ALBERT

Description: © The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Dunlea, A. G., Murray, R. W., Tada, R., Alvarez-Zarikian, C. A., Anderson, C. H., Gilli, A., Giosan, L., Gorgas, T., Hennekam, R., Irino, T., Murayama, M., Peterson, L. C., Reichart, G., Seki, A., Zheng, H., & Ziegler, M. Intercomparison of XRF core scanning results from seven labs and approaches to practical calibration. Geochemistry Geophysics Geosystems, 21(9), (2020): e2020GC009248, doi:10.1029/2020GC009248.

Description: X‐ray fluorescence (XRF) scanning of marine sediment has the potential to yield near‐continuous and high‐resolution records of elemental abundances, which are often interpreted as proxies for paleoceanographic processes over different time scales. However, many other variables also affect scanning XRF measurements and convolute the quantitative calibrations of element abundances and comparisons of data from different labs. Extensive interlab comparisons of XRF scanning results and calibrations are essential to resolve ambiguities and to understand the best way to interpret the data produced. For this study, we sent a set of seven marine sediment sections (1.5 m each) to be scanned by seven XRF facilities around the world to compare the outcomes amidst a myriad of factors influencing the results. Results of raw element counts per second (cps) were different between labs, but element ratios were more comparable. Four of the labs also scanned a set of homogenized sediment pellets with compositions determined by inductively coupled plasma‐optical emission spectrometry (ICP‐OES) and ICP‐mass spectrometry (MS) to convert the raw XRF element cps to concentrations in two ways: a linear calibration and a log‐ratio calibration. Although both calibration curves are well fit, the results show that the log‐ratio calibrated data are significantly more comparable between labs than the linearly calibrated data. Smaller‐scale (higher‐resolution) features are often not reproducible between the different scans and should be interpreted with caution. Along with guidance on practical calibrations, our study recommends best practices to increase the quality of information that can be derived from scanning XRF to benefit the field of paleoceanography.

Description: Funding for this research was provided by the U.S. National Science Foundation to R. W. M. (Grant 1130531). USSSP postcruise support was provided to Expedition 346 shipboard participants A. G. D., R. W. M., L. G., C. A. Z., and L. P. Portions of this material are based upon work supported while R. W. M. was serving at the National Science Foundation.

Description: © The Author(s), 2017. This is the author's version of the work. It is posted here under a nonexclusive, irrevocable, paid-up, worldwide license granted to WHOI. It is made available for personal use, not for redistribution. The definitive version was published in Marine Micropaleontology 138 (2018): 90-104, doi:10.1016/j.marmicro.2017.10.002.

Description: Transmission electron microscope (TEM) observation has revealed much about the basic cell biology of foraminifera. Yet, there remains much we do not know about foraminiferal cytology and physiology, especially for smaller benthic foraminifera, which inhabit a wide range of habitats. Recently, some TEM-coupled approaches have been developed to study correlative foraminiferal ecology and physiology in detail: Fluorescently Labeled Embedded Core (FLEC)-TEM for observing foraminiferal life-position together with their cytoplasmic ultrastructure, micro-X-ray computed tomography (CT)-TEM for observing and reconstructing foraminiferal cytoplasm in three dimensions (3D), and TEM-Nanometer-scale secondary ion mass spectrometry (NanoSIMS) for mapping of elemental and isotopic compositions at sub-micrometer resolutions with known ultrastructure. In this contribution, we review and illustrate these recent advances of TEM-coupled methods.

Description: This work was financially supported by the Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology, Japan (Scientific Research (C) grant number 17K05697 to HN) and the Swiss National Science Foundation (grant no. 200021_149333). JMB’s contributions were funded by US NSF grants OCE-0551001 and OCE-1634469, the WHOI Robert W. Morse Chair for Excellence in Oceanography, and The Investment in Science Fund at WHOI. The micro-X-ray CT imaging was performed under the cooperative research program of Center for Advanced Marine Core Research (CMCR), Kochi University (accept No. 17A021).

