Calcium isotopic composition of high-latitude proxy carrier Neogloboquadrina pachyderma (sin.)

International audienceThe accurate reconstruction of sea surface temperature (SST) history in climate-sensitive regions (e.g. tropical and polar oceans) became a challenging task in palaeoceanographic research. However, biogenic shell carbonate SST proxies successfully developed for tropical regions often fail in cool water environments. Their major regional shortcomings and the cryptic diversity now found within the major high latitude proxy carrier Neogloboquadrina pachyderma (sin.) highlight an urgent need to develop complementary SST proxies for these cool water regions. Here we incorporate the genetic component into a calibration study of a new SST proxy for the high latitudes. We found that the calcium isotopic composition (?44/40Ca) of calcite from genotyped net catches and core-top samples of the planktonic foraminifera Neogloboquadrina pachyderma (sin) is strongly related to temperature and unaffected by genetic variations. The temperature sensitivity has been found to be 0.17 (±0.04)? per 1°C highlighting its potential for downcore applications in open marine cool-water environments. Our results further indicate that however in extreme polar environments, below a critical threshold temperature of 2.0 (±0.5)°C and salinity of 33.0 (±0.5)? a prominent shift in biomineralization affect the Ca isotope composition of N. pachyderma (sin.) becoming insensitive to temperature. These findings highlight the need of systematic calibration studies to unravel the influencing factors on Ca isotope fractionation and to validate the proxies' applicability

Correspondence: No substantial long-term bias in the Cenozoic benthic foraminifera oxygen-isotope record

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Deglacial Variability in Okhotsk Sea Intermediate Water Ventilation and Biogeochemistry: Implications for North Pacific Nutrient Supply and Productivity

Highlights • Multi-proxy, multi-site reconstruction of Okhotsk Sea palaeo-productivity and mid-depth ventilation changes from 8 to 18 ka. • Link between hinterland river discharge and downstream Okhotsk Sea Intermediate Water (OSIW) ventilation/nutrient signatures. • Surplus Fe, Si(OH)4 export in OSIW during Bølling-Allerød to pelagic Pacific supported transient nutrient-replete conditions. • Subarctic and subtropical Pacific gyres disconnected during Bølling-Allerød, with restricted OSIW flow to lower latitudes. • Deglacial OSIW export and mid-depth Pacific biogeochemistry modulate millennial-scale regional CO2 source/sink conditions. The modern North Pacific plays a critical role in marine biogeochemical cycles, as an oceanic sink of CO2 and by bearing some of the most productive and least oxygenated waters of the World Ocean. The capacity to sequester CO2 is limited by efficient nutrient supply to the mixed layer, particularly from deeper water masses in the Pacific's subarctic and marginal seas. The region is in addition only weakly ventilated by North Pacific Intermediate Water (NPIW), which receives its characteristics from Okhotsk Sea Intermediate Water (OSIW). Here, we present reconstructions of intermediate water ventilation and productivity variations in the Okhotsk Sea that cover the last glacial termination between eight and 18 ka, based on a set of high-resolution sediment cores from sites directly downstream of OSIW formation. In a multi-proxy approach, we use total organic carbon (TOC), chlorin, biogenic opal, and CaCO3 concentrations as indicators for biological productivity. C/N ratios and XRF scanning-derived elemental ratios (Si/K and Fe/K), as well as chlorophycean algae counts document changes in Amur freshwater and sediment discharge that condition the OSIW. Stable carbon isotopes of epi- and shallow endobenthic foraminifera, in combination with 14C analyses of benthic and planktic foraminifera imply decreases in OSIW oxygenation during deglacial warm phases from c. 14.7 to 13 ka (Bølling-Allerød) and c. 11.4 to 9 ka (Preboreal). No concomitant decreases in Okhotsk Sea benthic-planktic ventilation ages are observed, in contrast to nearby, but southerly locations on the Japan continental margin. We attribute Okhotsk Sea mid-depth oxygenation decreases in times of enhanced organic matter supply to maxima in remineralization within OSIW, in line with multi-proxy evidence for maxima in primary productivity and supply of organic matter. Sedimentary C/N and Fe/K ratios indicate more effective entrainment of nutrients into OSIW and thus an increased nutrient load of OSIW during deglacial warm periods. Correlation of palynological and sedimentological evidence from our sites with hinterland reference records suggests that millennial-scale changes in OSIW oxygen and nutrient concentrations were largely influenced by fluvial freshwater runoff maxima from the Amur, caused by a deglacial northeastward propagation of the East Asian Summer Monsoon that increased precipitation and temperatures, in conjunction with melting of permafrost in the Amur catchment area. We suggest that OSIW ventilation minima and the high lateral supply of nutrients and organic matter during the Allerød and Preboreal are mechanistically linked to concurrent maxima in nutrient utilization and biological productivity in the subpolar Northwest Pacific. In this scenario, increased export of nutrients from the Okhotsk Sea during deglacial warm phases supported subarctic Pacific shifts from generally Fe-limiting conditions to transient nutrient-replete regimes through enhanced advection of mid-depth nutrient- and Fe-rich OSIW into the upper ocean. This mechanism may have moderated the role of the subarctic Pacific in the deglacial CO2 rise on millennial timescales by combining the upwelling of old carbon-rich waters with a transient delivery of mid-depth-derived bio-available Fe and silicate

