Single chamber Mg/Ca analyses of Globigerinoides ruber for paleo-proxy calibration using femtosecond LA-ICP-MS.

Mg/Ca is an independent proxy in paleoceanography to reconstruct past seawater temperature. Femtosecond Laser Ablation Inductively Coupled Plasma Mass Spectrometry (fs-LA-ICP-MS) was employed to determine the Mg/Ca composition of tests (shells) of the planktic foraminifer species Globigerinoides ruber albus (white chromotype) and G. ruber ruber (red/pink chromotype) sampled alive from the temperate to subtropical eastern North Atlantic with the research sailing yacht Eugen Seibold. Mg/Ca data are compared to (i) the measured in-situ temperature of ambient seawater, (ii) average mixed layer temperature, and (iii) sea surface temperature (SST). The pooled mean chamber Mg/Ca from each plankton tow site exhibits a positive relationship with SST. Two chamber-specific calibrations are derived, which are consistent with previous calibration equations for comparable paleo-archives. The results confirm fs-LA-ICP-MS as reliable method for determining Mg/Ca in G. ruber, and both the penultimate and antepenultimate chambers of adult specimens may provide comprehensible Mg/Ca temperatures of the surface ocean.

Oxygen rise in the tropical upper ocean during the Paleocene-Eocene Thermal Maximum.

The global ocean's oxygen inventory is declining in response to global warming, but the future of the low-oxygen tropics is uncertain. We report new evidence for tropical oxygenation during the Paleocene-Eocene Thermal Maximum (PETM), a warming event that serves as a geologic analog to anthropogenic warming. Foraminifera-bound nitrogen isotopes indicate that the tropical North Pacific oxygen-deficient zone contracted during the PETM. A concomitant increase in foraminifera size implies that oxygen availability rose in the shallow subsurface throughout the tropical North Pacific. These changes are consistent with ocean model simulations of warming, in which a decline in biological productivity allows tropical subsurface oxygen to rise even as global ocean oxygen declines. The tropical oxygen increase may have helped avoid a mass extinction during the PETM.

Weakened AMOC related to cooling and atmospheric circulation shifts in the last interglacial Eastern Mediterranean.

There is limited understanding of temperature and atmospheric circulation changes that accompany an Atlantic Meridional Overturning Circulation (AMOC) slowdown beyond the North Atlantic realm. A Peqi'in Cave (Israel) speleothem dated to the last interglacial period (LIG), 129-116 thousand years ago (ka), together with a large modern rainfall monitoring dataset, serve as the base for investigating past AMOC slowdown effects on the Eastern Mediterranean. Here, we reconstruct LIG temperatures and rainfall source using organic proxies (TEX86) and fluid inclusion water d-excess. The TEX86 data show a stepwise cooling from 19.8 ± 0.2° (ca. 128-126 ka) to 16.5 ± 0.6 °C (ca. 124-123 ka), while d-excess values decrease abruptly (ca. 126 ka). The d-excess shift suggests that rainfall was derived from more zonal Mediterranean air flow during the weakened AMOC interval. Decreasing rainfall d-excess trends over the last 25 years raise the question whether similar atmospheric circulation changes are also occurring today.

The Bering Strait was flooded 10,000 years before the Last Glacial Maximum.

The cyclic growth and decay of continental ice sheets can be reconstructed from the history of global sea level. Sea level is relatively well constrained for the Last Glacial Maximum (LGM, 26,500 to 19,000 y ago, 26.5 to 19 ka) and the ensuing deglaciation. However, sea-level estimates for the period of ice-sheet growth before the LGM vary by > 60 m, an uncertainty comparable to the sea-level equivalent of the contemporary Antarctic Ice Sheet. Here, we constrain sea level prior to the LGM by reconstructing the flooding history of the shallow Bering Strait since 46 ka. Using a geochemical proxy of Pacific nutrient input to the Arctic Ocean, we find that the Bering Strait was flooded from the beginning of our records at 46 ka until [Formula: see text] ka. To match this flooding history, our sea-level model requires an ice history in which over 50% of the LGM's global peak ice volume grew after 46 ka. This finding implies that global ice volume and climate were not linearly coupled during the last ice age, with implications for the controls on each. Moreover, our results shorten the time window between the opening of the Bering Land Bridge and the arrival of humans in the Americas.

Oceanic nutrient rise and the late Miocene inception of Pacific oxygen-deficient zones.

