delta 44/40Ca, Mg/Ca and delta 18O ratios of planktonic foraminifera from the Nordic Seas

A new approach for a solid delta44/40Ca temperature calibration of the polar to subpolar planktonic foraminifera N. pachyderma (sin.) is presented, based on a broad sample pool comprising North and South Atlantic genotyped net catches and Nordic Seas core top sample material. With this new additional SST proxy, the 'cold end' error of proxy temperature calibrations was addressed in combining delta44/40Ca, Mg/Ca and delta18O ratios in tests of N. pachyderma (sin.). At water temperatures below about 3.5°C, the proxy to temperature relationship recorded in the Mg/Ca and delta44/40Ca signal simultaneously disappears. Based on these 'cold-end' proxy-data we present a model demonstrating that the aberrant delta44/40Ca and Mg/Ca ratios in N. pachyderma (sin.) calcified in cold polar waters can be interpreted by a two-step chemical modification of vacuolized seawater during its cytosolar transport to the calcification site

Calcium isotopic composition of high-latitude proxy carrier Neogloboquadrina pachyderma (sin.)

The accurate reconstruction of sea surface temperature (SST) history in climate-sensitive regions (e.g. tropical and polar oceans) became a challenging task in palaeoceanographic research. Biogenic shell carbonate SST proxies successfully developed for tropical regions often fail in cool water environments. Their major regional shortcomings and the cryptic diversity now found within the major high latitude proxy carrier Neogloboquadrina pachyderma (sin.) highlight an urgent need to explore complementary SST proxies for these cool-water regions. Here we incorporate the genetic component into a calibration study of a new SST proxy for the high latitudes. We found that the calcium isotopic composition (δ44/40Ca) of calcite from genotyped net catches and core-top samples of the planktonic foraminifera Neogloboquadrina pachyderma (sin.) is related to temperature and unaffected by genetic variations. The temperature sensitivity has been found to be 0.17 (±0.02)‰ per 1°C, highlighting its potential for downcore applications in open marine cool-water environments. Our results further indicate that in extreme polar environments, below a critical threshold temperature of 2.0 (±0.5)°C associated with salinities below 33.0 (±0.5)‰, a prominent shift in biomineralization affects the δ44/40Ca of genotyped and core-top N. pachyderma (sin.), becoming insensitive to temperature. These findings highlight the need of more systematic calibration studies on single planktonic foraminiferal species in order to unravel species-specific factors influencing the temperature sensitivity of Ca isotope fractionation and to validate the proxies' applicability

Oxygen Isotope Variability within Nautilus Shell Growth Bands

Nautilus is often used as an analogue for the ecology and behavior of extinct externally shelled cephalopods. Nautilus shell grows quickly, has internal growth banding, and is widely believed to precipitate aragonite in oxygen isotope equilibrium with seawater. Pieces of shell from a wild-caught Nautilus macromphalus from New Caledonia and from a Nautilus belauensis reared in an aquarium were cast in epoxy, polished, and then imaged. Growth bands were visible in the outer prismatic layer of both shells. The thicknesses of the bands are consistent with previously reported daily growth rates measured in aquarium reared individuals. In situ analysis of oxygen isotope ratios using secondary ion mass spectrometry (SIMS) with 10 μm beam-spot size reveals inter- and intra-band δ18O variation. In the wild-caught sample, a traverse crosscutting 45 growth bands yielded δ18O values ranging 2.5‰, from +0.9 to -1.6 ‰ (VPDB), a range that is larger than that observed in many serial sampling of entire shells by conventional methods. The maximum range within a single band (~32 μm) was 1.5‰, and 27 out of 41 bands had a range larger than instrumental precision (±2 SD = 0.6‰). The results from the wild individual suggest depth migration is recorded by the shell, but are not consistent with a simple sinusoidal, diurnal depth change pattern. To create the observed range of δ18O, however, this Nautilus must have traversed a temperature gradient of at least ~12°C, corresponding to approximately 400 m depth change. Isotopic variation was also measured in the aquarium-reared sample, but the pattern within and between bands likely reflects evaporative enrichment arising from a weekly cycle of refill and replacement of the aquarium water. Overall, this work suggests that depth migration behavior in ancient nektonic mollusks could be elucidated by SIMS analysis across individual growth bands

Micron-scale intrashell oxygen isotope variation in cultured planktic foraminifers

