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Throughout Earth's history, CO2 is thought to have exerted a fundamental control on environmental change. Here we review and revise CO2 reconstructions from boron isotopes in carbonates and carbon isotopes in organic matter over the Cenozoic—the past 66 million years. We find close coupling between CO2 and climate throughout the Cenozoic, with peak CO2 levels of ∼1,500 ppm in the Eocene greenhouse, decreasing to ∼500 ppm in the Miocene, and falling further into the ice age world of the Plio–Pleistocene. Around two-thirds of Cenozoic CO2 drawdown is explained by an increase in the ratio of ocean alkalinity to dissolved inorganic carbon, likely linked to a change in the balance of weathering to outgassing, with the remaining one-third due to changing ocean temperature and major ion composition. Earth system climate sensitivity is explored and may vary between different time intervals. The Cenozoic CO2 record highlights the truly geological scale of anthropogenic CO2 change: Current CO2 levels were last seen around 3 million years ago, and major cuts in emissions are required to prevent a return to the CO2 levels of the Miocene or Eocene in the coming century. ▪ CO2 reconstructions over the past 66 Myr from boron isotopes and alkenones are reviewed and re-evaluated. ▪ CO2 estimates from the different proxies show close agreement, yielding a consistent picture of the evolution of the ocean-atmosphere CO2 system over the Cenozoic. ▪ CO2 and climate are coupled throughout the past 66 Myr, providing broad constraints on Earth system climate sensitivity. ▪ Twenty-first-century carbon emissions have the potential to return CO2 to levels not seen since the much warmer climates of Earth's distant past.

Funding was provided by an Antarctic Bursary awarded to J.A.S., ERC and NERC grants awarded to L.F.R. (278705, NE/S001743/1, NE/R005117/1) and L.F.R. and J.W.B.R. (NE/N003861/1). The Antarctic Cold Reversal (ACR; 14.7 to 13 thousand years ago; ka) phase of the last deglaciation saw a pause in the rise of atmospheric CO2 and Antarctic temperature, that contrasted with warming in the North. A re-expansion of sea ice and a northward shift in the position of the westerly winds in the Southern Ocean are well-documented, but the response of deep-sea biota and the primary drivers of habitat viability remain unclear. Here we present a new perspective on ecological changes in the deglacial Southern Ocean, including multi-faunal benthic assemblage (foraminifera and cold-water corals) and coral geochemical data (Ba/Ca and δ11B) from the Drake Passage. Our records show that, during the ACR, peak abundances of thick-walled benthic foraminifera Uvigerina bifurcata and corals are observed at shallow depths in the sub-Antarctic (∼300 m), while coral populations at greater depths and further south diminished. Our ecological and geochemical data indicate that habitat shifts were dictated by (i) a northward migration of food supply (primary production) into the Subantarctic Zone and (ii) poorly oxygenated seawater at depth during this Antarctic cooling interval. Publisher PDF

The ∼74 ka Toba eruption was one of the largest volcanic events of the Quaternary. There is much interest in determining the impact of such a large event, particularly on the climate and hominid populations at the time. Although the Toba eruption has been identified in both land and marine archives as the Youngest Toba Tuff, its precise place in the ice core record is ambiguous. Several volcanic sulfate signals have been identified in both Antarctic and Greenland ice cores and span the Toba eruption 40Ar/39Ar age uncertainty. Here, we measure sulfur isotope compositions in Antarctic ice samples from the Dome C (EDC) and Dronning Maud Land (EDML) ice cores at high temporal resolution across 11 of these potential Toba sulfate peaks to identify candidates with sulfur mass-independent fractionation (S-MIF), indicative of an eruption whose plume reached altitudes at or above the stratospheric ozone layer. Using this method, we identify several candidate sulfate peaks that contain stratospheric sulfur. We further narrow down potential candidates based on the isotope signatures by identifying sulfate peaks that are due to a volcanic event at tropical latitudes. In one of these sulfate peaks at 73.67 ka, we find the largest ever reported magnitude of S-MIF in volcanic sulfate in polar ice, with a Δ33S value of −4.75 ‰. As there is a positive correlation between the magnitude of the S-MIF signal recorded in ice cores and eruptive plume height, this could be a likely candidate for the Toba super-eruption, with a plume top height in excess of 45 km. These results support the 73.7±0.3 ka (1σ) 40Ar/39Ar age estimate for the eruption, with ice core ages of our candidates with the largest magnitude S-MIF at 73.67 and 73.74 ka. Finally, since these candidate eruptions occurred on the transition into Greenland Stadial 20, the relative timing suggests that Toba was not the trigger for the large Northern Hemisphere cooling at this time although we cannot rule out an amplifying effect.

This work was supported bythe Korea Ministry of Science and ICT (GP2020-038), by the Korea Ministry of Oceans and Fisheries (NP2011-040 and 1525011795), and by the Korea Polar Research Institute (Grants No. PE20350). W.-L.H. acknowledges the supports from the ArcticSGD, a project supported by the Norway Grants and the EEA Grants (2019/34/H/ST10/00645). Additional funds were contributed by the AWI Research Program PACES-II Workpackage 3.1 and 3.2. The response of Arctic Ocean biogeochemistry to subsurface flow driven by permafrost thaw is poorly understood. We present dissolved chloride and water isotopic data from the Chukchi Sea Shelf sediments that reveal the presence of a meteoric subsurface flow enriched in cations with a radiogenic Sr fingerprint. This subsurface fluid is also enriched in dissolved inorganic carbon and methane that bear isotopic compositions indicative of a carbon reservoir modified by reactions in a closed system. Such fluid characteristics are in stark contrast with those from other sites in the Chukchi Sea where the pore water composition shows no sign of meteoric input, but reflect typical biogeochemical reactions associated with early diagenetic sequences in marine sediment. The most likely source of the observed subsurface flow at the Chukchi Sea Shelf is from the degradation of permafrost that had extended to the shelf region during the Last Glacial Maximum. Our data suggest that the permafrost-driven subsurface flow most likely took place during the 2-3 oC warming in the Early Holocene Thermal Maximum (EHTM). This time scale is supported by numerical simulation of pore fluid profiles, which indicate that a minimum of several thousand years must have passed since the cessation of the subsurface methane-bearing fluid flow. Publisher PDF

