Redox capacity of rocks and sediments by high temperature chalcometric titration

We present an analytical method to quantify the absolute redox capacity, ΔO2, of geological materials. The protocol consists in a high temperature chalcometric titration by which a known amount of oxygen gas is exchanged between a solid state oxygen donor, CuO, and an oxygen acceptor, the sample, at elevated temper- ature. Calibration of the method using elemental C, native S and magnetite demonstrates that it effectively oxidizes C, S and Fe to their terminal oxidation state, C4+, S6+ and Fe3+, respectively. Because the metric is independent of processes of internal equilibration within the system, it can be used for quantitative assessments of redox fluxes in open geological systems, in the surface or deep Earth. Preliminary results suggest that the mass specific redox capacity, dO2, of geological materials span many orders of magnitude, ranging from less than 500 μmol O2/g for ultramafic rocks and lower crustal amphibolites, to more than 30000 μmol O2/g for black shales. This highlights a counterintuitive yet fundamental characteristic of our planet. Rocks characterized by elevated dO2 values are ubiquitous in the oxic Earth’s surface, while the upper mantle and lower crust are typically composed of rocks with much lower dO2. This work will contribute to provide a more nuanced and complete perspective on the sedimentary and geodynamic processes that have shaped the redox structure of the Earth

Materials and pathways of the organic carbon cycle through time

The cycle of organic carbon through the atmosphere, oceans, continents and mantle reservoirs is a hallmark of Earth. Over geological time, chemical exchanges between those reservoirs have produced a diversity of reduced carbon materials that differ in their molecular structures and reactivity. This reactive complexity challenges the canonical dichotomy between the surface and deep, short-term and long-term organic carbon cycle. Old and refractory carbon materials are not confined to the lithosphere but are ubiquitous in the surface environment, and the lithosphere hosts various forms of reduced carbon that can be very reactive. The biological and geological pathways that drive the organic carbon cycle have changed through time; from a synthesis of these changes, it emerges that although a biosphere is required to produce organic carbon, mortality is required to ensure its export to the lithosphere, and graphitization is essential for its long-term stabilization in the solid Earth. Among the by-products of the organic carbon cycle are the accumulation of a massive lithospheric reservoir of organic carbon, the accumulation of dioxygen in the atmosphere and the rise of a terrestrial biosphere. Besides driving surface weathering reactions, free dioxygen has allowed the evolution of new metabolic pathways to produce and respire organic carbon. From the evolution of photosynthesis until the expansion of biomineralization in the Phanerozoic, inorganic controls on the organic carbon cycle have diversified, tightening the connection between the biosphere and geosphere

Past carbonate preservation events in the deep Southeast Atlantic Ocean (Cape Basin) and their implications for Atlantic overturning dynamics and marine carbon cycling

Micropaleontological and geochemical analyses reveal distinct millennial-scale increases in carbonate preservation in the deep Southeast Atlantic (Cape Basin) during strong and prolonged Greenland interstadials that are superimposed on long-term (orbital-scale) changes in carbonate burial. These data suggest carbonate oversaturation of the deep Atlantic and a strengthened Atlantic Meridional Overturning Circulation (AMOC) during the most intense Greenland interstadials. However, proxy evidence from outside the Cape Basin indicate that AMOC changes also occurred during weaker and shorter Greenland interstadials. Here we revisit the link between AMOC dynamics and carbonate saturation in the deep Cape Basin over the last 400 kyr (sediment cores TN057-21, TN057-10 and ODP Site 1089) by reconstructing centennial changes in carbonate preservation using mm-scale X-ray fluorescence (XRF) scanning data. We observe close agreement between variations in XRF Ca/Ti, sedimentary carbonate content and foraminiferal shell fragmentation, reflecting a common control primarily through changing deep-water carbonate saturation. We suggest that the high-frequency (sub-orbital) component of the XRF Ca/Ti records indicates the fast and recurrent redistribution of carbonate ions in the Atlantic basin via the AMOC during both long/strong- and short/weak North Atlantic climate anomalies. In contrast, the low- frequency (orbital) XRF Ca/Ti component is interpreted to reflect slow adjustments through carbonate compensation, and/or changes in the deep-ocean respired carbon content. Our findings emphasize the recurrent influence of rapid AMOC variations on the marine carbonate system during past glacial periods, providing a mechanism for transferring the impacts of North Atlantic climate anomalies to the global carbon cycle via the Southern Ocean.J.G. acknowledges support from the Swiss National Science Foundation (grant 200021_163003), the German Research Foundation (grant GO 2294/2-1) and the Gates Cambridge Trust. L.C.S. acknowledges the Royal Society, the Cambridge Isaac Newton Trust and NERC grant NE/J010545/1. S.L.J was funded by the Swiss National Science Foundation (grants PP00P2-144811 and PP002_172915)

