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Circulation changes have been suggested to play an important role in the sequestration of atmospheric CO2 in the glacial ocean. However, previous studies have resulted in contradictory results regarding the strength of the Atlantic Meridional Overturning Circulation (AMOC) and three-dimensional, quantitative reconstructions of the glacial ocean constrained by multiple proxies remain scarce. Here we simulate the modern and glacial ocean using a coupled physical-biogeochemical, global, three-dimensional model constrained simultaneously by δ 13 C, radiocarbon, and δ 15 N to explore the effects of AMOC differences and Southern Ocean iron fertilization on the distributions of these isotopes and ocean carbon storage. We show that δ 13 C and radiocarbon data sparsely sampled at the locations of existing glacial sediment cores can be used to reconstruct the modern AMOC accurately. Applying this method to the glacial ocean we find that a surprisingly weak (6–9 Sv or about half of today's) and shallow AMOC maximizes carbon storage and best reproduces the sediment isotope data. Increasing the atmospheric soluble iron flux in the model's Southern Ocean intensifies export production, carbon storage, and further improves agreement with δ 13 C and δ 15 N reconstructions. Our best fitting simulation is a significant improvement compared with previous studies, and suggests that both circulation and export production changes were necessary to maximize carbon storage in the glacial ocean.

We use LA-ICP-MS depth profiling to explore the sensitivity of shell chemistry of the symbiotic planktic foraminifer Orbulina universa to diurnal changes in the holobiont physiology, over a wide range of seawater pH and DIC compositions. B/Ca and U/Ca vary in concert with diurnal Mg/Ca banding, forming compositional bands that are qualitatively consistent with physiological modification of seawater carbonate chemistry (pH, [ B ( OH ) 4 − / H CO 3 − ] and [ CO 3 2 − ]) within the foraminiferal microenvironment by the net effects of photosynthesis, respiration and calcification. The amplitude of B/Ca banding broadly conforms to banding predicted using the bulk-shell B/Ca sensitivity to the carbonate chemistry changes in the foraminiferal microenvironment. U/Ca banding tends to be greater than predicted using the published bulk-shell sensitivity of this proxy to carbonate chemistry. This either suggests that carbonate chemistry changes in the foraminiferal microenvironment are greater than predicted by modeling and/or the published bulk shell calibration does not accurately reflect the U/Ca sensitivity at the micro-scale. A fourfold increase in seawater DIC composition (1026 to 4019 μmol kg −1 ) is associated with significant increases in Sr/Ca and Mg/Ca partitioning, and a decrease in Mn/Ca partitioning into shell calcite. The accompanying fourfold increase in calcite saturation produces only a twofold increase in calcification rate (0.14 to 0.28, ±0.02 μm hr −1 ), suggesting that seawater carbonate chemistry exerts only a small effect on foraminiferal calcification rates, but does have a significant influence on trace element incorporation at both the inter-shell and bulk-shell scale.

Knowledge of the geometry and strength of the deep overturning circulation is central to the understanding of past climate variability on glacial–interglacial (G–I) timescales. In this study, neodymium (Nd) isotopic ratios on planktonic foraminifera are used to reconstruct the water mass source and mixing history of intermediate and deep water in the Southeast (SE) Atlantic and Southwest (SW) Pacific over the past 200 kyr from five sediment cores. Nd isotopes from a depth transect of cores in the SE Atlantic displayed a stronger geochemical gradient around 3.5 km at the LGM, with higher εNd values of ∼−6.0 below that boundary than those of ∼−7.8 above. In contrast, a similar εNd value (∼−9.5) is observed at both the intermediate and abyssal depths in the Holocene. The glacial upper ocean is 1.8 εNd units less radiogenic than the lower ocean, reflecting an increase in the amount of North Atlantic Component Water (NACW) in the upper SE Atlantic. A coherent Nd isotope change was observed in the SE Atlantic and SW Pacific intermediate and deep water with major excursion to more radiogenic εNd values during Marine Isotope Stage (MIS) 2, 4 and 6. This suggests the flux of NACW to the Southern Ocean was reduced during cold marine stages, possibly accompanied by changes in the water mass geometry. The constant 2 εNd-unit offset between intermediate water in the SE Atlantic and SW Pacific suggests the persistent propagation of less radiogenic NACW to the upper Pacific Ocean over the last glacial cycle. Moreover, the larger glacial vertical εNd gradients between the intermediate and deep waters in both the SE Atlantic and SW Pacific indicate a decreased proportion of NACW entrainment into the deep oceans, consistent with studies proposing reduced mixing between the upper and lower meridional overturning cells.