Cruise MSM57-1/-2 was funded by the German Research Foundation ( DFG ), the Research Center/Excellence Cluster “The Ocean in the Earth System” at MARUM–Center for Marine and Environmental Sciences, University of Bremen and funds from CAGE. This work is partly supported by the Research Council of Norway (RCN) through Petromaks2-NORCRUST (project number 255150 ) and the Centre of Excellence funding scheme for CAGE (project number 223259 ). APF’s contribution was part of the SEAMSTRESS project supported by starting grants from the Tromsø Research Foundation and the Research Council of Norway (grant nr. 2878659 ). Seafloor seepage sites along the Vestnesa Ridge off west-Svalbard have been, for decades, a natural laboratory for the studies of fluid flow and gas hydrate dynamics along passive continental margins. The lack of ground truth evidence for fluid composition and gas hydrate abundance deep in the sediment sequence however prohibits us from further assessing the current model of pockmark evolution from the region. A MARUM-MeBo 70 drilling cruise in 2016 aims to advance our understanding of the system by recovering sediments tens of meters below seafloor from two active pockmarks along Vestnesa Ridge. We report pore fluid composition data focusing on dissolved chloride, stable isotopes of water (δ18O and δD), and the isotopic composition of dissolved boron (δ11B). From one of the seepage sites, we detect a saline formation water with two layers where gas hydrates were recovered. This saline formation pore fluid is characterized by elevated chloride concentrations (up to 616 mM), high B/Cl ratios (9 × 10−4 mol/mol), high δ18O and δD isotopic signatures (+0.6‰ and +3.8‰, respectively) and low δ11B signatures (+35.0‰), which collectively hint to a high temperature modification at great depths. Based on the dissolved chloride concentration profiles, we estimated up to 47% of pore space occupied by gas hydrate in the sediments shallower than 11.5 mbsf. The observation of bubble fabric in the recovered gas hydrates suggests formation during past periods of intensive gaseous methane seepage. The presence of these gas hydrates without associated positive anomalies in dissolved chloride concentrations however suggests that the decomposition of gas hydrate is as fast as its formation. Such a state of gas hydrates can be attributed to a relatively low methane supply transported by the saline formation water at present. Our findings based on pore fluid composition corroborate previous inferences along Vestnesa Ridge that fluids sustaining seepage have migrated from great depths and that the variable gaseous and aqueous phases through the gas hydrate stability zone control the distributions of authigenic carbonates and gas hydrates. Publisher PDF

A conservative element in seawater, uranium is readily incorporated into the aragonitic skeletons of scleractinian corals, making them an important paleoclimate archive that can be absolutely dated with U-Th techniques. In addition, uranium concentrations (U/Ca ratios) in corals have been suggested to be influenced by the temperature and/or carbonate ion concentration of the ambient seawater based on empirical calibrations. Microsampling techniques have revealed strong heterogeneities in U/Ca within individual specimens in both surface and deep-sea corals, suggesting a biological control on the U incorporation into the skeletons. Here we further explore the mechanism of uranium incorporation in coral skeletons with the deep-sea species Desmophyllum dianthus, an ideal test organism for the biomineralization processes due to its relatively constant growth environment. We find a negative correlation between bulk coral U/Ca and temperature as well as ambient pH and [CO32–] that is consistent with previous studies. By sampling the growth bands of individual corals, we also find a twofold change in U/Ca within individual corals that is strongly correlated with the δ18O, δ13C, and other Me/Ca ratios of the bands. A similar correlation between U/Ca and stable isotopes as well as other Me/Ca ratios are observed in bulk deep-sea coral samples. With a numerical coral calcification model, we interpret the U/Ca-stable isotope correlation as a result of changes in uranium speciation in response to internal pH elevations in the extracellular calcifying fluid (ECF) of the corals, and suggest that the Ca2UO2(CO3)3(aq) complex, the dominant U species in seawater, may be the major species incorporated into the coral skeleton. Therefore, the correlation between U/Ca and ambient [CO32–] is likely a result of the response of the biomineralization process, especially the magnitude of internal pH elevation, to the growth environment of the corals. Our data suggest overall lower alkalinity pump rates in corals from low saturation seawater compared to those from high saturation seawater, and possible increases in Ca2+ supply from active pumping relative to seawater transport in response to the environmental stress of low saturation.

Enhanced overturning circulation in the glacial North Pacific caused warming, nutrient limitation, and lower atmospheric CO2., Although the Pacific Ocean is a major reservoir of heat and CO2, and thus an important component of the global climate system, its circulation under different climatic conditions is poorly understood. Here, we present evidence that during the Last Glacial Maximum (LGM), the North Pacific was better ventilated at intermediate depths and had surface waters with lower nutrients, higher salinity, and warmer temperatures compared to today. Modeling shows that this pattern is well explained by enhanced Pacific meridional overturning circulation (PMOC), which brings warm, salty, and nutrient-poor subtropical waters to high latitudes. Enhanced PMOC at the LGM would have lowered atmospheric CO2—in part through synergy with the Southern Ocean—and supported an equable regional climate, which may have aided human habitability in Beringia, and migration from Asia to North America.

Boron isotopes and trace element content measurements were funded by: the French National Research Agency projects ANR CARBORIC (Grant No. ANR-13-BS06-0013-04) and ANR HAMOC (Grant No. ANR-13-BS06-0003-02) at LSCE; NERC NE/N003861/1 & NE/S001743/1 at Bristol; NERC NE/N011716/1 at the University of St Andrews. The boron isotopic (δ11BSRM951) and trace element composition of marine carbonates are key proxies for understanding carbon cycling (pH) and palaeoceanographic change. However, comparability of results between laboratories requires carbonate reference materials. Here we report results of an inter‐laboratory comparison study to both assign δ11BSRM951 and trace element compositions to new marine carbonate reference materials (RM), NIST RM 8301 (Coral) and NIST RM 8301 (Foram) and to assess analytical variability among laboratories. Non‐certified reference values and expanded 95% uncertainties for δ11BSRM951 in NIST RM 8301 (Coral) (+24.17‰ ± 0.18‰) and NIST RM 8301 (Foram) (+14.51‰ ± 0.17‰) solutions were assigned by consensus approach using inter‐laboratory data. Differences reported among laboratories were considerably smaller than some previous inter‐laboratory comparisons, yet discrepancies could still lead to large differences in calculated seawater pH. Similarly, variability in reported trace element information values among laboratories (e.g., Mg/Ca ± 5%) was often greater than analytical precision (% RSD) within a single laboratory (e.g., Mg/Ca < 2%). Such differences potentially alter proxy‐reconstructed seawater temperature by more than 2 °C. These now well‐characterised solutions are useful reference materials to help the palaeoceanographic community build a comprehensive view of past ocean changes. Publisher PDF

