Biological export production controls upper ocean calcium carbonate dissolution and CO2 buffer capacity.

Marine biogenic calcium carbonate (CaCO3) cycles play a key role in ecosystems and in regulating the ocean's ability to absorb atmospheric carbon dioxide (CO2). However, the drivers and magnitude of CaCO3 cycling are not well understood, especially for the upper ocean. Here, we provide global-scale evidence that heterotrophic respiration in settling marine aggregates may produce localized undersaturated microenvironments in which CaCO3 particles rapidly dissolve, producing excess alkalinity in the upper ocean. In the deep ocean, dissolution of CaCO3 is primarily driven by conventional thermodynamics of CaCO3 solubility with reduced fluxes of CaCO3 burial to marine sediments beneath more corrosive North Pacific deep waters. Upper ocean dissolution, shown to be sensitive to ocean export production, can increase the neutralizing capacity for respired CO2 by up to 6% in low-latitude thermocline waters. Without upper ocean dissolution, the ocean might lose 20% more CO2 to the atmosphere through the low-latitude upwelling regions.

Next-generation ensemble projections reveal higher climate risks for marine ecosystems.

Projections of climate change impacts on marine ecosystems have revealed long-term declines in global marine animal biomass and unevenly distributed impacts on fisheries. Here we apply an enhanced suite of global marine ecosystem models from the Fisheries and Marine Ecosystem Model Intercomparison Project (Fish-MIP), forced by new-generation Earth system model outputs from Phase 6 of the Coupled Model Intercomparison Project (CMIP6), to provide insights into how projected climate change will affect future ocean ecosystems. Compared with the previous generation CMIP5-forced Fish-MIP ensemble, the new ensemble ecosystem simulations show a greater decline in mean global ocean animal biomass under both strong-mitigation and high-emissions scenarios due to elevated warming, despite greater uncertainty in net primary production in the high-emissions scenario. Regional shifts in the direction of biomass changes highlight the continued and urgent need to reduce uncertainty in the projected responses of marine ecosystems to climate change to help support adaptation planning.

Time of Emergence and Large Ensemble Intercomparison for Ocean Biogeochemical Trends.

Anthropogenically forced changes in ocean biogeochemistry are underway and critical for the ocean carbon sink and marine habitat. Detecting such changes in ocean biogeochemistry will require quantification of the magnitude of the change (anthropogenic signal) and the natural variability inherent to the climate system (noise). Here we use Large Ensemble (LE) experiments from four Earth system models (ESMs) with multiple emissions scenarios to estimate Time of Emergence (ToE) and partition projection uncertainty for anthropogenic signals in five biogeochemically important upper-ocean variables. We find ToEs are robust across ESMs for sea surface temperature and the invasion of anthropogenic carbon; emergence time scales are 20-30 yr. For the biological carbon pump, and sea surface chlorophyll and salinity, emergence time scales are longer (50+ yr), less robust across the ESMs, and more sensitive to the forcing scenario considered. We find internal variability uncertainty, and model differences in the internal variability uncertainty, can be consequential sources of uncertainty for projecting regional changes in ocean biogeochemistry over the coming decades. In combining structural, scenario, and internal variability uncertainty, this study represents the most comprehensive characterization of biogeochemical emergence time scales and uncertainty to date. Our findings delineate critical spatial and duration requirements for marine observing systems to robustly detect anthropogenic change.

Author Correction: Hot Spots of Carbon and Alkalinity Cycling in the Coastal Oceans.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Microbial evolutionary strategies in a dynamic ocean.

Marine microbes form the base of ocean food webs and drive ocean biogeochemical cycling. Yet little is known about the ability of microbial populations to adapt as they are advected through changing conditions. Here, we investigated the interplay between physical and biological timescales using a model of adaptation and an eddy-resolving ocean circulation climate model. Two criteria were identified that relate the timing and nature of adaptation to the ratio of physical to biological timescales. Genetic adaptation was impeded in highly variable regimes by nongenetic modifications but was promoted in more stable environments. An evolutionary trade-off emerged where greater short-term nongenetic transgenerational effects (low-γ strategy) enabled rapid responses to environmental fluctuations but delayed genetic adaptation, while fewer short-term transgenerational effects (high-γ strategy) allowed faster genetic adaptation but inhibited short-term responses. Our results demonstrate that the selective pressures for organisms within a single water mass vary based on differences in generation timescales resulting in different evolutionary strategies being favored. Organisms that experience more variable environments should favor a low-γ strategy. Furthermore, faster cell division rates should be a key factor in genetic adaptation in a changing ocean. Understanding and quantifying the relationship between evolutionary and physical timescales is critical for robust predictions of future microbial dynamics.

