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1. Comparison of δ 13 C analyses of individual foraminifer ( Orbulina universa ) shells by secondary ion mass spectrometry and gas source mass spectrometry

   https://doi.org/10.1002/rcm.9658  

   Wycech, Jody B. ; Kelly, Daniel Clay ; Kozdon, Reinhard ; Ishida, Akizumi ; Kitajima, Kouki ; Spero, Howard J. ; Valley, John W. ( November 2023 , Rapid Communications in Mass Spectrometry)

   The use of secondary ion mass spectrometry (SIMS) to perform micrometer‐scalein situcarbon isotope (δ¹³C) analyses of shells of marine microfossils called planktic foraminifers holds promise to explore calcification and ecological processes. The potential of this technique, however, cannot be realized without comparison to traditional whole‐shell δ¹³C values measured by gas source mass spectrometry (GSMS).

   Paired SIMS and GSMS δ¹³C values measured from final chamber fragments of the same shell of the planktic foraminiferOrbulina universaare compared. The SIMS–GSMS δ¹³C differences (Δ¹³C_SIMS‐GSMS) were determined via paired analysis of hydrogen peroxide‐cleaned fragments of modern cultured specimens and of fossil specimens from deep‐sea sediments that were either untreated, sonicated, and cleaned with hydrogen peroxide or vacuum roasted. After treatment, fragments were analyzed by a CAMECA IMS 1280 SIMS instrument and either a ThermoScientific MAT‐253 or a Fisons Optima isotope ratio mass spectrometer (GSMS).

   Paired analyses of cleaned fragments of cultured specimens (n = 7) yield no SIMS–GSMS δ¹³C difference. However, paired analyses of untreated (n = 18) and cleaned (n = 12) fragments of fossil shells yield average Δ¹³C_SIMS‐GSMSvalues of 0.8‰ and 0.6‰ (±0.2‰, 2 SE), respectively, while vacuum roasting of fossil shell fragments (n = 11) removes the SIMS–GSMS δ¹³C difference.

   The noted Δ¹³C_SIMS‐GSMSvalues are most likely due to matrix effects causing sample–standard mismatch for SIMS analyses but may also be a combination of other factors such as SIMS measurement of chemically bound water. The volume of material analyzed via SIMS is ~10⁵times smaller than that analyzed by GSMS; hence, the extent to which these Δ¹³C_SIMS‐GSMSvalues represent differences in analyte or instrument factors remains unclear.

    

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2. Reconstruction of Past Antarctic Temperature Using Present Seasonal δ18O–Inversion Layer Temperature: Unified Slope Equations and Applications

   https://doi.org/10.1175/JCLI-D-22-0012.1  

   Liu, Z. ; He, C. ; Yan, M. ; Buizert, C. ; Otto-Bliesner, B. L. ; Lu, F. ; Zeng, C. ( May 2023 , Journal of Climate)

   Reconstructing the history of polar temperature from ice core water isotope (δ¹⁸O) calibration has remained a challenge in paleoclimate research, because of our incomplete understanding of various temperature–δ¹⁸O relationships. This paper resolves this classical problem in a new framework called the unified slope equations (USE), which illustrates the general relations among spatial and temporalδ¹⁸O–surface temperature slopes. The USE is applied to the Antarctica temperature change during the last deglaciation in model simulations and observations. It is shown that the comparable Antarctica-mean spatial slope with deglacial temporal slope inδ¹⁸O–surface temperature reconstruction is caused, accidentally, by the compensation responses between theδ¹⁸O–inversion layer temperature relation and the inversion layer temperature itself. Furthermore, in light of the USE, we propose that the present seasonal slope ofδ¹⁸O–inversion layer temperature is an optimal paleothermometer that is more accurate and robust than the spatial slope. This optimal slope suggests the possibility of reconstructing past Antarctic temperature changes using present and future instrumental observations.

   This paper develops a new framework called the unified slope equations (USE) to provide, for the first time, a general relation among various spatial and temporal water isotope–temperature slopes. The application of the USE to Antarctic deglacial temperature change shows that the optimal paleothermometer is the seasonal slope of the inversion layer temperature.

    

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3. Seasonally Variable Aquifer Discharge and Cooler Climate in Bermuda During the Last Interglacial Revealed by Subannual Clumped Isotope Analysis

   https://doi.org/10.1029/2020PA004145  

   Zhang, Jade Z. ; Petersen, Sierra V. ; Winkelstern, Ian Z. ; Lohmann, Kyger C. ( May 2021 , Paleoceanography and Paleoclimatology)