In this study, we show that the rate of shell precipitation in the extant planktic foraminifer Orbulina universa is sufficiently rapid that 12 h calcification periods in 18O-labeled seawater can be resolved and accurately measured using secondary ion mass spectrometry (SIMS) for in situ δ18O analyses. Calcifying O. universa held at constant temperature (22 °C) were transferred every 12 h between ambient seawater (δ18Ow = −0.4‰ VSMOW) and seawater with enriched barium and δ18Ow = +18.6‰ VSMOW, to produce geochemically distinct layers of calcite, separated by calcite precipitated with an ambient geochemical signature. We quantify the position of the Ba-labeled calcite in the shell wall of O. universa via laser ablation ICP-MS depth profiling of trace element ratios, and then measure intrashell δ18Ocalcite in the same shells using SIMS with a 3 μm spot and an average precision of 0.6‰ (±2 SD). Measured δ18Ocalcite values in O. universa shell layers are within ±1.1‰ of predicted δ18Ocalcite values. Elemental and oxygen isotope data show that LA-ICP-MS and SIMS measurements can be cross-correlated within the spatial resolution of the two analytical techniques, and that δ18Ocalcite and elemental tracers appear to be precipitated synchronously with no measurable spatial offsets. These results demonstrate the capability of SIMS to resolve daily growth increments in foraminifer shells, and highlight its potential for paleoceanographic and biomineralization applications on microfossils

High‐resolution Mg/Ca and δ 18 O patterns in modern Neogloboquadrina pachyderma from the Fram Strait and Irminger Sea

Neogloboquadrina pachyderma is the dominant species of planktonic foraminifera found in polar waters and is therefore invaluable for paleoceanographic studies of the high latitudes. However, the geochemistry of this species is complicated due to the development of a thick calcite crust in its final growth stage and at greater depths within the water column. We analyzed the in situ Mg/Ca and δ18O in discrete calcite zones using LA‐ICP‐MS, EPMA and SIMS within modern N. pachyderma shells from the highly dynamic Fram Strait and the seasonally isothermal/isohaline Irminger Sea. Here we compare shell geochemistry to the measured temperature, salinity and δ18Osw in which the shells calcified to better understand the controls on N. pachyderma geochemical heterogeneity. We present a relationship between Mg/Ca and temperature in N. pachyderma lamellar calcite that is significantly different than published equations for shells that contained both crust and lamellar calcite. We also document highly variable SIMS δ18O results (up to a 3.3‰ range in single shells) on plankton tow samples which we hypothesize is due to the granular texture of shell walls. Finally, we document that the δ18O of the crust and lamellar calcite of N. pachyderma from an isothermal/isohaline environment are indistinguishable from each other, indicating that shifts in N. pachyderma δ18O are primarily controlled by changes in environmental temperature and/or salinity rather than differences in the sensitivities of the two calcite types to environmental conditions

Reassessing Mg/Ca temperature calibrations of <em>Neogloboquadrina pachyderma</em> (sinistral) using paired δ^44/40 and Mg/Ca measurements

The Mg/Ca temperature calibration of the polar to subpolar planktonic foraminifera Neogloboquadrina pachyderma (sinistral) (sinistral indicates left coiling) was refined by a multiproxy approach combining hydrographic temperature and salinity data with Mg/Ca, delta Ca-44/40, and delta O-18 values from Holocene Nordic seas core top samples. Reliable Mg/Ca-based temperature estimates are limited to foraminiferal tests that calcified in water masses with temperatures above similar to 3 degrees C at habitat depth. In these samples, Mg/Ca and delta Ca-44/40 values are positively correlated (Mg/Ca (mmol/mol) = 0.77 (+/- 0.22) x delta Ca-44/40 (parts per thousand SRM 915a) + 0.52 (+/- 0.12); n = 20, R-2 = 0.76). Both Mg/Ca- and delta Ca-44/40-derived temperatures projected onto their corresponding depth intervals reveal that the &quot;apparent'' calcification depth of N. pachyderma (sinistral) averaging the specimens' whole life cycle is bound to an isopycnal layer defined by water densities (sigma(t)) between 27.7 and 27.8. This implies that N. pachyderma (sinistral) prefers gradually deeper habitats with increasing sea surface temperatures, thus counterbalancing absolute temperature variations. Consequently, the total temperature range recorded in this foraminiferal species is restricted and only partly reflects environmental changes. On the basis of the new Mg/Ca, delta Ca-44/40, and delta O-18 multiproxy data set, we propose a linear Mg/Ca temperature relation for high-latitude N. pachyderma (sinistral): Mg/Ca (mmol/mol) = 0.13 (+/- 0.037) T (degrees C) + 0.35 (+/- 0.17); T &gt; 3 degrees C. In core top samples from polar waters with peak summer temperatures below similar to 3 degrees C, the temperature response in the Mg/Ca and delta Ca-44/40 proxy signal is inversed and poorly correlated. Both Mg/Ca- and delta Ca-44/40-derived temperature estimates pretend significantly higher calcification temperatures than maximum summer sea surface temperatures of these water masses