Emergence of Anthropogenic Signals in the Ocean Carbon Cycle.

Attribution of anthropogenically-forced trends in the climate system requires understanding when and how such signals will emerge from natural variability. We apply time-of-emergence diagnostics to a Large Ensemble of an Earth System Model, providing both a conceptual framework for interpreting the detectability of anthropogenic impacts in the ocean carbon cycle and observational sampling strategies required to achieve detection. We find emergence timescales ranging from under a decade to over a century, a consequence of the time-lag between chemical and radiative impacts of rising atmospheric CO2 on the ocean. Processes sensitive to carbonate-chemical changes emerge rapidly, such as impacts of acidification on the calcium-carbonate pump (10 years for the globally-integrated signal, 9-18 years regionally-integrated), and the invasion flux of anthropogenic CO2 into the ocean (14 globally, 13-26 regionally). Processes sensitive to the ocean's physical state, such as the soft-tissue pump, which depends on nutrients supplied through circulation, emerge decades later (23 globally, 27-85 regionally).

Seasonal to multiannual marine ecosystem prediction with a global Earth system model.

Climate variations have a profound impact on marine ecosystems and the communities that depend upon them. Anticipating ecosystem shifts using global Earth system models (ESMs) could enable communities to adapt to climate fluctuations and contribute to long-term ecosystem resilience. We show that newly developed ESM-based marine biogeochemical predictions can skillfully predict satellite-derived seasonal to multiannual chlorophyll fluctuations in many regions. Prediction skill arises primarily from successfully simulating the chlorophyll response to the El Niño-Southern Oscillation and capturing the winter reemergence of subsurface nutrient anomalies in the extratropics, which subsequently affect spring and summer chlorophyll concentrations. Further investigations suggest that interannual fish-catch variations in selected large marine ecosystems can be anticipated from predicted chlorophyll and sea surface temperature anomalies. This result, together with high predictability for other marine-resource-relevant biogeochemical properties (e.g., oxygen, primary production), suggests a role for ESM-based marine biogeochemical predictions in dynamic marine resource management efforts.

Global ensemble projections reveal trophic amplification of ocean biomass declines with climate change.

While the physical dimensions of climate change are now routinely assessed through multimodel intercomparisons, projected impacts on the global ocean ecosystem generally rely on individual models with a specific set of assumptions. To address these single-model limitations, we present standardized ensemble projections from six global marine ecosystem models forced with two Earth system models and four emission scenarios with and without fishing. We derive average biomass trends and associated uncertainties across the marine food web. Without fishing, mean global animal biomass decreased by 5% (±4% SD) under low emissions and 17% (±11% SD) under high emissions by 2100, with an average 5% decline for every 1 °C of warming. Projected biomass declines were primarily driven by increasing temperature and decreasing primary production, and were more pronounced at higher trophic levels, a process known as trophic amplification. Fishing did not substantially alter the effects of climate change. Considerable regional variation featured strong biomass increases at high latitudes and decreases at middle to low latitudes, with good model agreement on the direction of change but variable magnitude. Uncertainties due to variations in marine ecosystem and Earth system models were similar. Ensemble projections performed well compared with empirical data, emphasizing the benefits of multimodel inference to project future outcomes. Our results indicate that global ocean animal biomass consistently declines with climate change, and that these impacts are amplified at higher trophic levels. Next steps for model development include dynamic scenarios of fishing, cumulative human impacts, and the effects of management measures on future ocean biomass trends.

Hot Spots of Carbon and Alkalinity Cycling in the Coastal Oceans.

