The Mg/Ca–temperature relationship in brachiopod shells: calibrating a potential palaeoseasonality proxy

Brachiopods are long-lived, long-ranging, extant organisms, of which some groups precipitate a relatively diagenetically stable low magnesium calcite shell. Previous work has suggested that the incorporation of Mg into brachiopod calcite may be controlled by temperature (Brand et al., 2013). Here we build upon this work by using laser ablation sampling to define the intra-shell variations in two modern brachiopod species,Terebratulina retusa (Linnaeus, 1758) and Liothyrella neozelanica (Thomson, 1918). We studied three T. retusa shells collected live from the Firth of Lorne, Scotland, which witnessed annual temperature variations on the order of 7 °C, in addition to four L. neozelanica shells, which were dredged from a water depth transect (168–1488 m) off the north coast of New Zealand. The comparison of intra-shell Mg/Ca profiles with shell δ<sup>18</sup>O confirms a temperature control on brachiopod Mg/Ca and supports the use of brachiopod Mg/Ca as a palaeoseasonality indicator. Our preliminary temperature calibrations are Mg/Ca = 1.76 ± 0.27 e<sup>(0.16 ± 0.03)T</sup>, R<sup>2</sup> = 0.75, for T. retusa and Mg/Ca = 0.49 ± 1.27 e<sup>(0.2 ± 0.11)T</sup>, R<sup>2</sup> = 0.32, for L. neozelanica (errors are 95% confidence intervals)

Multi-elemental composition of authigenic carbonates in benthic foraminifera from the eastern Bering Sea continental margin (International Ocean Discovery Program Site U1343)

Bering Sea sediments represent exceptional archives, offering the potential to study past climates and biogeochemistry at a high resolution. However, abundant hydrocarbons of microbial origin, especially along the eastern Bering Sea continental margin, can hinder the applicability of palaeoceanographic proxies based on calcareous foraminifera, due to the formation of authigenic carbonates. Nonetheless, authigenic carbonates may also bear unique opportunities to reconstruct changes in the sedimentary redox environment. Here we use a suite of visual and geochemical evidence from single-specimens of the shallow infaunal benthic foraminiferal species Elphidium batialis Saidova (1961), recovered from International Ocean Discovery Program (IODP) Site U1343 in the eastern Bering Sea, to investigate the influence of authigenic carbonates on the foraminiferal trace metal composition. Our results demonstrate that foraminiferal calcite tests act as a nucleation template for secondary carbonate precipitation, altering their geochemistry where organoclastic sulphate reduction and anaerobic oxidation of methane cause the formation of low- and high-Mg calcite, respectively. The authigenic carbonates can occur as encrusting on the outside and/or inside of foraminiferal tests, in the form of recrystallization of the test wall, or as banding along natural laminations within the foraminiferal test walls. In addition to Mg, authigenic carbonates are enriched in U/Ca, Mn/Ca, Fe/Ca, and Sr/Ca, depending on the redox environment that they were formed in. Our results demonstrate that site-specific U/Ca thresholds are a promising tool to distinguish between diagenetically altered and pristine foraminiferal samples, important for palaeoceanographic reconstructions utilising the primary foraminiferal geochemistry. Consistent with previous studies, U/Mn ratios of foraminifera at IODP Site U1343 increase according to their degree of diagenetic alteration, suggesting a potential response of authigenic U/Mn to the microbial activity in turn linked to the sedimentary redox environment

Temperature and carbonate ion effects on Mg/Ca and Sr/Ca ratios in benthic foraminifera : aragonitic species Hoeglundina elegans