The modern Pacific Ocean hosts the largest oxygen-deficient zones (ODZs), where oxygen concentrations are so low that nitrate is used to respire organic matter. The history of the ODZs may offer key insights into ocean deoxygenation under future global warming. In a 12-My record from the southeastern Pacific, we observe a >10‰ increase in foraminifera-bound nitrogen isotopes (15N/14N) since the late Miocene (8 to 9 Mya), indicating large ODZs expansion. Coinciding with this change, we find a major increase in the nutrient content of the ocean, reconstructed from phosphorus and iron measurements of hydrothermal sediments at the same site. Whereas global warming studies cast seawater oxygen concentrations as mainly dependent on climate and ocean circulation, our findings indicate that modern ODZs are underpinned by historically high concentrations of seawater phosphate.

Deglacial increase of seasonal temperature variability in the tropical ocean.

The relatively stable Holocene climate was preceded by a pronounced event of abrupt warming in the Northern Hemisphere, the termination of the Younger Dryas (YD) cold period1,2. Although this transition has been intensively studied, its imprint on low-latitude ocean temperature is still controversial and its effects on sub-annual to decadal climate variability remain poorly understood1,3,4. Sea surface temperature (SST) variability at these timescales in the tropical Atlantic is expected to intensify under current and future global warming and has considerable consequences for environmental conditions in Africa and South America, and for tropical Pacific climate5-8. Here we present a 100-µm-resolution record obtained by mass spectrometry imaging (MSI) of long-chain alkenones in sediments from the Cariaco Basin9-11 and find that annually averaged SST remained stable during the transition into the Holocene. However, seasonality increased more than twofold and approached modern values of 1.6 °C, probably driven by the position and/or annual range of the Intertropical Convergence Zone (ITCZ). We further observe that interannual variability intensified during the early Holocene. Our results demonstrate that sub-decadal-scale SST variability in the tropical Atlantic is sensitive to abrupt changes in climate background, such as those witnessed during the most recent glacial to interglacial transition.

Enhanced ocean oxygenation during Cenozoic warm periods.

Dissolved oxygen (O2) is essential for most ocean ecosystems, fuelling organisms' respiration and facilitating the cycling of carbon and nutrients. Oxygen measurements have been interpreted to indicate that the ocean's oxygen-deficient zones (ODZs) are expanding under global warming1,2. However, models provide an unclear picture of future ODZ change in both the near term and the long term3-6. The paleoclimate record can help explore the possible range of ODZ changes in warmer-than-modern periods. Here we use foraminifera-bound nitrogen (N) isotopes to show that water-column denitrification in the eastern tropical North Pacific was greatly reduced during the Middle Miocene Climatic Optimum (MMCO) and the Early Eocene Climatic Optimum (EECO). Because denitrification is restricted to oxygen-poor waters, our results indicate that, in these two Cenozoic periods of sustained warmth, ODZs were contracted, not expanded. ODZ contraction may have arisen from a decrease in upwelling-fuelled biological productivity in the tropical Pacific, which would have reduced oxygen demand in the subsurface. Alternatively, invigoration of deep-water ventilation by the Southern Ocean may have weakened the ocean's 'biological carbon pump', which would have increased deep-ocean oxygen. The mechanism at play would have determined whether the ODZ contractions occurred in step with the warming or took centuries or millennia to develop. Thus, although our results from the Cenozoic do not necessarily apply to the near-term future, they might imply that global warming may eventually cause ODZ contraction.

Cenozoic megatooth sharks occupied extremely high trophic positions.

Trophic position is a fundamental characteristic of animals, yet it is unknown in many extinct species. In this study, we ground-truth the 15N/14N ratio of enameloid-bound organic matter (δ15NEB) as a trophic level proxy by comparison to dentin collagen δ15N and apply this method to the fossil record to reconstruct the trophic level of the megatooth sharks (genus Otodus). These sharks evolved in the Cenozoic, culminating in Otodus megalodon, a shark with a maximum body size of more than 15 m, which went extinct 3.5 million years ago. Very high δ15NEB values (22.9 ± 4.4‰) of O. megalodon from the Miocene and Pliocene show that it occupied a higher trophic level than is known for any marine species, extinct or extant. δ15NEB also indicates a dietary shift in sharks of the megatooth lineage as they evolved toward the gigantic O. megalodon, with the highest trophic level apparently reached earlier than peak size.

Isotope ratio infrared spectroscopy analysis of water samples without memory effects.