Ocean calcium carbonate (CaCO3) production and preservation play a key role in the global carbon cycle. Coastal and continental shelf (neritic) environments account for more than half of global CaCO3 accumulation. Previous neritic CaCO3 budgets have been limited in both spatial resolution and ability to project responses to environmental change. Here, a 1° spatially explicit budget for neritic CaCO3 accumulation is developed. Globally gridded satellite and benthic community area data are used to estimate community CaCO3 production. Accumulation rates (PgC yr-1) of four neritic environments are calculated: coral reefs/banks (0.084), seagrass-dominated embayments (0.043), and carbonate rich (0.037) and poor (0.0002) shelves. This analysis refines previous neritic CaCO3 accumulation estimates (~0.16) and shows almost all coastal carbonate accumulation occurs in the tropics, >50% of coral reef accumulation occurs in the Western Pacific Ocean, and 80% of coral reef, 63% of carbonate shelf, and 58% of bay accumulation occur within three global carbonate hot spots: the Western Pacific Ocean, Eastern Indian Ocean, and Caribbean Sea. These algorithms are amenable for incorporation into Earth System Models that represent open ocean pelagic CaCO3 production and deep-sea preservation and assess impacts and feedbacks of environmental change.

Rapid coastal deoxygenation due to ocean circulation shift in the NW Atlantic.

Global observations show that the ocean lost approximately 2% of its oxygen inventory over the last five decades 1-3, with important implications for marine ecosystems 4, 5. The rate of change varies with northwest Atlantic coastal waters showing a long-term drop 6, 7 that vastly outpaces the global and North Atlantic basin mean deoxygenation rates 5, 8. However, past work has been unable to resolve mechanisms of large-scale climate forcing from local processes. Here, we use hydrographic evidence to show a Labrador Current retreat is playing a key role in the deoxygenation on the northwest Atlantic shelf. A high-resolution global coupled climate-biogeochemistry model 9 reproduces the observed decline of saturation oxygen concentrations in the region, driven by a retreat of the equatorward-flowing Labrador Current and an associated shift toward more oxygen-poor subtropical waters on the shelf. The dynamical changes underlying the shift in shelf water properties are correlated with a slowdown in the simulated Atlantic Meridional Overturning Circulation 10. Our results provide strong evidence that a major, centennial-scale change of the Labrador Current is underway, and highlight the potential for ocean dynamics to impact coastal deoxygenation over the coming century.

Linked sustainability challenges and trade-offs among fisheries, aquaculture and agriculture.

Fisheries and aquaculture make a crucial contribution to global food security, nutrition and livelihoods. However, the UN Sustainable Development Goals separate marine and terrestrial food production sectors and ecosystems. To sustainably meet increasing global demands for fish, the interlinkages among goals within and across fisheries, aquaculture and agriculture sectors must be recognized and addressed along with their changing nature. Here, we assess and highlight development challenges for fisheries-dependent countries based on analyses of interactions and trade-offs between goals focusing on food, biodiversity and climate change. We demonstrate that some countries are likely to face double jeopardies in both fisheries and agriculture sectors under climate change. The strategies to mitigate these risks will be context-dependent, and will need to directly address the trade-offs among Sustainable Development Goals, such as halting biodiversity loss and reducing poverty. Countries with low adaptive capacity but increasing demand for food require greater support and capacity building to transition towards reconciling trade-offs. Necessary actions are context-dependent and include effective governance, improved management and conservation, maximizing societal and environmental benefits from trade, increased equitability of distribution and innovation in food production, including continued development of low input and low impact aquaculture.

Projections of climate-driven changes in tuna vertical habitat based on species-specific differences in blood oxygen affinity.

Oxygen concentrations are hypothesized to decrease in many areas of the ocean as a result of anthropogenically driven climate change, resulting in habitat compression for pelagic animals. The oxygen partial pressure, pO2 , at which blood is 50% saturated (P50 ) is a measure of blood oxygen affinity and a gauge of the tolerance of animals for low ambient oxygen. Tuna species display a wide range of blood oxygen affinities (i.e., P50 values) and therefore may be differentially impacted by habitat compression as they make extensive vertical movements to forage on subdaily time scales. To project the effects of end-of-the-century climate change on tuna habitat, we calculate tuna P50 depths (i.e., the vertical position in the water column at which ambient pO2 is equal to species-specific blood P50 values) from 21st century Earth System Model (ESM) projections included in the fifth phase of the Climate Model Intercomparison Project (CMIP5). Overall, we project P50 depths to shoal, indicating likely habitat compression for tuna species due to climate change. Tunas that will be most impacted by shoaling are Pacific and southern bluefin tunas-habitat compression is projected for the entire geographic range of Pacific bluefin tuna and for the spawning region of southern bluefin tuna. Vertical shifts in P50 depths will potentially influence resource partitioning among Pacific bluefin, bigeye, yellowfin, and skipjack tunas in the northern subtropical and eastern tropical Pacific Ocean, the Arabian Sea, and the Bay of Bengal. By establishing linkages between tuna physiology and environmental conditions, we provide a mechanistic basis to project the effects of anthropogenic climate change on tuna habitats.

