later, between 10 and 6 million years ago. Here we present records of sediment and foraminiferal geochemistry covering the greenhouse-icehouse climate transition. We report evidence for synchronous deepening and subsequent oscillations in the calcite compensation depth in the tropical Pacific and South Atlantic oceans from approximately 42 million years ago, with a permanent deepening 34 million years ago. The most prominent variations in the calcite compensation depth coincide with changes in seawater oxygen isotope ratios of up to 1.5 per mil, suggesting a lowering of global sea level through significant storage of ice in both hemispheres by at least 100 to 125 metres. Variations in benthic carbon isotope ratios of up to approximately 1.4 per mil occurred at the same time, indicating large changes in carbon cycling. We suggest that the greenhouse-icehouse transition was closely coupled to the evolution of atmospheric carbon dioxide, and that negative carbon cycle feedbacks may have prevented the permanent establishment of large ice sheets earlier than 34 million years ago.

Deep-sea temperature and circulation changes at the Paleocene-Eocene Thermal Maximum.

A rapid increase in greenhouse gas levels is thought to have fueled global warming at the Paleocene-Eocene Thermal Maximum (PETM). Foraminiferal magnesium/calcium ratios indicate that bottom waters warmed by 4 degrees to 5 degrees C, similar to tropical and subtropical surface ocean waters, implying no amplification of warming in high-latitude regions of deep-water formation under ice-free conditions. Intermediate waters warmed before the carbon isotope excursion, in association with downwelling in the North Pacific and reduced Southern Ocean convection, supporting changing circulation as the trigger for methane hydrate release. A switch to deep convection in the North Pacific at the PETM onset could have amplified and sustained warming.

340,000-year centennial-scale marine record of Southern Hemisphere climatic oscillation.

In order to investigate rapid climatic changes at mid-southern latitudes, we have developed centennial-scale paleoceanographic records from the southwest Pacific that enable detailed comparison with Antarctic ice core records. These records suggest close coupling of mid-southern latitudes with Antarctic climate during deglacial and interglacial periods. Glacial sections display higher variability than is seen in Antarctic ice cores, which implies climatic decoupling between mid- and high southern latitudes due to enhanced circum-Antarctic circulation. Structural and temporal similarity with the Greenland ice core record is evident in glacial sections and suggests a degree of interhemispheric synchroneity not predicted from bipolar ice core correlations.

Foraminiferal calcification response to glacial-interglacial changes in atmospheric CO2.

A record of foraminiferal shell weight across glacial-interglacial Termination I shows a response related to seawater carbonate ion concentration and allows reconstruction of a record of carbon dioxide in surface seawater that matches the atmospheric record. The results support suggestions that higher atmospheric carbon dioxide directly affects marine calcification, an effect that may be of global importance to past and future changes in atmospheric CO2. The process provides negative feedback to the influence of marine calcification on atmospheric carbon dioxide and is of practical importance to the application of paleoceanographic proxies.