Cryptic sulfur cycling is an enigmatic process in which sulfate is reduced to some lower-valence state sulfur species and subsequently quantitatively reoxidized; the rate and microbial energetics of this process and how prevalent it may be in the environment remain controversial. Here we investigate sulfur cycling in salt marsh sediments from Norfolk, England where we observe high ferrous iron concentrations with no depletion of sulfate or change in the sulfur isotope ratio of that sulfate, but a 5‰ increase in the oxygen isotope ratio in sulfate, indicating that sulfate has been through a reductive cycle replacing its oxygen atoms. This cryptic sulfur cycle was replicated in laboratory incubations using 18O-enriched water, demonstrating that the field results do not solely result from mixing processes in the natural environment. Numerical modeling of the laboratory incubations scaled to represent the salt marsh sediments suggests that the uptake rate of sulfate during this cryptic sulfur cycling is similar to the uptake rate of sulfate during the fastest microbial sulfate reduction that has been measured in the natural environment. The difference is that during cryptic sulfur cycling, all of the sulfur is subsequently reoxidized to sulfate. We discuss mechanisms for this pathway of sulfur cycling including the possible link to the subsurface iron cycle.

The deep Pacific Ocean holds the largest oceanic reservoir of carbon which may interchange with the atmosphere on climatologically important timescales. The circulation of the deep Pacific during the Last Glacial Maximum (LGM), however, is not well understood. Neodymium (Nd) isotopes of ferromanganese oxide coatings precipitated on planktonic foraminifera are a valuable proxy for deep ocean water mass reconstruction in paleoceanography. In this study, we present Nd isotope compositions ( e Nd ) of planktonic foraminifera for the Holocene and the LGM obtained from 55 new sites widely distributed in the Pacific Ocean. The Holocene planktonic foraminiferal e Nd results agree with the proximal seawater data, indicating that they provide a reliable record of modern bottom water Nd isotopes in the deep Pacific. There is a good correlation between foraminiferal e Nd and seawater phosphate concentrations ( R 2 = 0.80 ), but poorer correlation with silicate ( R 2 = 0.37 ). Our interpretation is that the radiogenic Nd isotope is added to the deep open Pacific through particle release from the upper ocean during deep water mass advection and aging. The data thus also imply the Nd isotopes in the Pacific are not likely to be controlled by silicate cycling. In the North Pacific, the glacial Nd isotopic compositions are similar to the Holocene values, indicating that the Nd isotope composition of North Pacific Deep Water (NPDW) remained constant (−3.5 to −4). During the LGM, the southwest Pacific cores throughout the water column show higher e Nd corroborating previous studies which suggested a reduced inflow of North Atlantic Deep Water to the Pacific. However, the western equatorial Pacific deep water does not record a corresponding radiogenic excursion, implying reduced radiogenic boundary inputs during the LGM probably due to a shorter duration of seawater–particle interaction in a stronger glacial deep boundary current. A significant negative glacial e Nd excursion is evident in mid-depth (1–2 km) cores of the eastern equatorial Pacific (EEP) which may suggest a stronger influence of NPDW return flow to the core sites and decreased local input in the EEP. Taken together, our Nd records do not support a dynamically slower glacial Pacific overturning circulation, and imply that the increased carbon inventory of Pacific deep water might be due to poor high latitude air–sea exchange and increased biological pump efficiency in glacial times.