Author Posting. © American Geophysical Union, 2006. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Paleoceanography 21 (2006): PA1007, doi:10.1029/2005PA001158.Core top samples from Atlantic (Little Bahama Banks (LBB)) and Pacific (Hawaii and Indonesia) depth transects have been analyzed in order to assess the influence of bottom water temperature (BWT) and aragonite saturation levels on Mg/Ca and Sr/Ca ratios in the aragonitic benthic foraminifer Hoeglundina elegans. Both the Mg/Ca and Sr/Ca ratios in H. elegans tests show a general decrease with increasing water depth. Although at each site the decreasing trends are consistent with the in situ temperature profile, Mg/Ca and Sr/Ca ratios in LBB are substantially higher than in Indonesia and Hawaii at comparable water depths with a greater difference observed with increasing water depth. Because we find no significant difference between results obtained on “live” and “dead” specimens, we propose that these differences are due to primary effects on the metal uptake during test formation. Evaluation of the water column properties at each site suggests that in situ CO3 ion concentrations play an important role in determining the H. elegans Mg/Ca and Sr/Ca ratios. The CO3 ion effect is limited, however, only to aragonite saturation levels ([ΔCO3]aragonite) below 15 μmol kg−1. Above this level, temperature exerts a dominant effect. Accordingly, we propose that Mg/Ca and Sr/Ca in H. elegans tests can be used to reconstruct thermocline temperatures only in waters oversaturated with respect to the mineral aragonite using the following relationships: Mg/Ca = (0.034 ± 0.002)BWT + (0.96 ± 0.03) and Sr/Ca = (0.060 ± 0.002)BWT + (1.53 ± 0.03) (for [ΔCO3]aragonite > 15 μmol kg−1). The standard error associated with these equations is about ±1.1°C. Reconstruction of deeper water temperatures is complicated because in undersaturated waters, changes in Mg/Ca and Sr/Ca ratios reflect a combination of changes in [CO3] and BWT. Overall, we find that Sr/Ca, rather than Mg/Ca, in H. elegans may be a more accurate proxy for reconstructing paleotemperatures.Yair Rosenthal acknowledges the support of Amtzia Genin and the Hebrew University, Forchheimer Fellowship, during his sabbatical in the Inter-University Institute in Eilat, Israel. This project has been funded by NSF Awards OCE 0220922 to Y.R. and OCE 0220776 to D.W.O. and B.K.L

Apparent preservation of primary foraminiferal Mg/Ca ratios and Mg-banding in recrystallized foraminifera

Trace element and δ18O values of foraminifera are widely used to reconstruct oceanic temperatures throughout the Cenozoic and beyond. Previous work evaluating the geochemistry of foraminifera with differing degrees of physical preservation have shown that Mg/Ca and δ18O paleothermometers give discrepant values in recrystallized tests, with planktonic oxygen isotopes often yielding significantly lower temperatures than Mg/Ca ratios. To study the mobility of elements during diagenesis, we performed microspatial trace element analyses in Eocene Morozovella. Element maps show that trace element banding is readily identifiable and preserved, to an extent, in texturally recrystallized tests. A reaction-diffusion model was used to test whether the preservation of Mg-banding and the decoupling of δ18O and Mg/Ca values could be the result of diffusively limited “closed-system” recrystallization. Results show that, in a closed system, internal features (such as Mg-banding) will dissipate prior to changes in bulk Mg/Ca composition, while the bulk δ18O value will typically change faster than Mg/Ca. This is observed regardless of what partitioning coefficient is used for Mg and demonstrates that the planktonic Mg/Ca proxy is more diagenetically robust than the δ18O proxy. Thus, this model can explain the observed decoupling of these two proxies. Furthermore, the preservation of intra-test Mg-banding shows potential for use in evaluating the preservation of primary Mg/Ca values and hence the accuracy of paleotemperature reconstructions

Spine-like structures in Paleogene muricate planktonic foraminifera

Muricate planktonic foraminifera comprise an extinct clade that was diverse and abundant in the Paleogene oceans and are widely used in palaeoclimate research as geochemical proxy carriers for the upper oceans. Their characteristic wall texture has surface projections called “muricae” formed by upward deflection and mounding of successive layers of the test wall. The group is generally considered to have lacked “true spines”: that is, acicular calcite crystals embedded in and projecting from the test surface such as occur in many modern and some Paleogene groups. Here we present evidence from polished sections, surface wall scanning electron microscope images and test dissections, showing that radially orientated crystalline spine-like structures occur in the centre of muricae in various species of Acarinina and Morozovella and projected from the test wall in life. Their morphology and placement in the wall suggest that they evolved independently of true spines. Nevertheless, they may have served a similar range of functions as spines in modern species, including aiding buoyancy and predation and especially harbouring algal photosymbionts, the function for which we suggest they probably first evolved. Our observations strengthen the analogy between Paleogene mixed-layer-dwelling planktonic foraminifera and their modern spinose counterparts

Calcareous nannofossils across the Eocene-Oligocene transition at Site 756 (Ninetyeast Ridge, Indian Ocean): implications for biostratigraphy and paleoceanographic clues