Trace metal composition and growth habit of cultured cold-water coral aragonite: proxy calibration experiments

5th Past Global Changes (PAGES) Ocean Sciences Meeting, 9-13 May 2017, ZaragozaWith life-spans of decades to more than 1000 years and skeletons suitable for precise U/Th dating, cold-water corals have the potential to provide climate and environmental information with a temporal resolution that can rarely be achieved in sediment cores. We have embarked on long-term culturing experiments using Desmophyllum dianthus (a solitary deep coral, typical lifespan 100 yr) in order to calibrate geochemical proxies for dissolved nutrients and the carbonate system (poster by Pelejero et al., this meeting), controlling seawater composition and pH in a flow-through aquarium. An early goal is to better understand and quantify skeletal extension patterns and growth rates on time scales of months-years, currently poorly known for this species. To locate regions of new skeletal growth for subsequent chemical analysis, we tested the suitability of Alizarin and Calcein dyes as a fluorescent markers of the growing surface of D. dianthus septa, both upon initiation and at critical time points during culturing experiments. This approach results in stained skeletal sections that are quickly and easily analyzed in 3D by confocal microscopy. Results showed that growth over several months was localized, and extension rates among and even within individual septa varied greatly. Calcein staining lines were particularly useful in selecting regions for analysis by laser ablation ICP-MS. Spiking aquarium seawater with periodically varied enriched Pb isotopes proved to be a relatively inexpensive way to verify growth intervals and confirm complex growth patterns interpreted from stain distribution. We will discuss initial results of analysis of new aragonite grown under tightly controlled seawater conditions with the aim of refining calibrations of the proxies P/Ca, Ba/Ca, U/Ca, and Li/Mg as proxies of dissolved nutrients, the carbonate system, and calcification temperaturePeer Reviewe

Oxygen Isotope Variability within Nautilus Shell Growth Bands

Nautilus is often used as an analogue for the ecology and behavior of extinct externally shelled cephalopods. Nautilus shell grows quickly, has internal growth banding, and is widely believed to precipitate aragonite in oxygen isotope equilibrium with seawater. Pieces of shell from a wild-caught Nautilus macromphalus from New Caledonia and from a Nautilus belauensis reared in an aquarium were cast in epoxy, polished, and then imaged. Growth bands were visible in the outer prismatic layer of both shells. The thicknesses of the bands are consistent with previously reported daily growth rates measured in aquarium reared individuals. In situ analysis of oxygen isotope ratios using secondary ion mass spectrometry (SIMS) with 10 μm beam-spot size reveals inter- and intra-band δ18O variation. In the wild-caught sample, a traverse crosscutting 45 growth bands yielded δ18O values ranging 2.5‰, from +0.9 to -1.6 ‰ (VPDB), a range that is larger than that observed in many serial sampling of entire shells by conventional methods. The maximum range within a single band (~32 μm) was 1.5‰, and 27 out of 41 bands had a range larger than instrumental precision (±2 SD = 0.6‰). The results from the wild individual suggest depth migration is recorded by the shell, but are not consistent with a simple sinusoidal, diurnal depth change pattern. To create the observed range of δ18O, however, this Nautilus must have traversed a temperature gradient of at least ~12°C, corresponding to approximately 400 m depth change. Isotopic variation was also measured in the aquarium-reared sample, but the pattern within and between bands likely reflects evaporative enrichment arising from a weekly cycle of refill and replacement of the aquarium water. Overall, this work suggests that depth migration behavior in ancient nektonic mollusks could be elucidated by SIMS analysis across individual growth bands