Absolutely dated deep-sea coral ∆14C, δ11B, and δ15N records reveal Southern Ocean’s role in rapid deglacial carbon cycle events., The Southern Ocean plays a crucial role in regulating atmospheric CO2 on centennial to millennial time scales. However, observations of sufficient resolution to explore this have been lacking. Here, we report high-resolution, multiproxy records based on precisely dated deep-sea corals from the Southern Ocean. Paired deep (∆14C and δ11B) and surface (δ15N) proxy data point to enhanced upwelling coupled with reduced efficiency of the biological pump at 14.6 and 11.7 thousand years (ka) ago, which would have facilitated rapid carbon release to the atmosphere. Transient periods of unusually well-ventilated waters in the deep Southern Ocean occurred at 16.3 and 12.8 ka ago. Contemporaneous atmospheric carbon records indicate that these Southern Ocean ventilation events are also important in releasing respired carbon from the deep ocean to the atmosphere. Our results thus highlight two distinct modes of Southern Ocean circulation and biogeochemistry associated with centennial-scale atmospheric CO2 jumps during the last deglaciation.

JWBR received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (Grant Agreement No. 805246) and from the Natural Environmental Research Council (NERC) grant NE/N011716/1. Boron isotopes in marine carbonates are increasingly used to reconstruct seawater pH and atmospheric pCO2 through Earth’s history. While isotope ratio measurements from individual laboratories are often of high quality, it is important that records generated in different laboratories can equally be compared. Within this Boron Isotope Intercomparison Project (BIIP), we characterised the boron isotopic composition (commonly expressed in δ11B) of two marine carbonates: Geological Survey of Japan carbonate reference materials JCp‐1 (coral Porites) and JCt‐1 (giant clam Tridacna gigas). Our study has three foci: (a) to assess the extent to which oxidative pre‐treatment, aimed at removing organic material from carbonate, can influence the resulting δ11B; (b) to determine to what degree the chosen analytical approach may affect the resultant δ11B; and (c) to provide well‐constrained consensus δ11B values for JCp‐1 and JCt‐1. The resultant robust mean and associated robust standard deviation (s*) for un‐oxidised JCp‐1 is 24.36 ± 0.45‰ (2s*), compared with 24.25 ± 0.22‰ (2s*) for the same oxidised material. For un‐oxidised JCt‐1, respective compositions are 16.39 ± 0.60‰ (2s*; un‐oxidised) and 16.24 ± 0.38‰ (2s*; oxidised). The consistency between laboratories is generally better if carbonate powders were oxidatively cleaned prior to purification and measurement. Publisher PDF

International audience; North Pacific atmospheric and oceanic circulations are key missing pieces in our understanding of the reorganization of the global climate system since the Last Glacial Maximum. Here, using a basin-wide compilation of planktic foraminiferal δ 18 O, we show that the North Pacific subpolar gyre extended~3°further south during the Last Glacial Maximum, consistent with sea surface temperature and productivity proxy data. Climate models indicate that the expansion of the subpolar gyre was associated with a substantial gyre strengthening, and that these gyre circulation changes were driven by a southward shift of the midlatitude westerlies and increased wind stress from the polar easterlies. Using single-forcing model runs, we show that these atmospheric circulation changes are a nonlinear response to ice sheet topography/albedo and CO 2. Our reconstruction indicates that the gyre boundary (and thus westerly winds) began to migrate northward at~16.5 ka, driving changes in ocean heat transport, biogeochemistry, and North American hydroclimate. Plain language summary Despite the North Pacific's importance in the global climate system, changes in the circulation of this region since the last ice age are poorly understood. Today, the North Pacific Ocean has distinct properties north and south of~40°N: To the south, the warm surface waters form a circulation cell that moves clockwise (the subtropical gyre); to the north, the cold surface waters form a circulation cell that moves anticlockwise (the subpolar gyre). This difference in surface ocean circulation north and south of~40°N is determined by the wind patterns. Here, using a compilation of oxygen isotopes measured in the carbonate shells of fossil plankton from sediment cores across the basin, which tracks changes in the spatial pattern of temperature, we reconstruct how the position of the boundary between the gyres changed since the last ice age. Our results show that the boundary between the gyres was shifted southward by~3°during the last ice age; this indicates that the westerly winds were also shifted southward at this time. Using numerical simulations of the climate, we find that this ice age shift in the westerly winds is primarily due to the presence of a large ice sheet over North America.

REZ is grateful to Lance Agavulin and Glen Morangie for their spiritual support. JWBR was supported by the European Research Council (ERC Grant 805246) and the Natural Environment Research Council (NERC grant NE/N011716/1). The aqueous boric, hydrofluoric, and fluoroboric acid systems are key to a variety of applications, including boron measurements in marine carbonates for CO2 system reconstructions, chemical analysis and synthesis, polymer science, sandstone acidizing, fluoroborate salt manufacturing, and more. Here we present a comprehensive study of chemical equilibria and boron isotope partitioning in the aqueous boric acid–hydrofluoric acid system. We work out the chemical speciation of the various dissolved compounds over a wide range of pH, total fluorine (FT), and total boron (BT) concentrations. We show that at low pH (0 ≤ pH ≤ 4) and FT ≫ BT, the dominant aqueous species is BF4−, a result relevant to recent advances in high precision measurements of boron concentration and isotopic composition. Using experimental data on kinetic rate constants, we provide estimates for the equilibration time of the slowest reaction in the system as a function of pH and [HF], assuming FT ≫ BT. Furthermore, we present the first quantum-chemical (QC) computations to determine boron isotope fractionation in the fluoroboric acid system. Our calculations suggest that the equilibrium boron isotope fractionation between BF3 and BF4− is slightly smaller than that calculated between B(OH)3 and B(OH)4−. Based on the QC methods X3LYP/6-311+G(d,p) (X3LYP+) and MP2/aug-cc-pVTZ (MP2TZ), α(BF3−BF4−) ≃ 1.030 and 1.025, respectively. However, BF4− is enriched in 11B relative to B(OH)4−, i.e., α(BF4−−B(OH)4−) ≃ 1.010 (X3LYP+) and 1.020 (MP2TZ), respectively. Selection of the QC method (level of theory and basis set) represents the largest uncertainty in the calculations. The effect of hydration on the calculated boron isotope fractionation turned out to be minor in most cases, except for BF4− and B(OH)3. Finally, we provide suggestions on best practice for boric acid–hydrofluoric acid applications in geochemical boron analyses. Postprint