The timing and modalities of calcareous phytoplankton community and evolutionary responses to the Eocene-Oligocene transition (EOT, ~34 Ma) are still under-investigated. In order to better constrain the dynamics of these pelagic primary producers during the climate transition, we conducted high resolution assemblage analysis on calcareous nannofossils across a ~19 m-thick interval of nannofossil ooze at Ocean Drilling Program (ODP) Site 756 (Ninetyeast Ridge, Indian Ocean; Peirce et al. 1989) (paleolatitude ~43° S; Zachos et al. 1992). We explored the diversity patterns against a new integrated planktonic foraminifera and calcareous nannofossil biostratigraphy produced for the site, as well as new benthic foraminifera and bulk sediment stable isotope (C, O) records, which documents ocean-climate changes, and provides independent chemostratigraphy. The study section spans nannofossil Zones NP20-NP23 (equivalent to CNE20-CNO4) and lasts 5.5 Myr. The results show that the hankeninid extinction falls within the ~4.5 m-thick EOT isotopic interval (0.67 m below the base of the second positive δ18O shift – EOIS), which is consistent with previous studies, making Hole 756C one of a few sites globally boasting both the familiar stepped δ18O and δ13C structure of the EOT and the primary biostratigraphic marker defining the base of the Oligocene. A series of potentially useful new calcareous nannofossil bioevents were identified that could help improve dating and correlation of this crucial interval. In this context, changes in calcareous nannofossil assemblages observed across EOT are interpreted in terms of modifications of paleoecological parameters that typically control the abundance and distribution of different taxa. Variations in sea surface temperature and nutrient availability are considered to be the most likely triggers for the calcareous phytoplankton changes observed across EOT. Specifically, our data suggest that increased nutrients in the mixed layer played a key role in shaping the late Eocene – early Oligocene calcareous nannofossil assemblages

Joint inversion of proxy system models to reconstruct paleoenvironmental time series from heterogeneous data

Paleoclimatic and paleoenvironmental reconstructions are fundamentally uncertain because no proxy is a direct record of a single environmental variable of interest; all proxies are indirect and sensitive to multiple forcing factors. One productive approach to reducing proxy uncertainty is the integration of information from multiple proxy systems with complementary, overlapping sensitivity. Mostly, such analyses are conducted in an ad hoc fashion, either through qualitative comparison to assess the similarity of single-proxy reconstructions or through step-wise quantitative interpretations where one proxy is used to constrain a variable relevant to the interpretation of a second proxy. Here we propose the integration of multiple proxies via the joint inversion of proxy system and paleoenvironmental time series models in a Bayesian hierarchical framework. The “Joint Proxy Inversion” (JPI) method provides a statistically robust approach to producing self-consistent interpretations of multi-proxy datasets, allowing full and simultaneous assessment of all proxy and model uncertainties to obtain quantitative estimates of past environmental conditions. Other benefits of the method include the ability to use independent information on climate and environmental systems to inform the interpretation of proxy data, to fully leverage information from unevenly and differently sampled proxy records, and to obtain refined estimates of proxy model parameters that are conditioned on paleo-archive data. Application of JPI to the marine Mg∕Ca and δ18O proxy systems at two distinct timescales demonstrates many of the key properties, benefits, and sensitivities of the method, and it produces new, statistically grounded reconstructions of Neogene ocean temperature and chemistry from previously published data. We suggest that JPI is a universally applicable method that can be implemented using proxy models of wide-ranging complexity to generate more robust, quantitative understanding of past climatic and environmental change

Revealing their true stripes: Mg/Ca banding in the Paleogene planktonic foraminifera genus Morozovella and implications for paleothermometry

The Mg/Ca ratio of foraminiferal calcite is a widely used empirical proxy for ocean temperature. Foraminiferal Mg/Ca-temperature relationships are based on extant species and are species-specific, introducing uncertainty when applying them to the fossil tests of extinct groups. Many modern species show remarkable heterogeneity in their intra-test Mg distributions, typically due to the presence of high Mg bands, which have a biological origin. Importantly, banding patterns differ between species, which could affect Mg/Ca-temperature relationships. Few studies have looked at intra-test variability in Mg/Ca ratios in extinct species of foraminifera, despite the obvious implications for paleothermometry. We used electron probe microanalysis (EPMA) to investigate intra-test Mg distributions in the fossil tests of two species of planktonic foraminifera from the extinct muricate mixed-layer-dwelling genus Morozovella, commonly used in Paleogene sea surface temperature reconstructions. Both M. aragonensis and M. crater show striking Mg banding patterns with multiple high and low Mg/Ca band pairs throughout the test wall in all chambers. The intra-test Mg variability in M. aragonensis and M. crater is similar to that in modern species widely used in paleoclimate reconstructions and banding patterns are consistent with published growth models for modern forms, albeit with subtle differences. The presence of Mg bands supports the application of Mg/Ca-palaeothermometry in extinct Morozovella species as well as the utility of EPMA for examining preservation of foraminifera tests in paleoclimatological studies. However, we emphasize the importance of rigorous assessments of inter- and intra-test Mg variability when using microanalytical techniques for foraminiferal Mg/Ca paleothermometry