RATIONALE: Since their introduction more than a decade ago, isotope ratio infrared spectroscopy (IRIS) systems have rapidly become the standard for oxygen (δ18 O) and hydrogen (δ2 H) isotope analysis of water samples. An important disadvantage of IRIS systems is the well-documented sample-to-sample memory effect, which requires each sample to be analyzed multiple times before the desired accuracy is reached, lengthening analysis times and driving up the costs of analyses. METHODS: We present an adapted set-up and calculation protocol for fully automated analysis of water samples using a Picarro L2140-i cavity ring-down spectroscopy instrument. The adaptation removes memory effects by use of a continuously moisturized nitrogen carrier gas. Water samples of 0.5 µL are measured on top of the water vapor background, after which isotope ratios are calculated by subtraction of the background from the sample peaks. RESULTS: With this new technique, single injections of water samples have internal precisions (1σ) below 0.05‰ for δ18 O values and 0.1‰ for δ2 H values, regardless of the isotope ratio of the previous sample. Precision is worse, however, when the isotope difference between the sample and background water is too large (i.e., exceeding approximately 9‰ for δ18 O values and 70‰ for δ2 H values). Isotope ratios show negligible drift across the four weeks within which the experiments were performed. The single-injection 1σ precision for 17 O excess (Δ'17 O) determined with this method is 60 per meg. CONCLUSIONS: Our experiments demonstrate that by removing sample-to-sample memory effects with a moisturized carrier gas, the time for measurement of δ18 O and δ2 H values using an IRIS system can be reduced markedly without compromising the analytical precision and accuracy. Thorough replication is needed to achieve sufficiently low uncertainties for Δ'17 O.

Southern Ocean upwelling, Earth's obliquity, and glacial-interglacial atmospheric CO2 change.

Previous studies have suggested that during the late Pleistocene ice ages, surface-deep exchange was somehow weakened in the Southern Ocean's Antarctic Zone, which reduced the leakage of deeply sequestered carbon dioxide and thus contributed to the lower atmospheric carbon dioxide levels of the ice ages. Here, high-resolution diatom-bound nitrogen isotope measurements from the Indian sector of the Antarctic Zone reveal three modes of change in Southern Westerly Wind-driven upwelling, each affecting atmospheric carbon dioxide. Two modes, related to global climate and the bipolar seesaw, have been proposed previously. The third mode-which arises from the meridional temperature gradient as affected by Earth's obliquity (axial tilt)-can explain the lag of atmospheric carbon dioxide behind climate during glacial inception and deglaciation. This obliquity-induced lag, in turn, makes carbon dioxide a delayed climate amplifier in the late Pleistocene glacial cycles.

High-precision stable isotope analysis of <5 µg CaCO3 samples by continuous-flow mass spectrometry.

RATIONALE: Oxygen (δ18 O) and carbon (δ13 C) isotope analysis of foraminifera and other CaCO3 samples has been a key technique for paleoceanographical and paleoclimatological research for more than 60 years. There is ongoing demand for the analysis of ever smaller CaCO3 samples, driven, for example, by the desire to analyse single specimen planktic foraminifera, or small samples of tooth enamel. METHODS: We present a continuous-flow mass spectrometric technique that uses cryo-focusing of sample CO2 to analyse CaCO3 samples in a weight range between 10 and 3 µg. These are considerably lower sample weights than achievable on most currently available standard instrumentation. The technique is automated, so that sample throughput lies at >60 samples per day. The method involves an on-line vial-flushing routine designed to remove machine drift due to blank CO2 build-up in the sample vials. RESULTS: In a series of experiments the effect of blank CO2 build-up is quantified, and outgassing from the chlorobutyl septa identified as the source. An improved flushing routine together with the use of a cryo-focusing step in the analysis is demonstrated to provide the analytical stability and sensitivity to analyse CaCO3 samples in a weight range between 10 and 3 µg at ≤0.1‰ precision (1σ) for both δ18 O and δ13 C values. The technique yields similarly precise results for the analysis of the structural carbonate fraction of small tooth enamel samples. CONCLUSIONS: This study demonstrates that high-precision oxygen and carbon isotope analysis is possible on CaCO3 samples smaller than 5 µg by use of a continuous-flow isotope technique. Of key importance are (1) the application of a cold trap that drastically reduces sample gas loss, and (2) a modified flushing regime that eliminates increasing background CO2 build-up in sample vials during longer automated sample runs.

A comparison of isotope ratio mass spectrometry and cavity ring-down spectroscopy techniques for isotope analysis of fluid inclusion water.