Funding was provided through a NERC Research Training Support Grant awarded NE/L002590/1 to Ben Taylor and NERC grant NE/N011716/1 awarded to James Rae and Andrea Burke. Planktic foraminifera census data have been used to reconstruct past temperatures through transfer functions, as well as changes in ocean ecosystems, chemistry and circulation. Here we present new multinet, plankton net and core-top census data from 20 sites in the Subpolar North Pacific. We combine these with previous data to provide an up to date compilation of North Pacific planktic foraminifera assemblage data. Our compilation is used to define 6 faunal zones: the subpolar zone; transitional zone; upwelling zone; subtropical zone; east equatorial zone; west equatorial zone; based on the distribution of 10 major species of planktic foraminifera. Two species of planktic foraminifera Neogloboquadrina pachyderma and Globigerina bulloides provide the basis for many subpolar paleo-reconstructions. Through the analysis of new multinet and CTD data we find that G. bulloides and N. pachyderma are predominantly found within 0–50 m of the water column and coincide with high food availability. N. pachyderma also shows a strong temperature control and can thrive in food poor waters where temperatures are low. Both species bloom seasonally, particularly during the spring bloom of March to June, with G. bulloides exhibiting greater seasonal variation. We suggest that percentage abundance of N. pachyderma in paleo-assemblages can be used to assess relative changes in past temperature, with G. bulloides abundance more likely to reflect changes in food availability. By comparing our core-top and multinet data, we also find a dissolution bias of G. bulloides over N. pachyderma in the North Pacific, which may enrich assemblages in the latter species. Postprint

Wally Broecker acknowledges funding from the Comer Science and Education Foundation. James W. B. Rae acknowledges funding from NERC standard grants NE/N003861/1 and NE/N011716/1, and support from the School of Earth and Environmental Sciences at the University of St Andrews during Wally Broecker’s visit, which sparked the discussions that led to this paper. In this contribution we explore constraints on the fractions of deep water present in the Indian and Pacific oceans which originated in the northern Atlantic and in the Southern Ocean. Based on PO4* we show that if ventilated Antarctic shelf waters characterize the Southern contribution, then the proportions could be close to 50–50. If instead a Southern Ocean bottom water value is used, the Southern contribution is increased to 75 %. While this larger estimate may best characterize the volume of water entering the Indo-Pacific from the Southern Ocean, it contains a significant portion of entrained northern water. We also note that ventilation may be highly tracer dependent: for instance Southern Ocean waters may contribute only 35 % of the deep radiocarbon budget, even if their volumetric contribution is 75 %. In our estimation, the most promising approaches involve using CFC-11 to constrain the amount of deep water formed in the Southern Ocean. Finally, we highlight the broad utility of PO4* as a tracer of deep water masses, including descending plumes of Antarctic Bottom Water and large-scale patterns of deep ocean mixing, and as a tracer of the efficiency of the biological pump. Publisher PDF

The B/Ca ratio of planktic foraminiferal calcite, a proxy for the surface ocean carbonate system, displays large negative excursions during the Paleocene-Eocene Thermal Maximum (PETM, 55.9 Ma), consistent with rapid ocean acidification at that time. However, the B/Ca excursion measured at the PETM exceeds a magnitude that modern pH calibrations can explain. Numerous other controls on the proxy have been suggested, including foraminiferal growth rate and the total concentration of dissolved inorganic carbon (DIC). Here we present new calibrations for B/Ca versus the combined effects of pH and DIC in the symbiont-bearing planktic foraminifer Orbulina universa, grown in culture solutions with simulated Paleocene seawater elemental composition (high [Ca], low [Mg], and low total boron concentration ([B]_T). We also investigate the isolated effects of low seawater [B]_T, high [Ca], reduced symbiont photosynthetic activity, and average shell growth rate on O. universa B/Ca in order to further understand the proxy systematics and to determine other possible influences on the PETM records. We find that average shell growth rate does not appear to determine B/Ca in high calcite saturation experiments. In addition, our “Paleocene” calibration shows higher sensitivity than the modern calibration at low [B(OH)_4−]/DIC. Given a large DIC pulse at the PETM, this amplification of the B/Ca response can more fully explain the PETM B/Ca excursion. However, further calibrations with other foraminifer species are needed to determine the range of foraminifer species-specific proxy sensitivities under these conditions for quantitative reconstruction of large carbon cycle perturbations.

Significance Debate lingers over what caused the last mass extinction 66 million years ago, with intense volcanism and extraterrestrial impact the most widely supported hypotheses. However, without empirical evidence for either’s exact environmental effects, it is difficult to discern which was most important in driving extinction. It is also unclear why recovery of biodiversity and carbon cycling in the oceans was so slow after an apparently sudden extinction event. In this paper, we show (using boron isotopes and Earth system modeling) that the impact caused rapid ocean acidification, and that the resulting ecological collapse in the oceans had long-lasting effects for global carbon cycling and climate. Our data suggest that impact, not volcanism, was key in driving end-Cretaceous mass extinction., Mass extinction at the Cretaceous–Paleogene (K-Pg) boundary coincides with the Chicxulub bolide impact and also falls within the broader time frame of Deccan trap emplacement. Critically, though, empirical evidence as to how either of these factors could have driven observed extinction patterns and carbon cycle perturbations is still lacking. Here, using boron isotopes in foraminifera, we document a geologically rapid surface-ocean pH drop following the Chicxulub impact, supporting impact-induced ocean acidification as a mechanism for ecological collapse in the marine realm. Subsequently, surface water pH rebounded sharply with the extinction of marine calcifiers and the associated imbalance in the global carbon cycle. Our reconstructed water-column pH gradients, combined with Earth system modeling, indicate that a partial ∼50% reduction in global marine primary productivity is sufficient to explain observed marine carbon isotope patterns at the K-Pg, due to the underlying action of the solubility pump. While primary productivity recovered within a few tens of thousands of years, inefficiency in carbon export to the deep sea lasted much longer. This phased recovery scenario reconciles competing hypotheses previously put forward to explain the K-Pg carbon isotope records, and explains both spatially variable patterns of change in marine productivity across the event and a lack of extinction at the deep sea floor. In sum, we provide insights into the drivers of the last mass extinction, the recovery of marine carbon cycling in a postextinction world, and the way in which marine life imprints its isotopic signal onto the geological record.