Reconstruction of intermediate water properties is important for understanding feedbacks within the ocean-climate system, particularly since these water masses are capable of driving high–low latitude teleconnections. Nevertheless, information about intermediate water mass evolution through the late Pleistocene remains limited. This paper examines changes in Antarctic Intermediate Water (AAIW), the most extensive intermediate water mass in the modern ocean through the last 400 kyr using the stable isotopic composition (δ18O and δ13C) and trace element concentration (Mg/Ca and B/Ca) of two benthic foraminiferal species from the same samples: epifaunal Planulina wuellerstorfi and infaunal Uvigerina peregrina. Our results confirm that the most reasonable estimates of AAIW temperature and Δ[CO2−3] are generated by Mg/CaU. peregrina and B/CaP. wuellerstorfi, respectively. We present a 400 kyr record of intermediate water temperature and Δ[CO2−3] from a sediment core from the Southwest Pacific (DSDP site 593; 40°30′S, 167°41′E, 1068 m water depth), which lies within the core of modern AAIW. Our results suggest that a combination of geochemical analyses on both infaunal and epifaunal benthic foraminiferal species yields important information about this critical water mass through the late Pleistocene. When combined with two nearby records of water properties from deeper depths, our data demonstrate that during interglacial stages of the late Pleistocene, AAIW and Circumpolar Deep Water (CPDW) have more similar water mass properties (temperature and δ13C), while glacial stages are typified by dissimilar properties between AAIW and CPDW in the Southwest Pacific. Our new Δ[CO2−3] record shows short time-scale variations, but a lack of coherent glacial–interglacial variability indicating that large quantities of carbon were not stored in intermediate waters during recent glacial periods.

It has been proposed that the rapid rise of atmospheric CO2 across the last deglaciation was driven by the release of carbon from an extremely radiocarbon-depleted abyssal ocean reservoir that was ‘vented’ to the atmosphere primarily via the deep- and intermediate overturning loops in the Southern Ocean. While some radiocarbon observations from the intermediate ocean appear to confirm this hypothesis, others appear to refute it. Here we use radiocarbon measurements in paired benthic- and planktonic foraminifera to reconstruct the benthic–planktonic 14C age offset (i.e. ‘ventilation age’) of intermediate waters in the western equatorial Atlantic. Our results show clear increases in local radiocarbon-based ventilation ages during Heinrich-Stadial 1 (HS1) and the Younger Dryas (YD). These are found to coincide with opposite changes of similar magnitude observed in the Pacific, demonstrating a ‘seesaw’ in the ventilation of the intermediate Atlantic and Pacific Oceans that numerical model simulations of North Atlantic overturning collapse indicate was primarily driven by North Pacific overturning. We propose that this Atlantic–Pacific ventilation seesaw would have combined with a previously identified North Atlantic–Southern Ocean ventilation seesaw to enhance ocean–atmosphere CO2 exchange during a ‘collapse’ of the North Atlantic deep overturning limb. Whereas previous work has emphasized a more passive role for intermediate waters in deglacial climate change (merely conveying changes originating in the Southern Ocean) we suggest instead that the intermediate water seesaw played a more active role via relatively subtle but globally coordinated changes in ocean dynamics that may have further influenced ocean–atmosphere carbon exchange.

The longevity of submarine plumes generated at sea-floor hydrothermal systems constrains the hydrothermal input of chemical species into the deep-ocean. Decades of observations of episodic “event plumes” suggest that a key process governing the dynamics of an hydrothermal cloud spreading out laterally from a buoyant rising plume is the production of internal layering. Here, we use analog experiments on turbulent, hot particle-laden plumes and clouds to show that this layering occurs where particle diffusive convection driven by the differential diffusion of heat and small mineral precipitates gives rise to a large scale double diffusive instability. Where hydrothermal clouds are enriched in fine minerals, this “particle diffusive convection” can extend the longevity of an event plume to 2 yr after its emplacement. The very long residence time imposed by diffusive convective effects enables complete dissolution of fine sulfide and sulfate minerals. We develop a new theoretical model that includes both sedimentation and dissolution processes to quantify the potential amount of iron produced by the dissolution of iron-sulfide minerals settling through the cloud by diffusive convection. A key prediction is that the concentration of dissolved iron in hydrothermal clouds can reach up to 19±3 nM19±3 nM, which represents about 5% of the global hydrothermal discharge. If these results are representative of all hydrothermal vent fields, hydrothermal systems could provide 75% of the global budget of dissolved iron in the deep-ocean. Regionally, this flux is expected to scale in magnitude with mid-ocean ridge heat flow, consistent with observations and global ocean models.

