Correlative geochemical imaging of Desmophyllum dianthus reveals biomineralisation strategy as a key coral vital effect.

The chemical and isotopic composition of stony coral skeletons form an important archive of past climate. However, these reconstructions are largely based on empirical relationships often complicated by "vital effects" arising from uncertain physiological processes of the coral holobiont. The skeletons of deep-sea corals, such as Desmophyllum dianthus, are characterised by micron-scale or larger geochemical heterogeneity associated with: (1) centres of calcification (COCs) where nucleation of new skeleton begins, and (2) fibres that thicken the skeleton. These features are difficult to sample cleanly using traditional techniques, resulting in uncertainty surrounding both the causes of geochemical differences and their influence on environmental signals. Here we combine optical, and in-situ chemical and isotopic, imaging tools across a range of spatial resolutions (~ 100 nm to 10 s of µm) in a correlative multimodal imaging (CMI) approach to isolate the microstructural geochemistry of each component. This reveals COCs are characterised by higher organic content, Mg, Li and Sr and lower U, B and δ11B compared to fibres, reflecting the contrasting biomineralisation mechanisms employed to construct each feature. CMI is rarely applied in Environmental/Earth Sciences, but here we illustrate the power of this approach to unpick the "vital effects" in D. dianthus, and by extension, other scleractinian corals.

Toward a Cenozoic history of atmospheric CO2.

The geological record encodes the relationship between climate and atmospheric carbon dioxide (CO2) over long and short timescales, as well as potential drivers of evolutionary transitions. However, reconstructing CO2 beyond direct measurements requires the use of paleoproxies and herein lies the challenge, as proxies differ in their assumptions, degree of understanding, and even reconstructed values. In this study, we critically evaluated, categorized, and integrated available proxies to create a high-fidelity and transparently constructed atmospheric CO2 record spanning the past 66 million years. This newly constructed record provides clearer evidence for higher Earth system sensitivity in the past and for the role of CO2 thresholds in biological and cryosphere evolution.

Large-scale culturing of Neogloboquadrina pachyderma, its growth in, and tolerance of, variable environmental conditions.

The planktic foraminifera Neogloboquadrina pachyderma is a calcifying marine protist and the dominant planktic foraminifera species in the polar oceans, making it a key species in marine polar ecosystems. The calcium carbonate shells of foraminifera are widely used in palaeoclimate studies because their chemical composition reflects the seawater conditions in which they grow. This species provides unique proxy data for past surface ocean hydrography, which can provide valuable insight to future climate scenarios. However, little is known about the response of N. pachyderma to variable and changing environmental conditions. Here, we present observations from large-scale culturing experiments where temperature, salinity and carbonate chemistry were altered independently. We observed overall low mortality, calcification of new chambers and addition of secondary calcite crust in all our treatments. In-culture asexual reproduction events also allowed us to monitor the variable growth of N. pachyderma's offspring. Several specimens had extended periods of dormancy or inactivity after which they recovered. These observations suggest that N. pachyderma can tolerate, adapt to and calcify within a wide range of environmental conditions. This has implications for the species-level response to ocean warming and acidification, for future studies aiming to culture N. pachyderma and use in palaeoenvironmental reconstruction.

Abrupt upwelling and CO2 outgassing episodes in the north-eastern Arabian Sea since mid-Holocene.

Identifying the causes and consequences of natural variations in ocean acidification and atmospheric CO2 due to complex earth processes has been a major challenge for climate scientists in the past few decades. Recent developments in the boron isotope (δ11B) based seawater pH and pCO2 (or pCO2sw) proxy have been pivotal in understanding the various oceanic processes involved in air-sea CO2 exchange. Here we present the first foraminifera-based δ11B record from the north-eastern Arabian Sea (NEAS) covering the mid-late Holocene (~ 8-1 ka). Our record suggests that the region was overall a moderate to strong CO2 sink during the last 7.7 kyr. The region behaved as a significant CO2 source during two short intervals around 5.5-4 ka and 2.8-2.5 ka. The decreased pH and increased CO2 outgassing during those abrupt episodes are associated with the increased upwelling in the area. The upwelled waters may have increased the nutrient content of the surface water through either increased supply or weaker export production. This new dataset from the coastal NEAS suggests that, as a potential result of changes in the strength of the El-Nino Southern Oscillation, the region experienced short episodes of high CO2 outgassing and pre-industrial ocean acidification comparable to or even greater than that experienced during the last ~ 200 years.