Complex spatio-temporal structure of the Holocene Thermal Maximum

Inconsistencies between Holocene climate reconstructions and numerical model simulations question the robustness of climate models and proxy temperature records. Climate reconstructions suggest an early-middle Holocene Thermal Maximum (HTM) followed by gradual cooling, whereas climate models indicate continuous warming. This discrepancy either implies seasonal biases in proxy-based climate reconstructions, or that the climate model sensitivity to forcings and feedbacks needs to be reevaluated. Here, we analyze a global database of Holocene paleotemperature records to investigate the spatiotemporal structure of the HTM. Continental proxy records at mid and high latitudes of the Northern Hemisphere portray a “classic” HTM (8–4 ka). In contrast, marine proxy records from the same latitudes reveal an earlier HTM (11–7ka), while a clear temperature anomaly is missing in the tropics. The results indicate a heterogeneous response to climate forcing and highlight the lack of globally synchronous HTM

Persistent non-solar forcing of Holocene storm dynamics in coastal sedimentary archives

Considerable climatic variability on decadal to millennial timescales has been documented for the past 11,500 years of interglacial climate. This variability has been particularly pronounced at a frequency of about 1,500 years, with repeated cold intervals in the North Atlantic. However, there is growing evidence that these oscillations originate from a cluster of different spectral signatures, ranging from a 2,500-year cycle throughout the period to a 1,000-year cycle during the earliest millennia. Here we present a reappraisal of high-energy estuarine and coastal sedimentary records from the southern coast of the English Channel, and report evidence for five distinct periods during the Holocene when storminess was enhanced during the past 6,500 years.We find that high storm activity occurred periodically with a frequency of about 1,500 years, closely related to cold and windy periods diagnosed earlier. We show that millennial-scale storm extremes in northern Europe are phase-locked with the period of internal ocean variability in the North Atlantic of about 1,500 years. However, no consistent correlation emerges between spectral maxima in records of storminess and solar irradiation. We conclude that solar activity changes are unlikely to be a primary forcing mechanism of millennial-scale variability in storminess

Ocean dynamics, not dust, have controlled equatorial Pacific productivity over the past 500,000 years

Biological productivity in the equatorial Pacific is relatively high compared with other low-latitude regimes, especially east of the dateline, where divergence driven by the trade winds brings nutrient-rich waters of the Equatorial Undercurrent to the surface. The equatorial Pacific is one of the three principal high-nutrient low-chlorophyll ocean regimes where biological utilization of nitrate and phosphate is limited, in part, by the availability of iron. Throughout most of the equatorial Pacific, upwelling of water from the Equatorial Undercurrent supplies far more dissolved iron than is delivered by dust, by as much as two orders of magnitude. Nevertheless, recent studies have inferred that the greater supply of dust during ice ages stimulated greater utilization of nutrients within the region of upwelling on the equator, thereby contributing to the sequestration of carbon in the ocean interior. Here we present proxy records for dust and for biological productivity over the past 500 ky at three sites spanning the breadth of the equatorial Pacific Ocean to test the dust fertilization hypothesis. Dust supply peaked under glacial conditions, consistent with previous studies, whereas proxies of export production exhibit maxima during ice age terminations. Temporal decoupling between dust supply and biological productivity indicates that other factors, likely involving ocean dynamics, played a greater role than dust in regulating equatorial Pacific productivity

Deglacial patterns of South Pacific overturning inferred from 231Pa and 230Th

The millennial‐scale variability of the Atlantic Meridional Overturning Circulation (AMOC) is well documented for the last glacial termination and beyond. Despite its importance for the climate system, the evolution of the South Pacific overturning circulation (SPOC) is by far less well understood. A recently published study highlights the potential applicability of the 231Pa/230Th‐proxy in the Pacific. Here, we present five sedimentary down‐core profiles of 231Pa/230Th‐ratios measured on a depth transect from the Pacific sector of the Southern Ocean to test this hypothesis using downcore records. Our data are consistent with an increase in SPOC as early as 20 ka that peaked during Heinrich Stadial 1. The timing indicates that the SPOC did not simply react to AMOC changes via the bipolar seesaw but were triggered via Southern Hemisphere processes