J. Shao and L.D. Stott were supported by an NSF grant (MG&G 1558990). W. R. Gray and R. Greenop were supported by NERC grants NE/N011716/1 and NE/N011716/1 to J.W.B. Rae. I. Pecher, H.L. Neil, and B. Davy were supported by RSNZ Marsden Fund grant UOA1022. R. Coffin was supported by a DOE-NETL contract to NRL subcontract to TAMUCC (#601970). Identifying processes within the Earth System that have modulated atmospheric pCO2 during each glacial cycle of the late Pleistocene stands as one of the grand challenges in climate science. The growing array of surface ocean pH estimates from the boron isotope proxy across the last glacial termination may reveal regions of the ocean that influenced the timing and magnitude of pCO2 rise. Here we present two new boron isotope records from the subtropical‐subpolar transition zone of the Southwest Pacific that span the last 20 kyr, as well as new radiocarbon data from the same cores. The new data suggest this region was a source of carbon to the atmosphere rather than a moderate sink as it is today. Significantly higher outgassing is observed between ~16.5‐14 kyrBP, associated with increasing δ13C and [CO3]2‐ at depth, suggesting loss of carbon from the intermediate ocean to the atmosphere. We use these new boron isotope records together with existing records to build a composite pH/pCO2 curve for the surface oceans. pH disequilibrium/CO2 outgassing was widespread throughout the last deglaciation, likely explained by upwelling of CO2 from the deep/intermediate ocean. During the Holocene, a smaller outgassing peak is observed at a time of relatively stable atmospheric CO2, which may be explained by regrowth of the terrestrial biosphere countering ocean CO2 release. Our stack is likely biased toward upwelling/CO2 source regions. Nevertheless, the composite pCO2 curve provides robust evidence that various parts of the ocean were releasing CO2 to the atmosphere over the last 25 kyr. Publisher PDF

The work is supported by the Research Council of Norway (RCN) through Petromaks2- NORCRUST (project number: 255150) and its Centre of Excellence funding scheme for CAGE (project number: 223259). J.-H. K. is supported by the project "Development on Geochemical Proxies of Isotope and Trace Element for Understanding of Earth and Universe Evolution Processes (GP2017-018)" funded by the Korea Ministry of Science and ICT (MSIT). Svalbard fjord cruise in 2016 with RV Helmer Hanssen for Science Research Program to S.-I.N. is fully supported by MSIT (NRF-2015M1A5A1037243, PN19090). Submarine groundwater discharge could impact the transport of critical solutes to the ocean. However, its driver(s), significance over geological time scales, and geographical coverage are poorly understood. We characterize a submarine groundwater seep from the continental slope off northern Norway where substantial amount of meteoric water was detected. We reconstruct the seepage history from textural relationships and U-Th geochronology of authigenic minerals. We demonstrate how glacial-interglacial dynamics promoted submarine groundwater circulation more than 100 km offshore and resulted in high fluxes of critical solutes to the ocean. This cryosphere-hydrosphere coupling is likely common in the circum-Arctic implying that future decay of glaciers and permafrost in a warming Arctic is expected to attenuate such a coupled process and thus decrease the export of critical solutes. Publisher PDF

Past climate records reveal many instances of rapid climate change that are often coincident with fast changes in atmospheric greenhouse gas concentrations, suggesting links and positive feedbacks between the carbon cycle and the physical climate system. The carbon reservoirs that might have played an important role during these past episodes of rapid change include near-surface soil and peatland carbon, permafrost, carbon stored in vegetation, methane hydrates in deep-sea sediments, volcanism, and carbon stored in parts of the ocean that are easily ventilated through changes in circulation. To determine whether similar changes might lie in store in our future, we must gain a better understanding of the physics, biogeochemistry, dynamics, and feedbacks involved in such events. Specifically, we need to ascertain the main natural sources of atmospheric carbon dioxide and methane linked to rapid climate events in the paleoclimate record, and understand the mechanisms, triggers, thresholds, and feedbacks that were involved. Our review contributes to this focus issue by synthesizing results from nine studies covering a broad range of past time episodes. Studies are categorized into (a) episodes of massive carbon release millions of years ago; (b) the transition from the last glacial to the current interglacial 19 000–11 000 years ago; and (c) the current era. We conclude with a discussion on major remaining research challenges and implications for future projections and risk assessment.

Coral skeletal growth is sensitive to environmental change and may be adversely impacted by an acidifying ocean. However, physiological processes can also buffer biomineralization from external conditions, providing apparent resilience to acidification in some species. These same physiological processes affect skeletal composition and can impact paleoenvironmental proxies. Understanding the mechanisms of coral calcification is thus crucial for predicting the vulnerability of different corals to ocean acidification and for accurately interpreting coral-based climate records. Here, using boron isotope ( δ 11 B ) measurements on cultured cold-water corals, we explain fundamental features of coral calcification and its sensitivity to environmental change. Boron isotopes are one of the most widely used proxies for past seawater pH, and we observe the expected sensitivity between δ 11 B and pH. Surprisingly, we also discover that coral δ 11 B is independently sensitive to seawater dissolved inorganic carbon (DIC). We can explain this new DIC effect if we introduce boric acid diffusion across cell membranes as a new flux within a geochemical model of biomineralization. This model independently predicts the sensitivity of the δ 11 B -pH proxy, without being trained to these data, even though calcifying fluid pH (pHCF) is constant. Boric acid diffusion can resolve why δ 11 B is a useful proxy across a range of calcifiers, including foraminifera, even when calcifying fluid pH differs from seawater. Our modeling shows that δ 11 B cannot be interpreted unequivocally as a direct tracer of pHCF. Constant pHCF implies similar calcification rates as seawater pH decreases, which can explain the resilience of some corals to ocean acidification. However, we show that this resilience has a hidden energetic cost such that calcification becomes less efficient in an acidifying ocean.