   Faunal analog reconstructions suggest that Last Interglacial (MIS 5e) sea surface temperatures were cooler around Bermuda and in the Caribbean than modern climate. Here we describe new and revised clumped isotope measurements ofCittarium picafossil shells supporting previous findings of cooler than modern temperatures in Bermuda during the Last Interglacial. We resolve temperature and δ¹⁸O_wdifferences between two closely located and apparently coeval sites described in Winkelstern et al. (2017),https://doi.org/10.1002/2016pa003014through reprocessing raw isotopic data with the updated Brand/IUPAC parameters. New subannual‐resolution clumped isotope data reveal large variations in δ¹⁸O_wout of phase with seasonal temperature changes (i.e., lower δ¹⁸O_wvalues in winter). Supported by modern δ¹⁸O_wmeasurements identifying similar processes occurring today, we suggest past variations in coastal δ¹⁸O_wwere driven by seasonally variable freshwater discharge from a subterranean aquifer beneath the island. Taken together, our results emphasize the importance of δ¹⁸O_win controlling carbonate δ¹⁸O, and suggest that typical assumptions of constant δ¹⁸O_wshould be made cautiously in nearshore settings and can contribute to less accurate reconstructions of paleotemperature.

    

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4. Reconstructing Pliocene West Pacific Warm Pool Hydroclimate Using In Situ Microanalyses on Fossil Planktic Foraminifer Shells

   https://doi.org/10.1029/2019PA003772  

   Wycech, J. ; Kelly, D. C. ; Fournelle, J. ; Kitajima, K. ; Kozdon, R. ; Orland, I. J. ( June 2020 , Paleoceanography and Paleoclimatology)

   A controversial aspect of Pliocene (5.3–2.6 Ma) climate is whether El Niño‐like (El Padre) conditions, characterized by a reduced trans‐equatorial sea‐surface temperature (SST) gradient, prevailed across the Pacific. Evidence for El Padre is chiefly based on reconstructions of sea‐surface conditions derived from the oxygen isotope (δ¹⁸O) and Mg/Ca compositions of shells belonging to the planktic foraminiferTrilobatus sacculifer. However, fossil shells of this species are a mixture of multiple carbonate phases—pre‐gametogenic, gametogenic (reproductive), and diagenetic calcites—that formed under different physiological and/or environmental conditions and are averaged in conventional whole‐shell analyses. Through in situ measurements of micrometer‐scale domains within Pliocene‐aged shells ofT. sacculiferfrom Ocean Drilling Program Site 806 in the western equatorial Pacific, we show that the δ¹⁸O of gametogenic calcite is 0.6–0.8‰ higher than pre‐gametogenic calcite, while the Mg/Ca ratios of these two phases are the same. Both the whole‐shell and pre‐gametogenic Mg/Ca records indicate that average early Pliocene SSTs were ~1°C warmer than modern, with present‐day SSTs being established during the latest Pliocene and early Pleistocene (~3.0–2.0 Ma). The measurement of multiple calcite phases by whole‐shell δ¹⁸O analyses masks a late Pliocene to earliest Pleistocene (3.6–2.2 Ma) decrease in seawater δ¹⁸O (δ¹⁸O_sw) values reconstructed from in situ pre‐gametogenic δ¹⁸O and Mg/Ca measurements. Our novel δ¹⁸O_swrecord indicates that sea‐surface salinities in the west Pacific warm pool were higher than modern prior to ~3.5 Ma, which is consistent with more arid conditions under an El Padre state.

    

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5. Variability and Controls on δ 18 O, d‐excess, and ∆′ 17 O in Southern Peruvian Precipitation

   https://doi.org/10.1029/2020JD034009  

   Aron, Phoebe G. ; Poulsen, Christopher J. ; Fiorella, Richard P. ; Levin, Naomi E. ; Acosta, Rene P. ; Yanites, Brian J. ; Cassel, Elizabeth J. ( December 2021 , Journal of Geophysical Research: Atmospheres)

   The isotopic composition of precipitation is used to trace water cycling and climate change, but interpretations of the environmental information recorded in central Andean precipitation isotope ratios are hindered by a lack of multi‐year records, poor spatial distribution of observations, and a predominant focus on Rayleigh distillation. To better understand isotopic variability in central Andean precipitation, we present a three‐year record of semimonthly δ¹⁸O_pand δ²H_pvalues from 15 stations in southern Peru and triple oxygen isotope data, expressed as ∆′¹⁷O_p, from 32 precipitation samples. Consistent with previous work, we find that elevation correlates negatively with δ¹⁸O_pand that seasonal δ¹⁸O_pvariations are related to upstream rainout and local convection. Spatial δ¹⁸O_pvariations and atmospheric back trajectories show that both eastern‐ and western‐derived air masses bring precipitation to southern Peru. Seasonal d‐excess_pcycles record moisture recycling and relative humidity at remote moisture sources, and both d‐excess_pand ∆′¹⁷O_pclearly differentiate evaporated and non‐evaporated samples. These results begin to establish the natural range of unevaporated ∆′¹⁷O_pvalues in the central Andes and set the foundation for future paleoclimate and paleoaltimetry studies in the region. This study highlights the hydrologic understanding that comes from a combination of δ¹⁸O_p, d‐excess_p, and ∆′¹⁷O_pdata and helps identify the evaporation, recycling, and rainout processes that drive water cycling in the central Andes.

    

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