RATIONALE: Online oxygen (δ18 O) and hydrogen (δ2 H) isotope analysis of fluid inclusion water entrapped in minerals is widely applied in paleo-fluid studies. In the state of the art of fluid inclusion isotope research, however, there is a scarcity of reported inter-technique comparisons to account for possible analytical offsets. Along with improving analytical precisions and sample size limitations, interlaboratory comparisons can lead to a more robust application of fluid inclusion isotope records. METHODS: Mineral samples-including speleothem, travertine, and vein material-were analyzed on two newly setup systems for fluid inclusion isotope analysis to provide an inter-platform comparison. One setup uses a crusher unit connected online to a continuous-flow pyrolysis furnace and an isotope ratio mass spectrometry (IRMS) instrument. In the other setup, a crusher unit is lined up with a cavity ring-down spectroscopy (CRDS) system, and water samples are analyzed on a continuous standard water background to achieve precisions on water injections better than 0.1‰ for δ18 O values and 0.4‰ for δ2 H values for amounts down to 0.2 µL. RESULTS: Fluid inclusion isotope analyses on the IRMS setup have an average 1σ reproducibility of 0.4‰ and 2.0‰ for δ18 O and δ2 H values, respectively. The CRDS setup has a better 1σ reproducibility (0.3‰ for δ18 O values and 1.1‰ for δ2 H values) and also a more rapid sample throughput (<30 min per sample). Fluid inclusion isotope analyses are reproducible at these uncertainties for water amounts down to 0.1 µL on both setups. Fluid inclusion isotope data show no systematic offsets between the setups. CONCLUSIONS: The close match in fluid inclusion isotope results between the two setups demonstrates the high accuracy of the presented continuous-flow techniques for fluid inclusion isotope analysis. Ideally, experiments such as the one presented in this study will lead to further interlaboratory comparison efforts and the selection of suitable reference materials for fluid inclusion isotopes studies.

Megacity development and the demise of coastal coral communities: Evidence from coral skeleton δ15 N records in the Pearl River estuary.

Historical coral skeleton (CS) δ18 O and δ15 N records were produced from samples recovered from sedimentary deposits, held in natural history museum collections, and cored into modern coral heads. These records were used to assess the influence of global warming and regional eutrophication, respectively, on the decline of coastal coral communities following the development of the Pearl River Delta (PRD) megacity, China. We find that, until 2007, ocean warming was not a major threat to coral communities in the Pearl River estuary; instead, nitrogen (N) inputs dominated impacts. The high but stable CS-δ15 N values (9‰-12‰ vs. air) observed from the mid-Holocene until 1980 indicate that soil and stream denitrification reduced and modulated the hydrologic inputs of N, blunting the rise in coastal N sources during the early phase of the Pearl River estuary urbanization. However, an unprecedented CS-δ15 N peak was observed from 1987 to 1993 (>13‰ vs. air), concomitant to an increase of NH4+ concentration, consistent with the rapid Pearl River estuary urbanization as the main cause for this eutrophication event. We suggest that widespread discharge of domestic sewage entered directly into the estuary, preventing removal by natural denitrification hotspots. We argue that this event caused the dramatic decline of the Pearl River estuary coral communities reported from 1980 to 2000. Subsequently, the coral record shows that the implementation of improved wastewater management policies succeeded in bringing down both CS-δ15 N and NH4+ concentrations in the early 2000s. This study points to the potential importance of eutrophication over ocean warming in coral decline along urbanized coastlines and in particular in the vicinity of megacities.

Glacial Indonesian Throughflow weakening across the Mid-Pleistocene Climatic Transition.

The Indonesian Throughflow (ITF) controls the oceanic flux of heat and salt between the Pacific and Indian Oceans and therewith plays an important role in modulating the meridional overturning circulation and low latitude hydrological cycle. Here, we report new sea surface temperature and aridity records from the west coast of Australia (IODP Site U1460), which allow us to assess the sensitivity of the eastern Indian Ocean to the major reorganization of Earth's climate that occurred during the Mid-Pleistocene Transition. Our records indicate glacial coolings at 1.55 and 0.65 million years ago that are best explained by a weakening of the ITF as a consequence of global sea level and tectonic changes. These coincide with the development of pronounced gradients in the carbon isotope composition of the different ocean basins and with substantial changes in regional aridity, suggesting that the restrictions of the ITF influenced both the evolution of global ocean circulation and the development of the modern hydrological cycle in Western Australia.

Nitrogen isotope evidence for expanded ocean suboxia in the early Cenozoic.

The million-year variability of the marine nitrogen cycle is poorly understood. Before 57 million years (Ma) ago, the 15N/14N ratio (δ15N) of foraminifera shell-bound organic matter from three sediment cores was high, indicating expanded water column suboxia and denitrification. Between 57 and 50 Ma ago, δ15N declined by 13 to 16 per mil in the North Pacific and by 3 to 8 per mil in the Atlantic. The decline preceded global cooling and appears to have coincided with the early stages of the Asia-India collision. Warm, salty intermediate-depth water forming along the Tethys Sea margins may have caused the expanded suboxia, ending with the collision. From 50 to 35 Ma ago, δ15N was lower than modern values, suggesting widespread sedimentary denitrification on broad continental shelves. δ15N rose at 35 Ma ago, as ice sheets grew, sea level fell, and continental shelves narrowed.

