Jeroen Groeneveld

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.

Assessing the effect of dissolution on planktonic foraminiferal Mg/Ca ratios: Evidence from Caribbean core tops

In order to assess the dissolution effect on foraminiferal Mg/Ca ratios, we analyzed Mg/Ca of seven planktonic foraminiferal species and four of their varieties from Caribbean core tops from ∼900–4700 m water depth. Depending on the foraminiferal species and variety, Mg/Ca start to decline linearly below Δ[CO32−] levels of ∼18–26 μmol/kg by ∼0.04–0.11 mmol/mol per 1 μmol/kg Δ[CO32−], similar to decreases of ∼0.5–0.8 mmol/mol per kilometer below ∼2500–3000 m water depth. Above these species-specific critical levels, Mg/Ca remains stable with higher intraspecific Mg/Ca variability than below. We developed routines to correct Mg/Ca from below these critical thresholds for dissolution effects, which reduce the overall intraspecific variability by ∼24–64%, and provide dissolution-corrected Mg/Ca appropriate to calculate Holocene paleotemperatures. When taking into account only dissolution-unaffected Mg/Ca from <2000 m, the systematic succession of foraminiferal species according to their Mg/Ca reflects expected calcification depths.

Early Pliocene increase in thermohaline overturning : a precondition for the development of the modern equatorial Pacific cold tongue

Unraveling the processes responsible for Earth’s climate transition from an “El Nino–like state” during the warm early Pliocene into a modern‐like “La Nina–dominated state” currently challenges the scientific community. Recently, the Pliocene climate switch has been linked to oceanic thermocline shoaling at ∼3 million years ago along with Earth’s final transition into a bipolar icehouse world. Here we present Pliocene proxy data and climate model results, which suggest an earlier timing of the Pliocene climate switch and a different chain of forcing mechanisms. We show that the increase in North Atlantic meridional overturning circulation between 4.8 and 4.0 million years ago, initiated by the progressive closure of the Central American Seaway, triggered overall shoaling of the tropical thermocline. This preconditioned the turnaround from a warm eastern equatorial Pacific to the modern equatorial cold tongue state about 1 million years earlier than previously assumed. Since ∼3.6–3.5 million years ago, the intensification of Northern Hemisphere glaciation resulted in a strengthening of the trade winds, thereby amplifying upwelling and biogenic productivity at low latitudes.

Changes in Caribbean surface hydrography during the Pliocene shoaling of the Central American Seaway

Pliocene d18O records of shallow and deep dwelling planktonic foraminifers from the Caribbean (Ocean Drilling Program sites 999 and 1000), the tropical east Pacific (sites 1241 and 851), and the Atlantic (site 925, Ceara Rise, and site 1006, western Great Bahama Bank) were used to examine Atlantic-Caribbean-Pacific atmospheric and oceanic linkages associated with the progressive closure of the Central American Seaway (5.5–3 Ma). Comparisons indicate the development of an inner-Caribbean salinity gradient in the mixed layer and salinity changes on precessional periodicities after 4.4 Ma (site 1000), when the Pacific-Caribbean throughflow became significantly restricted. The high-amplitude variability in salinity is also observed at site 1006, monitoring the Caribbean outflow into the Atlantic. Comparisons of Caribbean and Atlantic planktonic d18O records suggest the North Atlantic subtropical gyre as a major source for high-salinity surface waters. Precession-induced variations in the volume transport of Pacific surface water masses through the Panamanian Seaway are considered a main factor to explain the Caribbean salinity minima. Results from a coupled climate model point to changes in the El Nin˜o–Southern Oscillation state as a potential trigger for changes in the amount of Pacific inflow into the Caribbean.

Northern Hemisphere Glaciation during the Globally Warm Early Late Pliocene

The early Late Pliocene (3.6 to ∼3.0 million years ago) is the last extended interval in Earths history when atmospheric CO2 concentrations were comparable to todays and global climate was warmer. Yet a severe global glaciation during marine isotope stage (MIS) M2 interrupted this phase of global warmth ∼3.30 million years ago, and is seen as a premature attempt of the climate system to establish an ice-age world. Here we propose a conceptual model for the glaciation and deglaciation of MIS M2 based on geochemical and palynological records from five marine sediment cores along a Caribbean to eastern North Atlantic transect. Our records show that increased Pacific-to-Atlantic flow via the Central American Seaway weakened the North Atlantic Current and attendant northward heat transport prior to MIS M2. The consequent cooling of the northern high latitude oceans permitted expansion of the continental ice sheets during MIS M2, despite near-modern atmospheric CO2 concentrations. Sea level drop during this glaciation halted the inflow of Pacific water to the Atlantic via the Central American Seaway, allowing the build-up of a Caribbean Warm Pool. Once this warm pool was large enough, the Gulf Stream–North Atlantic Current system was reinvigorated, leading to significant northward heat transport that terminated the glaciation. Before and after MIS M2, heat transport via the North Atlantic Current was crucial in maintaining warm climates comparable to those predicted for the end of this century.