Reconciling fisheries catch and ocean productivity.

Photosynthesis fuels marine food webs, yet differences in fish catch across globally distributed marine ecosystems far exceed differences in net primary production (NPP). We consider the hypothesis that ecosystem-level variations in pelagic and benthic energy flows from phytoplankton to fish, trophic transfer efficiencies, and fishing effort can quantitatively reconcile this contrast in an energetically consistent manner. To test this hypothesis, we enlist global fish catch data that include previously neglected contributions from small-scale fisheries, a synthesis of global fishing effort, and plankton food web energy flux estimates from a prototype high-resolution global earth system model (ESM). After removing a small number of lightly fished ecosystems, stark interregional differences in fish catch per unit area can be explained (r = 0.79) with an energy-based model that (i) considers dynamic interregional differences in benthic and pelagic energy pathways connecting phytoplankton and fish, (ii) depresses trophic transfer efficiencies in the tropics and, less critically, (iii) associates elevated trophic transfer efficiencies with benthic-predominant systems. Model catch estimates are generally within a factor of 2 of values spanning two orders of magnitude. Climate change projections show that the same macroecological patterns explaining dramatic regional catch differences in the contemporary ocean amplify catch trends, producing changes that may exceed 50% in some regions by the end of the 21st century under high-emissions scenarios. Models failing to resolve these trophodynamic patterns may significantly underestimate regional fisheries catch trends and hinder adaptation to climate change.

Net primary productivity estimates and environmental variables in the Arctic Ocean: An assessment of coupled physical-biogeochemical models.

The relative skill of 21 regional and global biogeochemical models was assessed in terms of how well the models reproduced observed net primary productivity (NPP) and environmental variables such as nitrate concentration (NO3), mixed layer depth (MLD), euphotic layer depth (Zeu), and sea ice concentration, by comparing results against a newly updated, quality-controlled in situ NPP database for the Arctic Ocean (1959-2011). The models broadly captured the spatial features of integrated NPP (iNPP) on a pan-Arctic scale. Most models underestimated iNPP by varying degrees in spite of overestimating surface NO3, MLD, and Zeu throughout the regions. Among the models, iNPP exhibited little difference over sea ice condition (ice-free versus ice-influenced) and bottom depth (shelf versus deep ocean). The models performed relatively well for the most recent decade and toward the end of Arctic summer. In the Barents and Greenland Seas, regional model skill of surface NO3 was best associated with how well MLD was reproduced. Regionally, iNPP was relatively well simulated in the Beaufort Sea and the central Arctic Basin, where in situ NPP is low and nutrients are mostly depleted. Models performed less well at simulating iNPP in the Greenland and Chukchi Seas, despite the higher model skill in MLD and sea ice concentration, respectively. iNPP model skill was constrained by different factors in different Arctic Ocean regions. Our study suggests that better parameterization of biological and ecological microbial rates (phytoplankton growth and zooplankton grazing) are needed for improved Arctic Ocean biogeochemical modeling.

Tropical nighttime warming as a dominant driver of variability in the terrestrial carbon sink.

The terrestrial biosphere is currently a strong carbon (C) sink but may switch to a source in the 21st century as climate-driven losses exceed CO2-driven C gains, thereby accelerating global warming. Although it has long been recognized that tropical climate plays a critical role in regulating interannual climate variability, the causal link between changes in temperature and precipitation and terrestrial processes remains uncertain. Here, we combine atmospheric mass balance, remote sensing-modeled datasets of vegetation C uptake, and climate datasets to characterize the temporal variability of the terrestrial C sink and determine the dominant climate drivers of this variability. We show that the interannual variability of global land C sink has grown by 50-100% over the past 50 y. We further find that interannual land C sink variability is most strongly linked to tropical nighttime warming, likely through respiration. This apparent sensitivity of respiration to nighttime temperatures, which are projected to increase faster than global average temperatures, suggests that C stored in tropical forests may be vulnerable to future warming.

Incorporating adaptive responses into future projections of coral bleaching.

