L. D. Pena

Interlaboratory comparison study of calibration standards for foraminiferal Mg/Ca thermometry

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.

Identification and removal of Mn‐Mg‐rich contaminant phases on foraminiferal tests: Implications for Mg/Ca past temperature reconstructions

[1] The geochemical composition of foraminifera shells from an Ocean Drilling Program site in the Panama Basin has been analyzed by several analytical techniques (LA-ICP-MS, ICP-MS, XRD, SEM, EDX) in order to identify and evaluate the occurrence of contaminant phases which may bias paleoenvironmental reconstructions. LA-ICP-MS results on uncleaned tests indicate the presence of MnMg-rich contaminant phases at the inner surfaces of the foraminiferal shells (which have Mn/Ca ratios up to 400 mmol mol 1 and Mg/Ca ratios up to 50 mmol mol 1 ). We have rigorously assessed the ability of different cleaning protocols to remove these contaminant phases and have obtained satisfactory results only when a reductive step is included. The analysis of cleaning residuals collected after each of the different cleaning steps applied reveals that high Mn values are associated with at least two different contaminant phases, of which only one is linked to high Mg values. XRD analysis further reveals that the Mn-Mg-rich phase is the Ca-Mn-Mg carbonate kutnahorite (Ca(Mn, Mg)(CO3)2). Our results demonstrate that the presence of kutnahorite-like minerals can bias Mg/Ca ratios toward higher values (by 7–36%) and lead to significant overestimation of past seawater temperatures (by 0.9 up to 6.2� C, in the case of these Panama Basin samples). Components: 11,867 words, 13 figures, 3 tables.

El Niño–Southern Oscillation–like variability during glacial terminations and interlatitudinal teleconnections

Interannual-decadal variability in the equatorial Pacific El Nino–Southern Oscillation (ENSO) induces climate changes at global scale, but its potential influence during past global climate change is not yet well constrained. New high-resolution eastern equatorial Pacific proxy records of thermocline conditions present new evidence of strong orbital control in ENSO-like variability over the last 275,000 years. Recurrent intervals of saltier thermocline waters are associated with the dominance of La Nina–like conditions during glacial terminations, coinciding with periods of low precession and high obliquity. The parallel dominance of δ 13C-depleted waters supports the advection of Antarctic origin waters toward the tropical thermocline. This “oceanic tunneling” is proposed to have reinforced orbitally induced changes in ENSO-like variability, composing a complex high- and low-latitude feedback during glacial terminations.

Enhanced carbon pump inferred from relaxation of nutrient limitation in the glacial ocean

The modern Eastern Equatorial Pacific (EEP) Ocean is a large oceanic source of carbon to the atmosphere. Primary productivity over large areas of the EEP is limited by silicic acid and iron availability, and because of this constraint the organic carbon export to the deep ocean is unable to compensate for the outgassing of carbon dioxide that occurs through upwelling of deep waters. It has been suggested that the delivery of dust-borne iron to the glacial ocean could have increased primary productivity and enhanced deep-sea carbon export in this region, lowering atmospheric carbon dioxide concentrations during glacial periods. Such a role for the EEP is supported by higher organic carbon burial rates documented in underlying glacial sediments, but lower opal accumulation rates cast doubts on the importance of the EEP as an oceanic region for significant glacial carbon dioxide drawdown. Here we present a new silicon isotope record that suggests the paradoxical decline in opal accumulation rate in the glacial EEP results from a decrease in the silicon to carbon uptake ratio of diatoms under conditions of increased iron availability from enhanced dust input. Consequently, our study supports the idea of an invigorated biological pump in this region during the last glacial period that could have contributed to glacial carbon dioxide drawdown. Additionally, using evidence from silicon and nitrogen isotope changes, we infer that, in contrast to the modern situation, the biological productivity in this region is not constrained by the availability of iron, silicon and nitrogen during the glacial period. We hypothesize that an invigorated biological carbon dioxide pump constrained perhaps only by phosphorus limitation was a more common occurrence in low-latitude areas of the glacial ocean.

Characterization of contaminant phases in foraminifera carbonates by electron microprobe mapping

The advent of new microanalytical techniques such as electron microprobe mapping (EMP) and laser ablation microsamplers coupled to mass spectrometers (LA-ICP-MS) provides a new array of possibilities to explore in great detail the trace elements distribution in foraminiferal carbonates. Here we apply these techniques to characterize diagenetic phases present in foraminiferal shells from Ocean Drilling Program Site 1240 in the Panama Basin, a region characterized by the presence of manganese-rich minerals in the sediments. The combined application of these techniques allows us to characterize the elemental and spatial distribution on the surface and across the foraminiferal shells. Results illustrate the presence of at least two different Mn-rich contaminant phases in the foraminiferal carbonates: Mn-rich carbonates and ferromanganese oxides. Elemental maps also highlight the relevance of the foraminifera shell texture and porosity in the distribution and formation of these contaminant phases. In the case of Neogloboquadrina dutertrei, Mn phases form a continuous thin layer in the inner part of the chambers, whereas for Globigerinoides ruber, Mn phases have a rather patchy distribution and are usually found within the pores. Significant high magnesium concentrations are always associated with these Mn-rich phases. These new findings support the need of removing these Mn-rich contaminant phases in order to measure accurately the Mg/Ca ratios in the foraminifera shell and therefore obtain reliable Mg/Ca paleotemperature reconstructions.