Carbon isotope ratioss of coccolith-associated polysaccharides of Emiliania huxleyi as a function of growth rate and CO2 concentration

The calcite plates, or coccoliths, of haptophyte algae including Emiliania huxleyi are formed in intracellular vesicles in association with water–soluble acidic polysaccharides. These coccolith–associated polysaccharides (CAPs) are involved in regulating coccolith formation and have been recovered from sediment samples dating back to ∼180 Ma. Paired measurements of the carbon isotopic compositions of CAPs and coccolith calcite have been proposed as a novel paleo–pCO2 barometer, but additional proxy validation and development are still required. Here we present culture results quantifying carbon isotopic offsets between CAPs and other cellular components: bulk organic biomass, alkenones, and calcite. E. huxleyi was grown in nitrate–limited chemostat experiments at growth rates (µ) of 0.20–0.62/d and carbon dioxide concentrations of 10.7–17.6 µmol/kg. We find that CAPs are isotopically enriched by 4.5–10.1‰ relative to bulk organic carbon, exhibiting smaller isotopic offsets at faster growth rates and lower CO2 concentrations. This variability suggests that CAPs record a complementary signature of past growth conditions with different sensitivity than alkenones or coccolith calcite. By measuring the isotopic compositions of all three molecules and minerals of self-consistent origin, the ratio µ/[CO2(aq)] may be reconstructed with fewer assumptions than current approaches

Large variation in the Rubisco kinetics of diatoms reveals diversity among their carbon-concentrating mechanisms

While marine phytoplankton rival plants in their contribution to global primary productivity, our understanding of their photosynthesis remains rudimentary. In particular, the kinetic diversity of the CO₂-fixing enzyme, Rubisco, in phytoplankton remains unknown. Here we quantify the maximum rates of carboxylation (Kcatᶜ), oxygenation (Kcatᵒ), Michaelis constants (K m) for CO₂ (K C) and O₂ (K O), and specificity for CO₂ over O₂ (SC/O) for Form I Rubisco from 11 diatom species. Diatom Rubisco shows greater variation in KC (23-68 μM), SC/O (57-116mol mol⁻¹), and KO (413-2032 μM) relative to plant and algal Rubisco. The broad range of KC values mostly exceed those of C₄ plant Rubisco, suggesting that the strength of the carbon-concentrating mechanism (CCM) in diatoms is more diverse, and more effective than previously predicted. The measured k cat c for each diatom Rubisco showed less variation (2.1-3.7s⁻¹), thus averting the canonical trade-off typically observed between KC and kcatᶜ for plant Form I Rubisco. Uniquely, a negative relationship between KC and cellular Rubisco content was found, suggesting variation among diatom species in how they allocate their limited cellular resources between Rubisco synthesis and their CCM. The activation status of Rubisco in each diatom was low, indicating a requirement for Rubisco activase. This work highlights the need to better understand the correlative natural diversity between the Rubisco kinetics and CCM of diatoms and the underpinning mechanistic differences in catalytic chemistry among the Form I Rubisco superfamily

Silicon isotopes in Antarctic sponges : an interlaboratory comparison

Cycling of deepwater silicon (Si) within the Southern Ocean, and its transport into other ocean basins, may be an important player in the uptake of atmospheric carbon, and global climate. Recent work has shown that the Si isotope (denoted by δ29Si or δ30Si) composition of deep sea sponges reflects the availability of dissolved Si during growth, and is a potential proxy for past deep and intermediate water silicic acid concentrations. As with any geochemical tool, it is essential to ensure analytical precision and accuracy, and consistency between methodologies and laboratories. Analytical bias may exist between laboratories, and sponge material may have matrix effects leading to offsets between samples and standards. Here, we report an interlaboratory evaluation of Si isotopes in Antarctic and sub-Antarctic sponges. We review independent methods for measuring Si isotopes in sponge spicules. Our results show that separate subsamples of non-homogenized sponges measured by three methods yield isotopic values within analytical error for over 80% of specimens. The relationship between δ29Si and δ30Si in sponges is consistent with kinetic fractionation during biomineralization. Sponge Si isotope analyses show potential as palaeoceaongraphic archives, and we suggest Southern Ocean sponge material would form a useful additional reference standard for future spicule analyses

