Claire Rollion-Bard

pH control on oxygen isotopic composition of symbiotic corals

Abstract Boron, carbon and oxygen isotopic compositions were determined at the micrometre scale by high-resolution ion microprobe in a sample of modern coral (massive hermatypic coral, Porites lutea). The ion probe data show for B and O much larger isotopic variations at the micrometre scale than those measured at the millimetre scale by conventional techniques: δ18OPDB values range from −10.6±0.9‰ to −0.2±0.5‰ and δ11B values range from +18.6±1.5‰ to +30.6±1.6‰. By contrast, δ13C values show the same range of variations, from −4.6±0.65‰ to −2.2±0.67‰ at the micrometre and millimetre scales. The range of δ11B values indicates that significant pH variations, from ≈7.1 to ≈9.0, are present at the sites of calcification. The largest δ18O variations correspond to the highest δ11B values, i.e. to the highest pHs. This measurement of pH allows modelling the oxygen isotopic fractionation occurring during aragonite precipitation. Taking into account the rate of O isotopic equilibrium between dissolved carbonate species (H2CO3, HCO3− and CO32−) and water via the two reactions of hydration and hydroxylation, the full range of δ18O values measured at the micrometre scale can be modelled for residence times of dissolved carbonates in the calcifying fluid ranging between ≈1 h and at maximum ≈12 h. The pH controls the δ18O of the growing carbonate through the relative fractions of dissolved carbonate species and through the kinetics of their isotopic equilibration with water via hydration and hydroxylation. The so-called ‘vital effect’ systematically observed for δ18O in corals can thus be understood as representing an average of rapid pH variations due to coral biology during coral growth. Selectively measuring δ18O values in the zones of coral skeletons that have low δ11B values (i.e. formed at low pH) should significantly improve the quality of palaeoclimatic reconstructions based on δ18O values.

Oxygen dynamics in the aftermath of the Great Oxidation of Earth’s atmosphere

Significance The Great Oxidation of Earth’s atmosphere about 2.3 billion years ago began a series of geochemical events leading to elevated oxygen levels for the next 200 million years, with a collapse to much lower levels as these events played their course. This sequence of events is represented in rocks from the Republic of Gabon. We show oxygenation of the deep oceans when oxygen levels were likely their highest. By 2.08 billion years ago, however, oxygen dropped to levels possibly as low as any time in the last 2.3 billion years. These fluctuations can be explained as a direct consequence of the initial oxygenation of the atmosphere during the Great Oxidation Event. The oxygen content of Earth’s atmosphere has varied greatly through time, progressing from exceptionally low levels before about 2.3 billion years ago, to much higher levels afterward. In the absence of better information, we usually view the progress in Earth’s oxygenation as a series of steps followed by periods of relative stasis. In contrast to this view, and as reported here, a dynamic evolution of Earth’s oxygenation is recorded in ancient sediments from the Republic of Gabon from between about 2,150 and 2,080 million years ago. The oldest sediments in this sequence were deposited in well-oxygenated deep waters whereas the youngest were deposited in euxinic waters, which were globally extensive. These fluctuations in oxygenation were likely driven by the comings and goings of the Lomagundi carbon isotope excursion, the longest–lived positive δ13C excursion in Earth history, generating a huge oxygen source to the atmosphere. As the Lomagundi event waned, the oxygen source became a net oxygen sink as Lomagundi organic matter became oxidized, driving oxygen to low levels; this state may have persisted for 200 million years.

C and O isotopes in a deep-sea coral (Lophelia pertusa) related to skeletal microstructure