In order to better understand the effect of CO2 on the Earth system in the future, geologists may look to CO2-induced environmental change in Earth's past. Here we describe how CO2 can be reconstructed using the boron isotopic composition (δ11B) of marine calcium carbonate. We review the chemical principles that underlie the proxy, summarize the available calibration data, and detail how boron isotopes can be used to estimate ocean pH and ultimately atmospheric CO2 in the past. δ11B in a variety of marine carbonates shows a coherent relationship with seawater pH, in broad agreement with simple models for this proxy. Offsets between measured and predicted δ11B may in part be explained by physiological influences, though the exact mechanisms of boron incorporation into carbonate remain unknown. Despite these uncertainties, we demonstrate that δ11B may provide crucial constraints on past ocean acidification and atmospheric CO2.

Funding was provided by an Antarctic Bursary awarded to J.A.S., ERC and NERC grants awarded to L.F.R. (278705, NE/S001743/1, NE/R005117/1) and L.F.R. and J.W.B.R. (NE/N003861/1), and a NERC Stable isotope Grant. The Li/Mg, Sr/Ca and oxygen isotopic (δ18O) compositions of many marine biogenic carbonates are sensitive to seawater temperature. Corals, as cosmopolitan marine taxa with carbonate skeletons that can be precisely dated, represent ideal hosts for these geochemical proxies. However, efforts to calibrate and refine temperature proxies in cold-water corals (

The cause of changes in atmospheric carbon dioxide (CO2) during the recent ice ages is yet to be fully explained. Most mechanisms for glacial–interglacial CO2 change have centred on carbon exchange with the deep ocean, owing to its large size and relatively rapid exchange with the atmosphere1. The Southern Ocean is thought to have a key role in this exchange, as much of the deep ocean is ventilated to the atmosphere in this region2. However, it is difficult to reconstruct changes in deep Southern Ocean carbon storage, so few direct tests of this hypothesis have been carried out. Here we present deep-sea coral boron isotope data that track the pH—and thus the CO2 chemistry—of the deep Southern Ocean over the past forty thousand years. At sites closest to the Antarctic continental margin, and most influenced by the deep southern waters that form the ocean’s lower overturning cell, we find a close relationship between ocean pH and atmospheric CO2: during intervals of low CO2, ocean pH is low, reflecting enhanced ocean carbon storage; and during intervals of rising CO2, ocean pH rises, reflecting loss of carbon from the ocean to the atmosphere. Correspondingly, at shallower sites we find rapid (millennial- to centennial-scale) decreases in pH during abrupt increases in CO2, reflecting the rapid transfer of carbon from the deep ocean to the upper ocean and atmosphere. Our findings confirm the importance of the deep Southern Ocean in ice-age CO2 change, and show that deep-ocean CO2 release can occur as a dynamic feedback to rapid climate change on centennial timescales. Analysis of deep-sea coral boron isotope data, as a proxy for pH and thus CO2 chemistry, provides evidence of CO2 storage in the deep Southern Ocean during the last ice age, and its rapid release on millennial to centennial timescales during deglaciation.

This work was supported by the UK Natural Environment Research Council (award NE/I022973/1) to AAF and NA. Ocean acidification typically reduces calcification in tropical marine corals but the mechanism for this process is not understood. We use skeletal boron geochemistry (B/Ca and δ11B) to reconstruct the calcification fluid DIC of corals cultured over both high and low seawater pCO2 (180, 400 and 750 μatm). We observe strong positive correlations between calcification fluid pH and concentrations of the DIC species potentially implicated in aragonite precipitation (be they CO32- , HCO3- or HCO3-+CO32- ). Similarly, with the exception of one outlier, the fluid concentrations of precipitating DIC species are strongly positively correlated with coral calcification rate. Corals cultured at high seawater pCO2 usually have low calcification fluid pH and low concentrations of precipitating DIC, suggesting that a reduction in DIC substrate at the calcification site is responsible for decreased calcification. The outlier coral maintained high pHCF and DICCF at high seawater pCO2 but exhibited a reduced calcification rate indicating that the coral has a limited energy budget to support proton extrusion from the calcification fluid and meet other calcification demands. We find no evidence that increasing seawater pCO2 enhances diffusion of CO2 into the calcification site. Instead the overlying [CO2] available to diffuse into the calcification site appears broadly comparable between seawater pCO2 treatments, implying that metabolic activity (respiration and photosynthesis) generates a similar [CO2] in the vicinity of the calcification site regardless of seawater pCO2. Postprint

This work was funded by NERC studentship NE/I528185/1 awarded to W.R.G., NERC studentship NE/1492942/1 to B.T., NERC grant NE/N011716/1 awarded to J.W.B.R and A.B., and NERC grant NE/I013377/1 awarded to A.E.S. The interplay between ocean circulation and biological productivity affects atmospheric CO2 levels and marine oxygen concentrations. During the warming of the last deglaciation, the North Pacific experienced a peak in productivity and widespread hypoxia, with changes in circulation, iron supply and light limitation all proposed as potential drivers. Here we use the boron-isotope composition of planktic foraminifera from a sediment core in the western North Pacific to reconstruct pH and dissolved CO2 concentrations from 24,000 to 8,000 years ago. We find that the productivity peak during the Bølling–Allerød warm interval, 14,700 to 12,900 years ago, was associated with a decrease in near-surface pH and an increase in pCO2, and must therefore have been driven by increased supply of nutrient- and CO2-rich waters. In a climate model ensemble (PMIP3), the presence of large ice sheets over North America results in high rates of wind-driven upwelling within the subpolar North Pacific. We suggest that this process, combined with collapse of North Pacific Intermediate Water formation at the onset of the Bølling–Allerød, led to high rates of upwelling of water rich in nutrients and CO2, and supported the peak in productivity. The respiration of this organic matter, along with poor ventilation, probably caused the regional hypoxia. We suggest that CO2 outgassing from the North Pacific helped to maintain high atmospheric CO2 concentrations during the Bølling–Allerød and contributed to the deglacial CO2 rise. Postprint

In this contribution we explore constraints on the fractions of deep water present in Indian and Pacific Oceans which originated in the northern Atlantic and in the Southern Ocean. Based on PO4* we show that if ventilated Antarctic shelf waters characterize the Southern contribution, then the proportions are close to 50–50. If instead a Southern Ocean bottom water value is used, the Southern contribution is increased to 75 %. While this larger estimate may characterize the volume of water entering the Indo-Pacific from the Southern Ocean, it contains a significant portion of entrained northern water. We also note that ventilation may be highly tracer dependent: for instance Southern Ocean waters may contribute only 35 % of the deep radiocarbon budget, even if their volumetric contribution is 75 %. In our estimation, the most promising approaches involve using CFC-11 to constrain the amount of deep water formed in the Southern Ocean.