Foraminiferal Mg/Ca increase in the Caribbean during the Pliocene: Western Atlantic Warm Pool formation, salinity influence, or diagenetic overprint?

We constructed a high-resolution Mg/Ca record on the planktonic foraminifer Globigerinoides sacculifer in order to explore the change in sea surface temperature (SST) due to the shoaling of the Isthmus of Panama as well as the impact of secondary factors like diagenesis and large salinity fluctuations. The study covers the latest Miocene and the early Pliocene (5.6–3.9 Ma) and was combined with δ18O to isolate changes in sea surface salinity (SSS). Before 4.5 Ma, SSTMg/Ca and SSS show moderate fluctuations, indicating a free exchange of surface ocean water masses between the Pacific and the Atlantic. The increase in δ18O after 4.5 Ma represents increasing salinities in the Caribbean due to the progressive closure of the Panamanian Gateway. The increase in Mg/Ca toward values of maximum 7 mmol/mol suggests that secondary influences have played a significant role. Evidence of crystalline overgrowths on the foraminiferal tests in correlation with aragonite, Sr/Ca, and productivity cyclicities indicates a diagenetic overprint on the foraminiferal tests. Laser ablation inductively coupled plasma–mass spectrometry analyses, however, do not show significantly increased Mg/Ca ratios in the crystalline overgrowths, and neither do calculations based on pore water data conclusively result in significantly elevated Mg/Ca ratios in the crystalline overgrowths. Alternatively, the elevated Mg/Ca ratios might have been caused by salinity as the δ18O record of Site 1000 has been interpreted to represent large fluctuations in SSS, and cultivating experiments have shown an increase in Mg/Ca with increasing salinity. We conclude that the Mg/Ca record <4.5 Ma can only reliably be considered for paleoceanographical purposes when the minimum values, not showing any evidence of secondary influences, are used, resulting in a warming of central Caribbean surface water masses after 4.5 Ma of ∼2°C.

Reconstructing the southern South China Sea upper water column structure since the Last Glacial Maximum: Implications for the East Asian winter monsoon development

difference in the stable oxygen isotopes (Dd 18 O) and Mg/Ca‐based temperatures (DT) of surface‐dwelling (G. ruber) and thermocline‐dwelling (P. obliquiloculata) planktonic foraminifera and the temperature difference between alkenone‐ and P. obliquiloculata Mg/Ca‐based temperatures to estimate the upper ocean thermal gradient at International Marine Past Global Change Study (IMAGES) core MD01‐2390. Estimates of the upper ocean thermal gradient were used to reconstruct mixed layer dynamics. We find that our Dd 18 O estimates are biased by changes in salinity and, thus, do not display a true upper ocean thermal gradient. The D To fG. ruber and P. obliquiloculata as well as the alkenone and P. obliquiloculata suggest increased surface water mixing during the late glacial, likely due to enhanced EAWM winds. Surface water mixing was weaker during the late Holocene, indicating a weaker influence of winter monsoon winds. The weakest winter monsoon activity occurred between 6.5 ka and 2.5 ka. Inferred EAWM changes since the Last Glacial Maximum coincide with EAWM changes as recorded in Chinese loess sediments. We find that the intensity of the EAWM and the East Asian summer monsoon show an inverse behavior during the last glacial and deglaciation but covaried during the middle to late Holocene.