Lophelia pertusa is a deep-sea scleractinian coral (azooxanthellate) found on the continental margins of the major world oceans. Built of aragonite it can be precisely dated and measured for stable isotope composition (C–O) to reconstruct past oceanic conditions. However, the relation between stable isotope and skeleton microstructures, i.e. centres of calcification and surrounding fibres, is crucial for understanding the isotopic patterns. Values for δ18O and δ13C in Lophelia pertusa were determined at a micrometer scale using an ion microprobe (SIMS - Secondary Ion Mass Spectrometry). In this coral species, centres of calcification are large (50 µm) and arranged in lines. The centres of calcification have a restricted range of variation in δ18O (−2.8 ± 0.3 ‰ (V-PDB)), and a larger range in δ13C (14.3 to 10.9 ‰ (V-PDB)). Surrounding skeletal fibres exhibit large isotopic variation both for C and O (up to 12 ‰) and δ13C and δ18O are positively correlated. The C and O isotopic composition of the centres of calcification deviate from this linear trend at the lightest δ18O values of the surrounding fibres. The fine-scaled variation of δ18O is probably the result of two processes: (1) isotopic equilibrium calcification with at least 1 pH unit variation in the calcification fluid and (2) kinetic fractionation. The apparent δ13C disequilibrium in Lophelia pertusa may be the result of mixing between depleted δ13C metabolic CO2 (respiration) and DIC coming directly from seawater. This study underlines the close relationship between microstructure and stable isotopes in corals. This relationship must also be taken into consideration for major elements like Mg and trace elements (U-Sr-Ba) increasing the reliability of the geochemical tools used in paleoceanography.

In situ measurements of Li isotopes in foraminifera

In situ measurement of Li isotope ratios in foraminifera has been developed using a Cameca ims 1270 ion microprobe. In situ δ7Li analyses have been performed in biogenic calcite of planktonic foraminifera from various locations. Results show that for west Pacific mixed Globigerinoides and Globorotalia (22°S161°E), the isotopic variability between tests and within a single test, respectively, is not significantly greater than estimated analytical uncertainty (∼1.5‰). Mean δ7Li for several planktonic foraminifera tests corresponds to the seawater value, strongly suggesting negligible Li isotope fractionation relative to seawater, as previously inferred by Hall et al. (2005) using thermo-ionization mass spectrometer and multicollector-inductively coupled plasma-mass spectrometry techniques. Combined with scanning electron microscopy and ion microprobe imaging, micron-sized grains, enriched in lithium, silica and aluminum have been found in the foraminifera calcite matrix. A simple mixing model shows that 0.3–2 wt % of marine clays incorporated within the analyzed calcite would lower the foraminifera δ7Li value, by 3‰ to 10‰ relative to the isotopic composition of the pure calcite. By comparison, no such grains have been detected in corals. The presence of micron-sized silicate grains embedded within the foraminifera calcite is consistent with the Erez (2003) biomineralization model, involving calcite precipitation from seawater vacuoles. By contrast, coral calcium carbonate is instead precipitated from ions, which have been pumped or diffused through several membranes, impermeable to micrometric grains. Ion microprobe in situ δ7Li measurements in biogenic calcite present new methods for investigating both biomineralization processes and the past record of the ocean composition by exploring geochemical variations at a scale that is smaller in space and in time.

Recent Advances in Coral Biomineralization with Implications for Paleo-Climatology: A Brief Overview

Abstract The tropical oceans drive climatic phenomena such as the El Nino-southern oscillation (ENSO) and the Asian–Australian monsoon, which have global scale impacts. In order to understand future climatic developments, it is essential to understand how the tropical climate has developed in the past, on both short and longer timescales. However, good instrumental records are limited to the last few decades. The oxygen isotopic (δ 18 O) composition and strontium/calcium (Sr/Ca) ratio of massive corals have been widely used as proxies for past changes in sea surface temperature (SST) of the tropical and subtropical oceans, because the geochemistry of the skeleton is believed to vary as a function of several environmental parameters (such as seawater temperature, salinity, light, …). However, recent microanalytical studies have revealed large amplitude variations in Sr/Ca and oxygen isotopic composition in coral skeletons; variations that cannot be ascribed to changes in SST or in salinity. Such micro- and nanometer scale studies of geochemical variations in coral skeletons are still few and somewhat scattered in terms of the species studied and the problems addressed. But collectively they show the great potential for determining chemical variations at length scales of direct relevance to the biomineralization process. For example, it is now possible to measure geochemical variations within the two basic, micrometer-sized building blocks of the coral skeleton: Early mineralization zones (EMZ) and aragonite fibres. Such micro- and nanometer scale observations, in combination with controlled laboratory culturing of corals, hold the promise of yielding important new insights into the various biomineralization processes that may affect the chemical and isotopic composition of the skeletons. One aim of these efforts is to better understand the elemental and isotopic fractionation mechanisms in order to improve the conversion of the geochemical variability into environmental changes.