Description: We present monthly resolved records of strontium/calcium (Sr/Ca) and oxygen isotope (d18O) ratios from well-preserved fossil corals drilled during the Integrated Ocean Drilling Program (IODP) Expedition 310 'Tahiti Sea Level' and reconstruct sea surface conditions in the central tropical South Pacific Ocean during two time windows of the last deglaciation. The two Tahiti corals examined here are uranium/thorium (U/Th)-dated at 12.4 and 14.2 ka, which correspond to the Younger Dryas (YD) cold reversal and the Bølling-Allerød (B-A) warming of the Northern Hemisphere, respectively. The coral Sr/Ca records indicate that annual average sea surface temperature (SST) was 2.6-3.1 °C lower at 12.4 ka and 1.0-1.6 °C lower at 14.2 ka relative to the present, with no significant changes in the amplitude of the seasonal SST cycle. These cooler conditions were accompanied by seawater d18O (d18Osw) values higher by ~0.8 per mill and ~0.6 per mill relative to the present at 12.4 and 14.2 ka, respectively, implying more saline conditions in the surface waters. Along with previously published coral Sr/Ca records from the island [Cohen and Hart (2004), Deglacial sea surface temperatures of the western tropical Pacific: A new look at old coral. Paleoceanography 19, PA4031, doi:10.1029/2004PA001084], our new Tahiti coral records suggest that a shift toward lower SST by ~1.5 °C occurred from 13.1 to 12.4 ka, which was probably associated with a shift toward higher d18Osw by ~0.2 per mill. Along with a previously published coral Sr/Ca record from Vanuatu [Corrège et al. (2004), Interdecadal variation in the extent of South Pacific tropical waters during the Younger Dyras event. Nature 428, 927-929], the Tahiti coral records provide new evidence for a pronounced cooling of the western to central tropical South Pacific during the Northern Hemisphere YD event.

Description: Suborbital climate variability during the last glacial period is suggested to have involved a 1500-year pacing cycle, but the expression and spatial distribution of the ~1500-year oscillation during interglacials remains unclear. We generated a multidecade resolution record of alkenone sea surface temperature (SST) in the northwestern Pacific off central Japan during the Holocene. The SST record showed centennial and millennial variability with an amplitude of ~1 °C throughout the entire Holocene. Spectral analysis for SST variation revealed a statistically significant peak with 1470-year periodicity. The SST variation partly correlated with the variations of ice-rafted hematite-stained grain content in North Atlantic sediments. These findings indicate that the mean latitude of the Kuroshio Extension has varied on a 1500-year cycle, and suggest that a climatic link exists between the North Pacific gyre system and the high-latitude North Atlantic thermohaline circulation. The regular pacing at 1500-year intervals seen throughout both the Holocene and the last glacial period suggests that the oscillation was a response to external forcing.

Description: Various biomarkers (n-alkanes, n-alcohols, and sterols) have been studied in a piston core TSP-2PC taken from the Southern Ocean to reconstruct the paleoenvironmental changes in the subantarctic region for the last two deglaciations. Mass accumulation rates of terrestrial (higher molecular weight n-alkanes and n-alcohols) and marine (dinosterol and brassicasterol) biomarkers increased significantly at the last two glacials and stayed low during interglacial peaks (early Holocene and the Eemian). These records indicate that the enhanced atmospheric transport of continental materials and the increased marine biological productivity were synchronously linked in the Southern Ocean at the last two glacials. This suggests that increased glacial dust inputs have relieved iron limitation in the subantarctic Southern Ocean. These two processes, however, were not linked at the cooling phase from the Eemian to marine isotope stage (MIS) 5d. During this period, paleoproductivity may have been influenced by the latitudinal migration of the high-production zone associated with the Antarctic Polar Front.

Description: Here we provide extensive micropaleontological and geochemical dataset of shallow-marine deposits that includes palynology and palynomorph component, carbonate fine-fraction stable-isotope, benthic foraminiferal stable-isotope, X-ray fluorescence (XRF), and glycerol dialkyl glycerol tetraether (GDGT) data. Samples were originally collected from the Mossy Grove core, nearby Jackson, central Mississippi, US Gulf Coastal Plain, between August 19, 1991 and September 5, 1991 (Dockery III et al., 1991). The dataset was generated between October 2015 and June 2019 and covers the latest Eocene and earliest Oligocene (~37.5-33.1 million years ago). These data were intended to yield unique multi-proxy records of the critical Eocene-Oligocene Transition, the most prominent climate event in the last 100 million years of Earth's history. Methods for age model, palynology and palynomorph component, carbonate fine-fraction stable-isotope, benthic foraminiferal stable-isotope, X-ray fluorescence (XRF), and glycerol dialkyl glycerol tetraether (GDGT) data follow De Lira Mota et al. (in review).

