[1] The various cleaning steps required for preparation of foraminiferal samples for Mg/Ca (and Sr/Ca) analysis are evaluated for their relative importance and effects on measured elemental ratios. It is shown that the removal of silicate contamination is the most important step for the measurement of Mg/Ca ratios. In an example, bulk sample Mg/Ca decreases from 10.5 to 2.5 mmol mol À1 during clay removal. Oxidation of organic material causes a lowering of sample Mg/Ca in the order of 10% or approximately 1°C when converted to temperature. Use of dilute acid leaching to remove adsorbed contaminants causes partial dissolution of the sample carbonate and a corresponding decrease in Mg/Ca. Reductive treatment also causes dissolution of the sample and a decrease in the Mg/Ca ratio of up to 10-15%. Sample preparation for Sr/Ca analysis does not require the same degree of rigor as is necessary for Mg/Ca work. The ''within-run'' reproducibility of the method described here for G. ruber in a core-top sample from the Arabian Sea was ±1.8% (mean sample ratio was 4.72 mmol mol
À1). When converted to temperature, this becomes 28 ± 0.2°C. The equivalent result for Sr/Ca was ±0.5% (mean ratio = 1.44 mmol mol À1 ).Components: 9070 words, 10 figures.
Earth's climate underwent a fundamental change between 1250 and 700 thousand years ago, the mid-Pleistocene transition (MPT), when the dominant periodicity of climate cycles changed from 41 thousand to 100 thousand years in the absence of substantial change in orbital forcing. Over this time, an increase occurred in the amplitude of change of deep-ocean foraminiferal oxygen isotopic ratios, traditionally interpreted as defining the main rhythm of ice ages although containing large effects of changes in deep-ocean temperature. We have separated the effects of decreasing temperature and increasing global ice volume on oxygen isotope ratios. Our results suggest that the MPT was initiated by an abrupt increase in Antarctic ice volume 900 thousand years ago. We see no evidence of a pattern of gradual cooling, but near-freezing temperatures occur at every glacial maximum.
[1] Abstract: An inductively coupled plasma-atomic emission spectroscopy (ICP-AES) method for the accurate and precise simultaneous measurement of the Mg/Ca and Sr/Ca content of carbonates was established. While a precision of <0.3% (1s standard deviation (SD)) is easily obtainable for both Mg/ Ca and Sr/Ca analysis, a Ca matrix effect complicates achieving similar levels of accuracy with conventional calibration procedures. An alternative ratio calibration procedure is proposed which overcomes the Ca matrix effects and ensures the accuracy of the Mg/Ca and Sr/Ca analysis of marine carbonates to <0.3%, almost an order of magnitude better than conventional calibration methods. The longer-term precision is <0.1% if the batch run average values are corrected for longer-term drift. The method is suitable for analysis of foraminiferal calcite and coral aragonite and can easily be adjusted for the analysis of other carbonates or microsamples.
International audience[1] Thirteen laboratories from the USA and Europe participated in an intercomparison study of Mg/Ca and Sr/Ca measurements in foraminifera. The study included five planktonic species from surface sediments from different geographical regions and water depths. Each of the laboratories followed their own cleaning and analytical procedures and had no specific information about the samples. Analysis of solutions of known Mg/Ca and Sr/Ca ratios showed that the intralaboratory instrumental precision is better than 0.5% for both Mg/Ca and Sr/Ca measurements, regardless whether ICP-OES or ICP-MS is used. The interlaboratory precision on the analysis of standard solutions was about 1.5% and 0.9% for Mg/Ca and Sr/Ca measurements, respectively. These are equivalent to Mg/Ca-based temperature repeatability and reproducibility on the analysis of solutions of +/- 0.2 degreesC and +/- 0.5 degreesC, respectively. The analysis of foraminifera suggests an interlaboratory variance of about +/-8% (%RSD) for Mg/Ca measurements, which translates to reproducibility of about +/- 2 - 3 degreesC. The relatively large range in the reproducibility of foraminiferal analysis is primarily due to relatively poor intralaboratory repeatability (about +/- 1 - 2 degreesC) and a bias (about 1 degreesC) due to the application of different cleaning methods by different laboratories. Improving the consistency of cleaning methods among laboratories will, therefore, likely lead to better reproducibility. Even more importantly, the results of this study highlight the need for standards calibration among laboratories as a first step toward improving interlaboratory compatibility
An interlaboratory study of Mg/Ca and Sr/Ca ratios in three commercially available carbonate reference materials (BAM RS3, CMSI 1767, and ECRM 752‐1) was performed with the participation of 25 laboratories that determine foraminiferal Mg/Ca ratios worldwide. These reference materials containing Mg/Ca in the range of foraminiferal calcite (0.8 mmol/mol to 6 mmol/mol) were circulated with a dissolution protocol for analysis. Participants were asked to make replicate dissolutions of the powdered samples and to analyze them using the instruments and calibration standards routinely used in their laboratories. Statistical analysis was performed in accordance with the International Standardization Organization standard 5725, which is based on the analysis of variance (ANOVA) technique. Repeatability (RSDr%), an indicator of intralaboratory precision, for Mg/Ca determinations in solutions after centrifuging increased with decreasing Mg/Ca, ranging from 0.78% at Mg/Ca = 5.56 mmol/mol to 1.15% at Mg/Ca = 0.79 mmol/mol. Reproducibility (RSDR%), an indicator of the interlaboratory method precision, for Mg/Ca determinations in centrifuged solutions was noticeably worse than repeatability, ranging from 4.5% at Mg/Ca = 5.56 mmol/mol to 8.7% at Mg/Ca = 0.79 mmol/mol. Results of this study show that interlaboratory variability is dominated by inconsistencies among instrument calibrations and highlight the need to improve interlaboratory compatibility. Additionally, the study confirmed the suitability of these solid standards as reference materials for foraminiferal Mg/Ca (and Sr/Ca) determinations, provided that appropriate procedures are adopted to minimize and to monitor possible contamination from silicate mineral phases.
[1] A method has been developed for rapid and precise simultaneous determination of nine element/Ca ratios in foraminiferal tests directly from intensity ratios using external, matrix-matched standards on a quadrupole inductively coupled plasma-mass spectrometer (ICP-MS). All quantification isotopes are determined in pulse mode to avoid cross-calibration. Small argide ( Zn are corrected by using two additional Mg and Zn standards. A stable signal, conducive for high-precision measurements, is obtained by cone conditioning. Variable calcium concentration has negligible effect on Li, Al, Mn, and Sr, but Ca concentrations for standards and samples need to be constrained at a similar level for precise measurements of Zn, Cd, and U. Aliquots of samples are first analyzed for Ca concentrations on an inductively coupled plasma-atomic emission spectrometer (ICP-AES), and the remaining solutions are diluted to Ca concentration of 100 ppm for ratio measurements to assure data quality. The long-term reproducibility of the method yielded precisions of Li/Ca = 2.4%, B/Ca = 4.2%, Mg/Ca = 1.4%, Al/Ca = 14%, Mn/Ca = 0.9%, Zn/Ca = 2.8% (1.2$7.8 mmol/mol) and 5.1% (0.5$1.2 mmol/mol), Sr/Ca = 0.9%, Cd/Ca = 2.4% (0.07$0.24 mmol/mol) and 4.8% (0.01$0.07 mmol/mol), and U/Ca = 2.5% for foraminiferal samples as small as 60 mg.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.