We report here the results of a multi-proxy study to reconstruct surface water pCO2 concentrations in the northern Arabian Sea. Our results show that [delta]11B and Mg/Ca measurements of the planktonic foraminifer Globigerinoides sacculifer yield consistent pCO2 values with those reconstructed from the [delta]13C of alkenones when used in conjunction with foraminifera [delta]13C and Cd/Ca values. They reveal that this area of the oceans has been a constant source of CO2 to the atmosphere during the interval 5-29 ka, and that the intensity of this source was greatest between 11 and 17 ka, when atmospheric CO2 levels were rising rapidly. We interpret our data as reflecting variation in the strength of the Asian Summer Monsoon (ASM), thus indicating that the strength of the ASM varied in phase with summer insolation over the Tibetan plateau between 5 and 29 ka. In contrast to a previous study (Clemens and Prell, 2003), we observe no significant lag between the rise in insolation and the response of the ASM. Rather, our data support a recent study by Rohling et al. (2009) that northern hemisphere climatic forcing factors play a greater role in controlling the intensity of the ASM during times of intense monsoon activity, and that the southern hemisphere forcing is more important during times of weak monsoons.

The Mg/Ca ratio of foraminiferal calcite is a widely accepted and applied empirical proxy for ocean temperature. The analysis of foraminifera preserved in ocean sediments has been instrumental in developing our understanding of global climate, but the mechanisms behind the proxy are largely unknown. Analogies have been drawn to the inorganic precipitation of calcite, where the endothermic substitution of Mg for Ca is favoured at higher temperatures. However, evidence suggests that foraminiferal Mg incorporation may be more complex: foraminiferal magnesium is highly heterogeneous at the sub-micron scale, and high Mg areas coincide with elevated concentrations of organic molecules, Na, S and other trace elements. Fundamentally, the incorporation mode of Mg in foraminifera is unknown. Here we show that Mg is uniformly substituted for Ca within the calcite mineral lattice. The consistency of Mg-specific X-ray spectra gathered from nano-scale regions across the shell (‘test’) reveals that the coordination of Mg is uniform. The similarity of these spectra to that produced by dolomite shows that Mg is present in an octahedral coordination, ideally substituted for Ca in a calcite crystal structure. This demonstrates that Mg is heterogeneous in concentration, but not in structure. The degree of this uniformity implies the action of a continuous Mg incorporation mechanism, and therefore calcification mechanism, across these compositional bands in foraminifera. This constitutes a fundamental step towards a mechanistic understanding of foraminiferal calcification processes and the incorporation of calcite-bound palaeoenvironment proxies, such as Mg.

An oxygen isotope record of biogenic carbonate from paleolake Riwasa in northwestern (NW) India provides a history of the Indian Summer Monsoon (ISM) from ∼11 to 6 kyr B.P. The lake was dry throughout the Late Glacial period when aeolian sands were deposited. Lacustrine sedimentation commenced in the early Holocene and the lake deepened significantly at ∼9.4 kyr B.P., indicating a strengthening of the ISM in response to summer insolation forcing. This high lake stand was interrupted by an abrupt desiccation, which is marked by a 12-cm limestone hardground that formed during a period of sub-aerial exposure after ∼8.3 kyr B.P. The base of the hardground surface coincides with the beginning of the ‘8.2-kyr B.P. cooling event’ in the North Atlantic that has been associated with a glacial outburst flood and slowdown of Atlantic meridional overturning circulation. The hardground provides robust evidence of a weakening of the ISM on the Indian subcontinent at ∼8.2 kyr B.P., and supports previous results of a strong teleconnection between monsoon Asia and North Atlantic climate. Lacustrine sedimentation resumed at ∼7.9 kyr B.P. suggesting the 8.2-kyr desiccation of paleolake Riwasa represented an abrupt response of the ISM to forcing from the North Atlantic.