Description: Elemental composition of the sediment core was determined using two XRF techniques. 2,098 samples on the original core section were directly analyzed at a resolution of ~1.2 cm across the interval 17.1-109.4 m with a hand-held XRF analyzer at the core store of the Mississippi Department of Environmental Quality, in Jackson, Mississippi. A further 179 samples were collected every 20-30 cm downcore, spanning the interval 106.8-151.6 m, and were subsequently finely ground and dried before analysis as pressed powders in wax pellets. Pellets were analyzed with a Bruker S8 TIGER XRF spectrometer with an 8 min analysis time, at the School of Chemistry, University of Birmingham. We selected the (Al+Fe+K+Ti)/Ca ratio as a paleoenvironmental indicator of terrigenous-derived versus marine planktonic carbonate sediment 79,80. The two methodologies were cross-calibrated over an interval of overlap between 106.8 and 109.4 m, with a total of ~80 samples, spanning a range of compositions, cross-correlated from both analysis methods.

Description: Samples were processed for GDGTs at the Birmingham Molecular Climatology Laboratory, University of Birmingham. Lipids were extracted from ~10-15 g of homogenized sediment by ultrasonic extraction using dichloromethane (DCM):methanol (3:1). The total lipid extract was fractionated by silica gel chromatography using n-hexane, n-hexane:DCM (2:1), DCM, and methanol to produce four separate fractions, the last of which contained the GDGTs. Procedural blanks were also analyzed to ensure the absence of laboratory contaminants. Samples were filtered using hexane:isopropanol (99:1) through a 0.4 µm PTFE filter (Alltech part 2395), before being dried under a continuous stream of N2. Samples were then sent to the University of Bristol for analysis by LC-APCI-MS. HPLC-APCI-MS analyses were conducted at the National Environmental Isotope Facility, Organic Geochemistry Unit, School of Chemistry, University of Bristol, with a ThermoFisher Scientific Accela Quantum Access triple quadrupole MS in selected ion monitoring (SIM) mode. Normal phase separation was achieved using two ultra-high performance silica columns (Acquity UPLC BEH HILIC columns, 50 mm × ID 2.1 mm × 1.7 µm, 130 Å; Waters) were fitted with a 2.1 mm × 5 mm guard cartridge after Hopmans et al. (2016). The HPLC pump was operated at a flow rate of 200 µL min-1. GDGT determinations were based on single injections. A 15 µL aliquot was injected via an autosampler, with analyte separation performed under a gradient elution. The initial solvent hexane:iso-propanol (IPA) (98.2:1.8 v/v) eluted isocratically for 25 min, followed by an increase in solvent polarity to 3.5 % IPA in 25 min, and then by a sharp increase to 10 % IPA in 30 min (Hopmans et al., 2016). A 45 min washout period was applied between injections, whereby the column was flushed by injecting 25 µL hexane:isopropanol (99:1 v/v). GDGT peaks were integrated manually using Xcalibur software. In-house generated standard solutions were measured daily to assess system performance. One peat standard was run in a sequence for every 10 samples and integrated in the same way as the unknowns. Selected ion monitoring (SIM) was used to monitor abundance of the [M+H] + ion of the different GDGTs instead of full-scan acquisition in order to improve the signal-to-noise ratio and therefore yield higher sensitivity and reproducibility. SIM parameters were set to detect the protonated molecules of isoprenoid and branched GDGTs using the m/z (Schoon et al., 2013). The majority of sediments were found to contain a full range of both isoprenoid and branched GDGTs. Sea surface temperature (SST) estimations from GDGT assemblages are show based on two methodologies: the BAYSPAR Bayesian regression model of Tierney and Tingley (2014, 2015) using the 'analogue' version for deep-time applications; and, the OPTiMAL Gaussian process model of Dunkley Jones et al. (2020). When plotting BAYSPAR SSTs we distinguish samples with BIT indices greater than and less than 0.4, as high BIT can be associated with a small warm bias (Weijers et al., 2006). For the OPTiMAL model we apply its own internal screening criteria that quantifies the extent that fossil GDGT assemblages are non-analogue relative to the modern calibration data, using the Dnearest criteria with a cut-off value of 0.5. All but one pre-NIE GDGT assemblages have Dnearest values that exceed 0.5, whereas eight samples above this level have values less than 0.5.Only OPTiMAL SST data that pass the Dnearest screening criteria are shown.