Oxygen depletion recorded in upper waters of the glacial Southern Ocean

Oxygen depletion in the upper ocean is commonly associated with poor ventilation and storage of respired carbon, potentially linked to atmospheric CO2 levels. Iodine to calcium ratios (I/Ca) in recent planktonic foraminifera suggest that values less than ~2.5 μmol mol−1 indicate the presence of O2-depleted water. Here we apply this proxy to estimate past dissolved oxygen concentrations in the near surface waters of the currently well-oxygenated Southern Ocean, which played a critical role in carbon sequestration during glacial times. A down-core planktonic I/Ca record from south of the Antarctic Polar Front (APF) suggests that minimum O2 concentrations in the upper ocean fell below 70 μmol kg−1 during the last two glacial periods, indicating persistent glacial O2 depletion at the heart of the carbon engine of the Earth’s climate system. These new estimates of past ocean oxygenation variability may assist in resolving mechanisms responsible for the much-debated ice-age atmospheric CO2 decline

Calcification, Dissolution and Test Properties of Modern Planktonic Foraminifera From the Central Atlantic Ocean

The mass of well-preserved calcite in planktonic foraminifera shells provides an indication of the calcification potential of the surface ocean. Here we report the shell weight of 8 different abundant planktonic foraminifera species from a set of core-top sediments along the Mid-Atlantic Ridge. The analyses showed that near the equator, foraminifera shells of equivalent size weigh on average 1/3 less than those from the middle latitudes. The carbonate preservation state of the samples was assessed by high resolution X-ray microcomputed tomographic analyses of Globigerinoides ruber and Globorotalia truncatulinoides specimens. The specimen preservation was deemed good and does not overall explain the observed shell mass variations. However, G. ruber shell weights might be to some extent compromised by residual fine debris internal contamination. Deep dwelling species possess heavier tests than their surface-dwelling counterparts, suggesting that the weight of the foraminifera shells changes as a function of the depth habitat. Ambient seawater carbonate chemistry of declining carbonate ion concentration with depth cannot account for this interspecies difference. The results suggest a depth regulating function for plankton calcification, which is not dictated by water column acidity

The Giant Pacific Oyster (Crassostrea gigas) as a modern analog for fossil ostreoids: Isotopic (Ca, O, C) and elemental (Mg/Ca, Sr/Ca, Mn/Ca) proxies

Modern analogs are an essential part of palaeoclimate studies, because they provide the basis for the understanding of geochemical signatures of fossils. Ostreoids are common in many sedimentary sequences and because of their fast growth, high temporal resolution sampling of past seasonal variability is possible. Here, two shell structures of modern Giant Pacific Oysters (Crassostrea gigas), the chalky substance and foliate layers, have been sampled for trace element distributions (Mg, Sr, Mn) and stable isotope variability (C, O, Ca). Oxygen isotopes exhibit a clear seasonal signature. Mean carbon isotope values of different oysters agree within 0.1‰, but ontogenic variability is complicated by shell growth patterns and potential small vital effects. The calcium isotope ratios are found to be constant throughout ontogeny within analytical precision at a value of δ44/40Ca = 0.68 ± 0.16‰ (2 sd) SRM–915a which is consistent with other bivalve species. Calcium isotope ratios in oyster shell material might thus be a possible proxy for palaeo seawater calcium isotope ratios. Element/Ca ratios are significantly higher in the chalky substance than in the foliate layers and especially high Sr/Ca and Mn/Ca ratios are observed for the first growth season of the oysters. Mg/Ca ratios in the chalky substance show a negative correlation with δ18O values, compatible with a temperature dependence, whereas this correlation is absent in the foliate layers. Seasonal changes of Sr/Ca are controlled by metabolic processes, whereas for Mn/Ca an additional environmental control is evident

Changes in micronutrient supply to the surface Southern Ocean (Atlantic Sector) across the glacial termination

Major deepwater masses upwell and reach the surface in the Southern Ocean, forming an important conduit supplying nutrients and micronutrients to the surface and playing a key role in the regulation of global climate through ocean-atmosphere gas exchange. Here, we reconstruct changes in micronutrient distribution in this region in response to past changes in upwelling, oceanic mixing, and sea-ice seasonality. We present two downcore (Zn/Si)(opal) records from the Scotia Sea and Drake Passage region, which we interpret in the context of micronutrient distribution in the Atlantic sector of the Southern Ocean over the last glacial termination. Previous work shows that micronutrient availability in the surface waters in the South Atlantic appear to be controlled dominantly by upwelling and mixing of micronutrient rich deepwaters, which are additionally fuelled by the terrestrial sediment sources of the Scotia Arc and South Georgia. This is supported by our reconstructions, which show micronutrient availability to the west of the Scotia Arc and South Georgia are consistently lower than to the east over the last glacial termination due to downstream transport and mixing into surface waters of continentally derived material in the Antarctic Circumpolar Current. Micronutrient availability in this region was at a minimum from 20 to 25 ky BP, coinciding with maximum sea-ice coverage, and increased due to an expansion of the seasonal sea-ice zone and increased mixing of subsurface waters. Our findings are consistent with largely diminished upwelling of micronutrients during the maximum glacial extent, and reduced mixing due to the presence of persistent sea-ice. During the deglacial there was an increase in micronutrient availability, as well as other nutrients and inorganic carbon, within the Antarctic Circumpolar Current as a result of an increase in deep oceanic upwelling, mixing and strengthened zonal transport