The boron isotope composition of foraminifera provides a powerful tracer for CO2 change over geological time. This proxy is based on the equilibrium of boron and its isotopes in seawater, which is a function of pH. However while the chemical principles underlying this proxy are well understood, its reliability has previously been questioned, due to the difficulty of boron isotope (δ11B) analysis on foraminferal samples and questions regarding calibrations between δ11B and pH. This chapter reviews the current state of the δ11B-pH proxy in foraminfera, including the pioneering studies that established this proxy’s potential, and the recent work that has improved understanding of boron isotope systematics in foraminifera and applied this tracer to the geological record. The theoretical background of the δ11B-pH proxy is introduced, including an accurate formulation of the boron isotope mass balance equations. Sample preparation and analysis procedures are then reviewed, with discussion of sample cleaning, the potential influence of diagenesis, and the strengths and weaknesses of boron purification by column chromatography versus microsublimation, and analysis by NTIMS versus MC-ICPMS. The systematics of boron isotopes in foraminifera are discussed in detail, including results from benthic and planktic taxa, and models of boron incorporation, fractionation, and biomineralisation. Benthic taxa from the deep ocean have δ11B within error of borate ion at seawater pH. This is most easily explained by simple incorporation of borate ion at the pH of seawater. Planktic foraminifera have δ11B close to borate ion, but with minor offsets. These may be driven by physiological influences on the foraminiferal microenvironment; a novel explanation is also suggested for the reduced δ11B-pH sensitivities observed in culture, based on variable calcification rates. Biomineralisation influences on boron isotopes are then explored, addressing the apparently contradictory observations that foraminifera manipulate pH during chamber formation yet their δ11B appears to record the pH of ambient seawater. Potential solutions include the influences of magnesium-removal and carbon concentration, and the possibility that pH elevation is most pronounced during initial chamber formation under favourable environmental conditions. The steps required to reconstruct pH and pCO2 from δ11B are then reviewed, including the influence of seawater chemistry on boron equilibrium, the evolution of seawater δ11B, and the influence of second carbonate system parameters on δ11B-based reconstructions of pCO2. Applications of foraminiferal δ11B to the geological record are highlighted, including studies that trace CO2 storage and release during recent ice ages, and reconstructions of pCO2 over the Cenozoic. Relevant computer codes and data associated with this article are made available online.

Deep water formation in the North Atlantic and Southern Ocean is widely thought to influence deglacial CO_2 rise and climate change; here we suggest that deep water formation in the North Pacific may also play an important role. We present paired radiocarbon and boron isotope data from foraminifera from sediment core MD02-2489 at 3640 m in the North East Pacific. These show a pronounced excursion during Heinrich Stadial 1, with benthic-planktic radiocarbon offsets dropping to ~350 years, accompanied by a decrease in benthic δ^(11)B. We suggest that this is driven by the onset of deep convection in the North Pacific, which mixes young shallow waters to depth, old deep waters to the surface, and low-pH water from intermediate depths into the deep ocean. This deep water formation event was likely driven by an increase in surface salinity, due to subdued atmospheric/monsoonal freshwater flux during Heinrich Stadial 1. The ability of North Pacific Deep Water (NPDW) formation to explain the excursions seen in our data is demonstrated in a series of experiments with an intermediate complexity Earth system model. These experiments also show that breakdown of stratification in the North Pacific leads to a rapid ~30 ppm increase in atmospheric CO_2, along with decreases in atmospheric δ^(13)C and Δ^(14)C, consistent with observations of the early deglaciation. Our inference of deep water formation is based mainly on results from a single sediment core, and our boron isotope data are unavoidably sparse in the key HS1 interval, so this hypothesis merits further testing. However, we note that there is independent support for breakdown of stratification in shallower waters during this period, including a minimum in δ^(15)N, younging in intermediate water ^(14)C, and regional warming. We also re-evaluate deglacial changes in North Pacific productivity and carbonate preservation in light of our new data and suggest that the regional pulse of export production observed during the Bolling-Allerod is promoted by relatively stratified conditions, with increased light availability and a shallow, potent nutricline. Overall, our work highlights the potential of NPDW formation to play a significant and hitherto unrealized role in deglacial climate change and CO_2 rise.

This work was aided by a Nuffield Summer Studentship granted to MJH, a U.S. Science Support Program (USSSP) Post-Expedition Activity award for IODP Exp. 342 to PMH, a Flint Postdoctoral Fellowship to DEP, a NERC PhD Studentship granted to JWBR, and a URF and Wolfson merit award to DNS. Pelagic ecosystem function is integral to global biogeochemical cycling, and plays a major role in modulating atmospheric CO2 concentrations (pCO2). Uncertainty as to the effects of human activities on marine ecosystem function hinders projection of future atmospheric pCO2. To this end, events in the geological past can provide informative case studies in the response of ecosystem function to environmental and ecological changes. Around the Cretaceous–Palaeogene (K–Pg) boundary, two such events occurred: Deccan large igneous province (LIP) eruptions and massive bolide impact at the Yucatan Peninsula. Both perturbed the environment, but only the impact coincided with marine mass extinction. As such, we use these events to directly contrast the response of marine biogeochemical cycling to environmental perturbation with and without changes in global species richness. We measure this biogeochemical response using records of deep-sea carbonate preservation. We find that Late Cretaceous Deccan volcanism prompted transient deep-sea carbonate dissolution of a larger magnitude and timescale than predicted by geochemical models. Even so, the effect of volcanism on carbonate preservation was slight compared with bolide impact. Empirical records and geochemical models support a pronounced increase in carbonate saturation state for more than 500 000 years following the mass extinction of pelagic carbonate producers at the K–Pg boundary. These examples highlight the importance of pelagic ecosystems in moderating climate and ocean chemistry. Postprint