Revisiting diagenesis on the Ontong Java Plateau: Evidence for authigenic crust precipitation in Globorotalia tumida

The calcite tests of foraminifera lie in marine sediments for thousands to millions of years, before being analysed to generate trace element and isotope palaeoproxy records. These sediments constitute a distinct physio-chemical environment from the conditions in which the tests formed. Storage in sediments can modify the trace element and isotopic content of foraminiferal calcite through diagenetic alteration, which has the potential to confound their palaeoceanographic interpretation. A previous study of G. tumida from the Ontong Java Plateau, western equatorial Pacific, found that preferential dissolution of higher-Mg chamber calcite, and the preservation of a low-Mg crust on the tests significantly reduced whole-test Mg/Ca and Sr/Ca [Brown and Elderfield, 1996]. Here, we revisit these specimens with a combination of synchrotron X-ray computed tomography (sXCT) and electron probe micro-analyses (EPMA) to re-evaluate the nature of their diagenetic alteration. The dissolution of higher-Mg calcite with depth was directly observed in the sXCT data, confirming the inference of the previous study. The sXCT data further reveal a thickening of the chemically and structurally distinct calcite crust with depth. We propose that these crusts have a diagenetic origin, driven by the simultaneous dissolution of high-Mg chamber calcite and precipitation of low-Mg crust from the resulting modified pore-water solution. While the breadth of the study is limited by the nature of the techniques, the observation of both dissolution and re-precipitation of foraminiferal calcite serves to demonstrate the action of two simultaneous diagenetic alteration processes, with significant impacts on the resulting palaeoproxy signals.The authors would like to acknowledge Aleksey Sadekov, Gerald Langer, India Weidle, Alberto de Fanis, Andrew Bodey, Joan Vila-Comamala and Ulrich Wagner for their help with the project. The work was funded by the Diamond Light Source and by the ERC (2010-NEWLOG ADG-267931 grant to HE).This is the author accepted manuscript. The final version is available from Wiley via http://dx.doi.org/10.1002/2014PA00275

The DeepMIP contribution to PMIP4: methodologies for selection, compilation and analysis of latest Paleocene and early Eocene climate proxy data, incorporating version 0.1 of the DeepMIP database

This is the final version of the article. Available from European Geosciences Union via the DOI in this record.Data availability. The data referenced in this manuscript are provided as Supplement Data Files 1 to 8. In the final version, these files will form DeepMIP database version 0.1 and will be accessible online via a citable DOI reference.The early Eocene (56 to 48 million years ago) is inferred to have been the most recent time that Earth's atmospheric CO2 concentrations exceeded 1000 ppm. Global mean temperatures were also substantially warmer than those of the present day. As such, the study of early Eocene climate provides insight into how a super-warm Earth system behaves and offers an opportunity to evaluate climate models under conditions of high greenhouse gas forcing. The Deep Time Model Intercomparison Project (DeepMIP) is a systematic model–model and model–data intercomparison of three early Paleogene time slices: latest Paleocene, Paleocene–Eocene thermal maximum (PETM) and early Eocene climatic optimum (EECO). A previous article outlined the model experimental design for climate model simulations. In this article, we outline the methodologies to be used for the compilation and analysis of climate proxy data, primarily proxies for temperature and CO2. This paper establishes the protocols for a concerted and coordinated effort to compile the climate proxy records across a wide geographic range. The resulting climate “atlas” will be used to constrain and evaluate climate models for the three selected time intervals and provide insights into the mechanisms that control these warm climate states. We provide version 0.1 of this database, in anticipation that this will be expanded in subsequent publications.Natural Environment Research Council (NERC)GNS Science Global Change through Time ProgrammeNational Science Foundation (NSF)KU Leuve