Atmospheric CO2 during the Mid-Piacenzian Warm Period and the M2 glaciation.

The Piacenzian stage of the Pliocene (2.6 to 3.6 Ma) is the most recent past interval of sustained global warmth with mean global temperatures markedly higher (by ~2-3 °C) than today. Quantifying CO2 levels during the mid-Piacenzian Warm Period (mPWP) provides a means, therefore, to deepen our understanding of Earth System behaviour in a warm climate state. Here we present a new high-resolution record of atmospheric CO2 using the δ11B-pH proxy from 3.35 to 3.15 million years ago (Ma) at a temporal resolution of 1 sample per 3-6 thousand years (kyrs). Our study interval covers both the coolest marine isotope stage of the mPWP, M2 (~3.3 Ma) and the transition into its warmest phase including interglacial KM5c (centered on ~3.205 Ma) which has a similar orbital configuration to present. We find that CO2 ranged from [Formula: see text]ppm to [Formula: see text]ppm, with CO2 during the KM5c interglacial being [Formula: see text]ppm (at 95% confidence). Our findings corroborate the idea that changes in atmospheric CO2 levels played a distinct role in climate variability during the mPWP. They also facilitate ongoing data-model comparisons and suggest that, at present rates of human emissions, there will be more CO2 in Earth's atmosphere by 2025 than at any time in at least the last 3.3 million years.

The effect of matrix interferences on in situ boron isotope analysis by laser ablation multi-collector inductively coupled plasma mass spectrometry.

RATIONALE: Boron isotope analysis of marine carbonates by laser ablation multi-collector inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) offers the potential for rapid sample throughput, and the means to examine micron-scale variations in the δ11 B signatures of fossil skeletons and shells/tests of marine organisms. Existing studies demonstrate an acceptable level of reproducibility is achievable, but also typically show a level of accuracy outside the limits required by most applications. Here we investigate matrix interference effects as a cause of inaccuracy and imprecision. METHODS: Analyses were performed on a standard format Thermo Scientific Neptune Plus MC-ICP mass spectrometer coupled to a New Wave Research 193 nm ArF laser ablation system. The effects of matrix interference on δ11 B analysis were investigated through analyses of a set of reference materials with differing B/Ca ratios. Three approaches to correct for matrix-induced effects were trialled: (1) use of matrix-matched standards, (2) utilisation of the relationship between δ11 B inaccuracy and11 B/43 Ca, 11 B/40 ArCa4+ or 11 B/Cainterference from three reference materials with known δ11 B values and varying B/Ca ratios, and (3) direct characterisation of the (sloping) interference itself. RESULTS: Matrix interference from scattered Ca ions on 10 B can impede both the accuracy and the reproducibility of δ11 B analysis by LA-MC-ICP-MS. Based on analyses of two in-house reference materials, deep sea coral PS69/3181 and inorganic calcite UWC-1, we find approach 2, following the 11 B/Cainterference relationship, gives the best mean accuracies (within 0.4‰ of solution values) and external reproducibilities (± 0.5‰ 2 SD for PS69/3181). This approach has been applied to analyses of an annual growth cycle of a Siderastrea siderea coral and eight Cibicidoides wuellerstorfi benthic foraminifera. Both coral and foraminifera data match solution MC-ICP-MS analyses within reported uncertainties. CONCLUSIONS: LA-MC-ICP-MS can produce accurate and precise δ11 B data to a 0.5‰ (2σ) level on <0.3 ng B after correction for Ca interference effects.

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.