The authors would like to thank NERC for funding AGMC (NE/G524228/1) and JWBR (NE/F007345/1) via PhD studentships and the Royal Society for funding DNS via a University Research Fellowship and a Wolfson Merit Award. The work was supported by NERC grant NE/H006273/1. OS acknowledges the Ministry of Education, Culture, Sports, Science and Technology for funding via Japan Society of Promotion of Science (No. 1800410000) enabling the research at Bristol. The data is deposited at www.pangaea.de, (doi:10.1594/PANGAEA.837987). The impact of global change on marine ecosystems is a major concern for the future. Examples from the geological past may provide insight into how ecosystems respond to major shifts in environment. Here we use the progressive closure of the Central American Seaway over the last 10 Myrs, and the resulting new environmental conditions and niches on either side of the Panama Isthmus, as a time series documenting the reaction of planktic foraminifers to environmental change and vicariance. Our main finding is that the size and shape evolution of both investigated species is strongly influenced by temperature, despite their different ecology. The surface dweller Trilobatus sacculifer conserved the same shape on both sides of the Isthmus for most of the studied interval, and diverged only recently when environment diverged on both sides of the Isthmus. The shape response is a combination of a change in mean shape and in percentage of morphotypes occurring within T. sacculifer. This suggests a minor role of vicariance and the potential to react to changes in the local environment through ecotypic or plastic variation. This interpretation is corroborated by extensive phenotypic variability in the absence of genetic differentiation today in this species. The shape of the deeper-living species Gt. tumida, in contrast, diverged on both sides of the Isthmus at a time that coincides with the cut-off of the connection of its habitat. This divergence combines a response to temperature and to location, suggesting local adaptation in response to vicariance. These different reactions highlight both a high potential for adaptation, but also sensitivity to temperature variations. The species-specific responses to environmental pressures indicate the difficulty in upscaling from one species to foraminifers in general. Postprint

In this study we make the first attempt to inter-calibrate boron isotope (δ11B) measurements on marine biogenic carbonates measured by four different laboratories, each using a different analytical technique. The importance of such calibrations lies in the major implications of relatively small changes in δ11B (less than 2‰), which are typical of palaeoclimate applications of the δ11B-pH proxy. Despite the variety of mass spectrometric techniques used by the different laboratories in this study (two variants of negative ion thermal ionisation mass spectrometry and two variants of multicollector inductively coupled plasma mass spectrometry), for samples without a complex sample matrix, such as boric acid, there are no significant interlaboratory biases: the pooled 2sd of these samples is 0.39‰, which is within the measurement uncertainties reported by each laboratory (which range between 0.18 and 0.80‰). For seawater, a common in-house reference material, we find a similarly good agreement (δ11B = 39.65 ± 0.41‰, 2sd) despite four different sample preparation procedures. Reported δ11B for calcium carbonate samples have a pooled 2sd of 1.46‰, which is larger than the measurement uncertainty reported by each laboratory. We have attempted to identify the source of this interlaboratory variability, and find that overall sample size (in terms of available B) and B/Ca ratio (i.e. amount of boron relative to matrix) may play a role, but the exact mechanisms remain uncertain. Observed variations in reported δ11B for the CaCO3 samples are, however, relatively systematic for each laboratory for a given sample matrix (i.e. similar B/Ca and amount of boron for analysis). This implies that relative differences in δ11B in a sample set of a given matrix can be reconstructed by the four laboratories involved in this study more accurately than the absolute boron isotope ratios.

Radiocarbon and uranium-thorium dating results are presented from a genus of calcitic Antarctic cold-water octocorals (family Coralliidae), which were collected from the Marie Byrd Seamounts in the Amundsen Sea (Pacific sector of the Southern Ocean) andwhich to date have not been investigated geochemically. The geochronological results are set in contextwith solution and laser ablation-basedelement/Ca ratios (Li, B,Mg,Mn, Sr,Ba, U,Th). Octocoral radiocarbon ages on living corals are in excellent agreement with modern ambient deep-water Δ14C, while multiple samples of individual fossil coral specimens yielded reproducible radiocarbon ages. Provided that local radiocarbon reservoir ages can be derived for a given time, fossil Amundsen Sea octocorals should be reliably dateable by means of radiocarbon. In contrast to the encouraging radiocarbon findings, the uranium-series data are more difficult to interpret. The uranium concentration of these calcitic octocorals is an order of magnitude lower than in the aragonitic hexacorals that are conventionally used for geochronological investigations. While modern and Late Holocene octocorals yield initial δ234U in good agreement with modern seawater, our results reveal preferential inward diffusion of dissolved alpha-recoiled 234U and its impact on fossil coral δ234U. Besides alpha-recoil related 234U diffusion, high-resolution sampling of two fossil octocorals further demonstrates that diagenetic uraniummobility has offset apparent coral U-series ages. Combined with the preferential alpha-recoil 234U diffusion, this process has prevented fossil octocorals from preserving a closed system U-series calendar age for longer than a few thousand years. Moreover, several corals investigated contain significant initial thorium, which cannot be adequately corrected for because of an apparently variable initial 232Th/230Th. Our results demonstrate that calcitic cold-water corals are unsuitable for reliable U-series dating. Mg/Ca ratios within single octocoral specimens are internally strikingly homogeneous, and appear promising in terms of their response to ambient temperature. Magnesium/lithium ratios are significantly higher than usually observed in other deep marine calcifiers and for many of our studied corals are remarkably close to seawater compositions. Although this family of octocorals is unsuitable for glacial deep-water Δ14C reconstructions, our findings highlight some important differences between hexacoral (aragonitic) and octocoral (calcitic) biomineralisation. Calcitic octocorals could still be useful for trace element and some isotopic studies, such as reconstruction of ambient deep water neodymium isotope composition or pH, via boron isotopic measurements.

Amorphous calcium carbonate (ACC) has been identified or inferred to exist in many groups of marine organisms that produce biominerals widely used as geochemical archives (e.g. foraminifera, molluscs, echinoderms). However, little is known about trace element incorporation into ACC, and thus it is not understood how precipitation through an ACC precursor might impact the fidelity of climate proxies and biomineralisation models built on the skeletal geochemistry of these marine calcifiers. To address this, we investigated the incorporation of Li, B, Na, Mg, Mn, Sr, Ba, and U into inorganic amorphous calcium magnesium carbonates precipitated from seawater under a variety of different carbonate chemistries, Mg/Ca ratios, and in the presence of aspartic and glutamic acid, two of the most common intracrystalline amino acids found in foraminifera and corals. ACC is highly enriched in most of these trace elements relative to the crystalline carbonates yet similar in some respects in terms of the factors influencing trace element partitioning. For example, ACC B/Ca is sensitive to the carbonate system, whilst Mg/Ca and Sr/Ca are largely a function of their respective ratio in seawater. In general, we find that most of the variance in the distribution coefficients of the other trace elements can be explained by some combination of the seawater carbonate chemistry and the seawater or ACC Mg/Ca ratio. Postprint