The residence time of Southern Ocean surface waters and the 100,000-year ice age cycle.

From 1.25 million to 700,000 years ago, the ice age cycle deepened and lengthened from 41,000- to 100,000-year periodicity, a transition that remains unexplained. Using surface- and bottom-dwelling foraminifera from the Antarctic Zone of the Southern Ocean to reconstruct the deep-to-surface supply of water during the ice ages of the past 1.5 million years, we found that a reduction in deep water supply and a concomitant freshening of the surface ocean coincided with the emergence of the high-amplitude 100,000-year glacial cycle. We propose that this slowing of deep-to-surface circulation (i.e., a longer residence time for Antarctic surface waters) prolonged ice ages by allowing the Antarctic halocline to strengthen, which increased the resistance of the Antarctic upper water column to orbitally paced drivers of carbon dioxide release.

Transient hydrodynamic effects influence organic carbon signatures in marine sediments.

Ocean dynamics served an important role during past dramatic climate changes via impacts on deep-ocean carbon storage. Such changes are recorded in sedimentary proxies of hydrographic change on continental margins, which lie at the ocean-atmosphere-earth interface. However, interpretations of these records are challenging, given complex interplays among processes delivering particulate material to and from ocean margins. Here we report radiocarbon (14C) signatures measured for organic carbon in differing grain-size sediment fractions and foraminifera in a sediment core retrieved from the southwest Iberian margin, spanning the last ~25,000 yr. Variable differences of 0-5000 yr in radiocarbon age are apparent between organic carbon in differing grain-sizes and foraminifera of the same sediment layer. The magnitude of 14C differences co-varies with key paleoceanographic indices (e.g., proximal bottom-current density gradients), which we interpret as evidence of Atlantic-Mediterranean seawater exchange influencing grain-size specific carbon accumulation and translocation. These findings underscore an important link between regional hydrodynamics and interpretations of down-core sedimentary proxies.

Natural forcing of the North Atlantic nitrogen cycle in the Anthropocene.

Human alteration of the global nitrogen cycle intensified over the 1900s. Model simulations suggest that large swaths of the open ocean, including the North Atlantic and the western Pacific, have already been affected by anthropogenic nitrogen through atmospheric transport and deposition. Here we report an ∼130-year-long record of the 15N/14N of skeleton-bound organic matter in a coral from the outer reef of Bermuda, which provides a test of the hypothesis that anthropogenic atmospheric nitrogen has significantly augmented the nitrogen supply to the open North Atlantic surface ocean. The Bermuda 15N/14N record does not show a long-term decline in the Anthropocene of the amplitude predicted by model simulations or observed in a western Pacific coral 15N/14N record. Rather, the decadal variations in the Bermuda 15N/14N record appear to be driven by the North Atlantic Oscillation, most likely through changes in the formation rate of Subtropical Mode Water. Given that anthropogenic nitrogen emissions have been decreasing in North America since the 1990s, this study suggests that in the coming decades, the open North Atlantic will remain minimally affected by anthropogenic nitrogen deposition.

Causes of ice age intensification across the Mid-Pleistocene Transition.

During the Mid-Pleistocene Transition (MPT; 1,200-800 kya), Earth's orbitally paced ice age cycles intensified, lengthened from ∼40,000 (∼40 ky) to ∼100 ky, and became distinctly asymmetrical. Testing hypotheses that implicate changing atmospheric CO2 levels as a driver of the MPT has proven difficult with available observations. Here, we use orbitally resolved, boron isotope CO2 data to show that the glacial to interglacial CO2 difference increased from ∼43 to ∼75 µatm across the MPT, mainly because of lower glacial CO2 levels. Through carbon cycle modeling, we attribute this decline primarily to the initiation of substantive dust-borne iron fertilization of the Southern Ocean during peak glacial stages. We also observe a twofold steepening of the relationship between sea level and CO2-related climate forcing that is suggestive of a change in the dynamics that govern ice sheet stability, such as that expected from the removal of subglacial regolith or interhemispheric ice sheet phase-locking. We argue that neither ice sheet dynamics nor CO2 change in isolation can explain the MPT. Instead, we infer that the MPT was initiated by a change in ice sheet dynamics and that longer and deeper post-MPT ice ages were sustained by carbon cycle feedbacks related to dust fertilization of the Southern Ocean as a consequence of larger ice sheets.