In situ multiple sulfur isotope analysis by SIMS of pyrite, chalcopyrite, pyrrhotite, and pentlandite to refine magmatic ore genetic models

With growing interest in the application of in situ multiple sulfur isotope analysis to a variety of mineral systems, we report here the development of a suite of sulfur isotope standards for distribution relevant to magmatic, magmatic-hydrothermal, and hydrothermal ore systems. These materials include Sierra pyrite (FeS2), Nifty-b chalcopyrite (CuFeS2), Alexo pyrrhotite (Fe(1 −x)S), and VMSO pentlandite ((Fe,Ni)9S8) that have been chemically characterized by electron microprobe analysis, isotopically characterized for δ33S, δ34S, and δ36S by fluorination gas-source mass spectrometry, and tested for homogeneity at the micro-scale by secondary ion mass spectrometry. Beam-sample interaction as a function of crystallographic orientation is determined to have no effect on δ34S and Δ33S isotopic measurements of pentlandite. These new findings provided the basis for a case study on the genesis of the Long-Victor nickel-sulfide deposit located in the world class Kambalda nickel camp in the southern Kalgoorlie Terrane of Western Australia. Results demonstrate that precise multiple sulfur isotope analyses from magmatic pentlandite, pyrrhotite and chalcopyrite can better constrain genetic models related to ore-forming processes. Data indicate that pentlandite, pyrrhotite and chalcopyrite are in isotopic equilibrium and display similar Δ33S values + 0.2‰.This isotopic equilibrium unequivocally fingerprints the isotopic signature of the magmatic assemblage. The three sulfide phases show slightly variable δ34S values (δ34Schalcopyrite = 2.9 ± 0.3‰, δ34Spentlandite = 3.1 ± 0.2‰, and δ34Spyrrhotite = 3.9 ± 0.5‰), which are indicative of natural fractionation. Careful in situ multiple sulfur isotope analysis of multiple sulfide phases is able to capture the subtle isotopic variability of the magmatic sulfide assemblage, which may help resolve the nature of the ore-forming process. Hence, this SIMS-based approach discriminates the magmatic sulfur isotope signature from that recorded in metamorphic- and alteration-related sulfides, which may not be resolved during bulk rock fluorination analysis. The results indicate that, unlike the giant dunite-hosted komatiite systems that thermo-mechanically assimilated volcanogenic massive sulfides proximal to vents and display negative Δ33S values, the Kambalda ores formed in relatively distal environments assimilating abyssal sulfidic shales

Proxy evidence for state-dependence of climate sensitivity in the Eocene greenhouse

Despite recent advances, the link between the evolution of atmospheric CO2 and climate during the Eocene greenhouse remains uncertain. In particular, modelling studies suggest that in order to achieve the global warmth that characterised the early Eocene, warmer climates must be more sensitive to CO2 forcing than colder climates. Here, we test this assertion in the geological record by combining a new high-resolution boron isotope-based CO2 record with novel estimates of Global Mean Temperature. We find that Equilibrium Climate Sensitivity (ECS) was indeed higher during the warmest intervals of the Eocene, agreeing well with recent model simulations, and declined through the Eocene as global climate cooled. These observations indicate that the canonical IPCC range of ECS (1.5 to 4.5 °C per doubling) is unlikely to be appropriate for high-CO2 warm climates of the past, and the state dependency of ECS may play an increasingly important role in determining the state of future climate as the Earth continues to warm