Opening the gateways for diatoms primes Earth for Antarctic glaciation

The abrupt onset of Antarctic glaciation during the Eocene–Oligocene Transition (?33.7 Ma, Oi1) is linked to declining atmospheric pCO2 levels, yet the mechanisms that forced pCO2 decline remain elusive. Biogenic silicon cycling is inextricably linked to both long and short term carbon cycling through the diatoms, siliceous walled autotrophs which today account for up to 40% of primary production. It is hypothesised that during the Late Eocene a sharp rise in diatom abundance could have contributed to pCO2 drawdown and global cooling by increasing the proportion of organic carbon buried in marine sediment. Diatom and sponge silicon isotope ratios (?30Si) are here combined for the first time to reconstruct the late Eocene–early Oligocene ocean silicon cycle and provide new insight into the role of diatom productivity in Antarctic glaciation. At ODP site 1090 in the Southern Ocean, a 0.6‰ rise in diatom ?30Si through the late Eocene documents increasing diatom silicic acid utilisation with high, near modern values attained by the earliest Oligocene. A concomitant 1.5‰ decline in sponge ?30Si at ODP site 689 on the Maud Rise tracks an approximate doubling of intermediate depth silicic acid concentration in the high southern latitudes. Intermediate depth silicic acid concentration peaked at ?31.5 Ma, coincident with the final establishment of a deepwater pathway through the Tasman Gateway and Drake Passage. These results suggest that upwelling intensification related to the spin-up of a circum-Antarctic current may have driven late Eocene diatom proliferation. Organic carbon burial associated with higher diatom abundance and export provides a mechanism that can account for pCO2 drawdown not only at, but also prior to, Antarctic glaciation as required by a pCO2 ‘threshold’ mechanism for ice sheet growth

Dynamics of a stepped carbon-isotope excursion: Ultra high-resolution study of Early Toarcian environmental change

International audienceIn the Toarcian (Early Jurassic; ~183 Myr ago), the ocean-atmosphere system was subject to one of the larg- est perturbations of the carbon cycle in the last 250 Myr known as the Toarcian Oceanic Anoxic Event (T- OAE). This event was accompanied by a -6‰ negative carbon-isotope excursion (CIE) caused by massive injection of isotopically light carbon into the ocean-atmosphere system, possibly from destabilisation of gas hydrates. This study reveals the pacing and sequence of events leading up to the CIE and to widespread de position of organic-rich sediments. The very high-resolution isotopic record from exceptionally well- preserved carbonate and organic matter from the Paris Basin enables recognition of increased CO2 levels ~130 kyr in advance of the major negative CIE. An accelerated increase in the pCO2 is registered ~25 kyr be- fore the onset of this negative excursion and was so rapid and so intense that it led to a water column under-saturated with respect to calcium carbonate in the Paris Basin. Undersaturation is expressed as a dramatic drop in the accumulation of the biogenic calcite produced by the surface-dwelling calcifiers. These environ- mental perturbations, representing precursor phases of CO2 injection, predate the first step towards relative- ly light carbon-isotope in carbonate and organic matter and are tentatively attributed to Karoo-Ferrar magmatism. This negative shift was registered slightly earlier in terrestrial carbon than marine carbonate. Subsequent global warming is credited with liberating isotopically light carbon, and ultimately fostered an- oxia in the Paris Basin: the response of these cumulative inputs of carbon to the Earth system. Isotopic and sedimentological evidence indicates continuously elevated phytoplanktonic productivity throughout the first step of the negative CIE, suggesting that the biological pump accelerated the drawdown of excess carbon leading to temporary recovery of carbonate sedimentation, ~45 kyr after the first step of the CIE. This re- establishment of the saturation state of the water column was only fleeting before the later stepwise release of isotopically light carbon