A rapid, simple, and low-blank pumped ion-exchange column chromatography technique for boron purification from carbonate and seawater matrices

Funding: This work is supported by the European Research Council under the European Union's Horizon 2020 research and innovation program (Grant 805246) to J.W.B.R., H.J., a Natural Environmental Research Council (NERC)-IAPETUS2 Doctoral Training Programme (DTP) Studentship to NE/S007431/1 C.X., a NERC-IAPETUS DTP Studentship NE/RO12253/1 to M.T., a Leverhulme Trust Early Career Fellowship ECF-2023-199 to H.J., a NERC UK IODP grant NE/P000878/1 to S.B. and S.N., and a Taiwanese MOST Grant 111-2116M-002-032-MY3 to S.N.Boron isotope ratios (δ11B) are used across the Earth Sciences and are increasing analyzed by Multi-Collector Inductively Coupled Plasma Mass Spectrometry (MC-ICPMS). Accurate δ11B MC-ICPMS analysis requires boron purification from the sample matrix using ion-exchange column chromatography. However, the traditional gravity-drip column method is time-consuming and prone to airborne contamination due to its long duration and open resin surface. To address these issues, we designed a novel, simple, and reliable column chromatography technique called “peri-columns.” This method uses a peristaltic pump to generate vacuum on a commonly used column set up. This method uses sealed collection beakers and does not require solutions to pass through pump tubing, minimizing contamination. The duration is reduced by eight-fold, processing 12 samples in just 1.5 hr. It also yields low and consistent total procedural blanks, averaging 11 pg. The efficiency and efficacy of this method were tested by repeated boron purification from calcium carbonate and high-sodium matrices with international and in-house reference materials. The results matched those obtained using the gravity column method and fell within our laboratory long-term and international certified values. The mean δ11B and 2SD (standard deviation) of repeatedly processed NIST 8301f were 14.57 ± 0.26‰ (n = 31), NIST 8301c was 24.19 ± 0.33‰ (n = 10), STAiG-F1 was 16.20 ± 0.26‰ (n = 13), and seawater was 39.52 ± 0.32‰ (n = 10). All the components of our techniques are commercially available, and it is easily adaptable to other laboratories and isotope systems.Publisher PDFPeer reviewe

A record of Neogene seawater δ11B reconstructed from paired δ11B analyses on benthic and planktic foraminifera

The work was supported by NERC grants NE/I006176/1 (Gavin L. Foster and Caroline H. Lear), NE/H006273/1 (Gavin L. Foster), NE/I006168/1 and NE/K014137/1 and a Royal Society Research Merit Award (Paul A. Wilson), a NERC Independent Research Fellowship NE/K00901X/1 (Mathis P. Hain) and a NERC studentship (Rosanna Greenop).The boron isotope composition (δ11B) of foraminiferal calcite reflects the pH and the boron isotope composition of the seawater the foraminifer grew in. For pH reconstructions, the δ11B of seawater must therefore be known, but information on this parameter is limited. Here we reconstruct Neogene seawater δ11B based on the δ11B difference between paired measurements of planktic and benthic foraminifera and an estimate of the coeval water column pH gradient from their δ13C values. Carbon cycle model simulations underscore that the ΔpH-Δδ13C relationship is relatively insensitive to ocean and carbon cycle changes, validating our approach. Our reconstructions suggest that δ11Bsw was ∼37.5‰ during the early and middle Miocene (roughly 23-12 Ma) and rapidly increased during the late Miocene (between 12 and 5 Ma) towards the modern value of 39.61 ‰. Strikingly, this pattern is similar to the evolution of the seawater isotope composition of Mg, Li and Ca, suggesting a common forcing mechanism. Based on the observed direction of change, we hypothesize that an increase in secondary mineral formation during continental weathering affected the isotope composition of riverine input to the ocean since 14 Ma.Publisher PDFPeer reviewe