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.
Evidence is emerging that the tropical climate system played a major role in global climate change during the last deglaciation. However, existing studies show that deglacial warming was asynchronous across the tropical band, complicating the identification of causal mechanisms. The Orca Basin in the northern Gulf of Mexico is ideally located to record subtropical Atlantic sea-surface temperature (SST) warming in relation to meltwater input from the Laurentide Ice Sheet. Paired ␦ 18 O and Mg/Ca data on the planktonic foraminifer Globigerinoides ruber from core EN32-PC6 are used to separate deglacial changes in SST and ␦ 18 O of seawater. SST as calculated from Mg/Ca data increased by Ͼ3 ؇C from ca. 17.2 to 15.5 ka in association with Heinrich event 1 and was not in phase with Greenland air temperature. Subtracting temperature effects from ␦ 18 O values in G. ruber reveals two excursions representing Laurentide meltwater input to the Gulf of Mexico, one of Ͼ1.5‰ from ca. 16.1 to 15.6 ka and a second major spike of Ͼ2.5‰ from ca. 15.2 to 13.0 ka that encompassed meltwater pulse 1A and peaked ca. 13.8 ka during the Bølling-Å llerød. Conversion to salinity through the use of a Laurentide meltwater end member of ؊25‰ indicates that near-surface salinity decreased by 2‰-4‰ during these spikes. These results suggest that Gulf of Mexico SST warming preceded peak Laurentide Ice Sheet decay and the Bølling-Å llerød interval by Ͼ2 k.y. and that heat was retained in the subtropical Atlantic during Heinrich event 1, consistent with modulation of deglacial climate by thermohaline circulation.
Abstract. Foraminiferal magnesium shows increasing promise as a paleothermometer, but the accuracy and precision are limited by biases introduced by partial dissolution, salinity variations, Mg-rich gametogenic calcite, and contaminant phases. We improved cleaning methods and reduced errors introduced by partial dissolution by sampling from well-preserved cores in the equatorial Atlantic and the Caribbean Sea with different dissolution histories. All cores reveal a synchronous 25% increase in Mg/Ca from the stage 2/3 boundary to the Holocene core top, indicating that dissolution is not a controlling factor. Modern temperatures estimated from core top Mg/Ca are 24.5ø-25.0øC, equal to mean annual water temperatures at 50-100 m. We estimate that sea surface temperature increased by 2.6øC (+1.3) from the last glacial maximum to the Holocene. Holocene values were comparable to those during isotope stage 5e. Our data indicate that biases from contaminant p•ses and partial dissolution can be reduced. This paleothermometer holds promise if uncertainties introduced by salinity variations and gametogenic calcite can be constrained.
The Deepwater Horizon (DWH) spill released 4.9 million barrels of oil into the Gulf of Mexico (GoM) over 87 days. Sediment and water sampling efforts were concentrated SW of the DWH and in coastal areas. Here we present geochemistry data from sediment cores collected in the aftermath of the DWH event from 1000 – 1500 m water depth in the DeSoto Canyon, NE of the DWH wellhead. Cores were analyzed at high-resolution (at 2 mm and 5 mm intervals) in order to evaluate the concentration, composition and input of hydrocarbons to the seafloor. Specifically, we analyzed total organic carbon (TOC), aliphatic, polycyclic aromatic hydrocarbon (PAHs), and biomarker (hopanes, steranes, diasteranes) compounds to elucidate possible sources and transport pathways for deposition of hydrocarbons. Results showed higher hydrocarbon concentrations during 2010-2011 compared to years prior to 2010. Hydrocarbon inputs in 2010-2011 were composed of a mixture of sources including terrestrial, planktonic, and weathered oil. Our results suggest that after the DWH event, both soluble and highly insoluble hydrocarbons were deposited at enhanced rates in the deep-sea. We proposed two distinct transport pathways of hydrocarbon deposition: 1) sinking of oil-particle aggregates (hydrocarbon-contaminated marine snow and/or suspended particulate material), and 2) advective transport and direct contact of the deep plume with the continental slope surface sediments between 1000-1200 m. Our findings underline the complexity of the depositional event observed in the aftermath of the DWH event in terms of multiple sources, variable concentrations, and spatial (depth-related) variability in the DeSoto Canyon, NE of the DWH wellhead.
The objective of this study was to investigate the impacts of the Deepwater Horizon (DWH) oil discharge at the seafloor as recorded in bottom sediments of the DeSoto Canyon region in the northeastern Gulf of Mexico. Through a close coupling of sedimentological, geochemical, and biological approaches, multiple independent lines of evidence from 11 sites sampled in November/December 2010 revealed that the upper ~1 cm depth interval is distinct from underlying sediments and results indicate that particles originated at the sea surface. Consistent dissimilarities in grain size over the surficial ~1 cm of sediments correspond to excess 234Th depths, which indicates a lack of vertical mixing (bioturbation), suggesting the entire layer was deposited within a 4–5 month period. Further, a time series from four deep-sea sites sampled up to three additional times over the following two years revealed that excess 234Th depths, accumulation rates, and 234Th inventories decreased rapidly, within a few to several months after initial coring. The interpretation of a rapid sedimentation pulse is corroborated by stratification in solid phase Mn, which is linked to diagenesis and redox change, and the dramatic decrease in benthic formanifera density that was recorded in surficial sediments. Results are consistent with a brief depositional pulse that was also reported in previous studies of sediments, and marine snow formation in surface waters closer to the wellhead during the summer and fall of 2010. Although sediment input from the Mississippi River and advective transport may influence sedimentation on the seafloor in the DeSoto Canyon region, we conclude based on multidisciplinary evidence that the sedimentation pulse in late 2010 is the product of marine snow formation and is likely linked to the DWH discharge.
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