Pleistocene variability of the Subtropical Convergence at East Tasman Plateau: Evidence from planktonic foraminiferal Mg/Ca (ODP Site 1172A)

Combined measurements of Mg/Ca and stable oxygen isotopes in tests of the planktonic foraminifer G. bulloides from Ocean Drilling Program (ODP) Site 1172A (East Tasman Plateau) allowed us to reconstruct sea surface temperature (SSTMg/Ca), sea surface salinity (SSS), and hence variations in the Subtropical Convergence (STC) in the southwestern Tasman Sea over the last four major glacial-interglacial changes. During interglacials the commonly enhanced SSTMg/Ca and SSS correspond to a lowered marine productivity and a lowered terrigenous flux, implying that the STC separating cool, high-nutrient Subantarctic Surface Water from warm, saline, oligotrophic Subtropical Surface Water and hence the band of zonal westerlies responsible for the eolian dust flux were located south of East Tasman Plateau. The warm East Australian Current was well established during warm periods and propagated far south. During glacial times, SSTMg/Ca and SSS were lower, while both marine productivity and eolian flux increased. Such conditions prevailed during glacial Marine Isotope Stages MIS 12, MIS 10, and to a lesser degree MIS 6 and implied the extended northward influence of Subantarctic SurfaceWater and a shift of the STC to <44�S. The overall climatic signal at Site 1172A appears to be largely attenuated when compared to published climate records from comparable latitudes to the west and to the east. SSTMg/Ca amplitudes were more pronounced in the subantarctic Indian Ocean and at Chatham Rise. They exhibit a consistent pattern suggesting that latitudinal shifts of the STC occurred synchronously in the subantarctic Indian Ocean and at Chatham Rise but were largely damped at East Tasman Plateau due to the influence of the East Australian Current.

Modern and late Pleistocene B/Ca ratios of the benthic foraminifer Planulina wuellerstorfi determined with laser ablation ICP-MS

Incorporation of boron into foraminiferal shells is thought to be primarily governed by the carbonate chemistry of the ambient seawater, suggesting that it can be reconstructed from B/Ca ratios. To this end, B/Ca ratios of the benthic foraminifer Planulina wuellerstorfi from South Atlantic core top samples have been analyzed using laser ablation−inductively coupled plasma−mass spectroscopy (LA-ICP-MS) to provide additional information on intratest trace element heterogeneity. Results show that boron is heterogeneously distributed within and between shells, with content variations of approximately ±43% displayed within a single shell. B/Ca is higher in the youngest chambers, opposite to the observed between-chamber variability of Mg/Ca. This may be explained by ontogenetic changes of physiological processes that increase the pH of the calcifying fluid and thus the borate concentration while decreasing Mg/Ca to promote calcification. Despite this heterogeneity, mean B/Ca ratios are positively correlated with the deepwater calcite saturation state (Δ[CO32–]), in line with previous studies. We apply this empirical relationship to reconstruct Δ[CO32–] for the late Pleistocene to Holocene using samples from a depth transect in the equatorial Atlantic. Reconstructed Δ[CO32–] values confirm previous studies suggesting that CaCO3-oversaturated North Atlantic Deep Water was reduced during glacial periods, whereas CaCO3-undersaturated Antarctic Bottom Water expanded vertically and propagated northwards. In summary, our data demonstrate that bulk B/Ca in P. wuellerstorfi reliably reflects variations in Δ[CO32–], despite the strong physiological control of boron incorporation.

South Atlantic interocean exchange as the trigger for the Bølling warm event

The North Atlantic Ocean underwent an abrupt temperature increase of 9 °C at high latitudes within a couple of decades during the transition from Heinrich event 1 (H1) to the Bolling warm event, but the mechanism responsible for this warming remains uncertain. Here we address this issue, presenting high-resolution last deglaciation planktic and benthic foraminiferal records of temperature and oxygen isotopic composition of seawater (δ 18 Osw) for the subtropical South Atlantic. We identify a warming of ~6.5 °C and an increase in δ 18 O sw of 1.2‰ at the permanent thermocline during the transition, and a simultaneous warming of ~3.5 °C with no significant change in δ 18 O sw at intermediate depths. Most of the warming can be explained by tilting the South Atlantic east-west isopycnals from a flattened toward a steepened position associated with a collapsed (H1) and strong (Bolling) Atlantic meridional overturning circulation (AMOC). However, this zonal seesaw explains an increase of just 0.3‰ in permanent thermocline δ 18 O sw . Considering that δ 18 O sw at the South Atlantic permanent thermocline is strongly influenced by the inflow of salty Indian Ocean upper waters, we suggest that a strengthening in the Agulhas leakage took place at the transition from H1 to the Bolling, and was responsible for the change in δ 18 O sw recorded in our site. Our records high-light the important role played by Indian-Atlantic interocean exchange as the trigger for the resumption of the AMOC and the Bolling warm event.