Climate warming threatens to increase mass coral bleaching events, and several studies have projected the demise of tropical coral reefs this century. However, recent evidence indicates corals may be able to respond to thermal stress though adaptive processes (e.g., genetic adaptation, acclimatization, and symbiont shuffling). How these mechanisms might influence warming-induced bleaching remains largely unknown. This study compared how different adaptive processes could affect coral bleaching projections. We used the latest bias-corrected global sea surface temperature (SST) output from the NOAA/GFDL Earth System Model 2 (ESM2M) for the preindustrial period through 2100 to project coral bleaching trajectories. Initial results showed that, in the absence of adaptive processes, application of a preindustrial climatology to the NOAA Coral Reef Watch bleaching prediction method overpredicts the present-day bleaching frequency. This suggests that corals may have already responded adaptively to some warming over the industrial period. We then modified the prediction method so that the bleaching threshold either permanently increased in response to thermal history (e.g., simulating directional genetic selection) or temporarily increased for 2-10 years in response to a bleaching event (e.g., simulating symbiont shuffling). A bleaching threshold that changes relative to the preceding 60 years of thermal history reduced the frequency of mass bleaching events by 20-80% compared with the 'no adaptive response' prediction model by 2100, depending on the emissions scenario. When both types of adaptive responses were applied, up to 14% more reef cells avoided high-frequency bleaching by 2100. However, temporary increases in bleaching thresholds alone only delayed the occurrence of high-frequency bleaching by ca. 10 years in all but the lowest emissions scenario. Future research should test the rate and limit of different adaptive responses for coral species across latitudes and ocean basins to determine if and how much corals can respond to increasing thermal stress.

Ecosystem size structure response to 21st century climate projection: large fish abundance decreases in the central North Pacific and increases in the California Current.

Output from an earth system model is paired with a size-based food web model to investigate the effects of climate change on the abundance of large fish over the 21st century. The earth system model, forced by the Intergovernmental Panel on Climate Change (IPCC) Special report on emission scenario A2, combines a coupled climate model with a biogeochemical model including major nutrients, three phytoplankton functional groups, and zooplankton grazing. The size-based food web model includes linkages between two size-structured pelagic communities: primary producers and consumers. Our investigation focuses on seven sites in the North Pacific, each highlighting a specific aspect of projected climate change, and includes top-down ecosystem depletion through fishing. We project declines in large fish abundance ranging from 0 to 75.8% in the central North Pacific and increases of up to 43.0% in the California Current (CC) region over the 21st century in response to change in phytoplankton size structure and direct physiological effects. We find that fish abundance is especially sensitive to projected changes in large phytoplankton density and our model projects changes in the abundance of large fish being of the same order of magnitude as changes in the abundance of large phytoplankton. Thus, studies that address only climate-induced impacts to primary production without including changes to phytoplankton size structure may not adequately project ecosystem responses.

A parahydrogen based NMR study of Pt catalysed alkyne hydrogenation.

A parahydrogen based NMR study of the platinum(ii) bis-phosphine triflate catalysed hydrogenation of alkynes in methanol reveals that platinum bis-phosphine alkyl cations and methanol functionalised platinum bis-phosphine alkylether cations, are responsible for the observed alkene and vinylether products.

Palladium catalysed alkyne hydrogenation and oligomerisation: a parahydrogen based NMR investigation.

The role phosphine ligands play in the palladium(ii)-bis-phosphine-hydride cation catalysed hydrogenation of diphenylacetylene is explored through a PHIP (parahydrogen induced polarization) NMR study. The precursors Pd(LL')(OTf)(2) (1a-e) [LL' = dcpe (PCy(2)CH(2)CH(2)PCy(2)), dppe, dppm, dppp, cppe (PCy(2)CH(2)CH(2)PPh(2))] are used. Alkyl palladium intermediates of the type [Pd(LL')(CHPhCH(2)Ph)](OTf) ( and ) are detected and demonstrated to play an active role in hydrogenation catalysis. Magnetization transfer experiments reveal chemical exchange from the alpha-H of the alkyl ligand of (LL' = dcpe) and linkage isomer ' (LL' = cppe) into trans-stilbene on the NMR timescale. Activation parameters (DeltaH( not equal) and DeltaS( not equal)) for this transformation have been determined. These experiments, coupled with GC/MS data, indicate that the catalytic activity is greater in methanol, where it follows the order: dcpe > cppe > dppp > dppe > dppm, than in CD(2)Cl(2). All five of the phosphine systems described are less active than those based on bcope [where bcope is (C(8)H(14))PCH(2)-CH(2)P(C(8)H(14))] and (t)bucope [where (t)bucope is (C(8)H(14))PC(6)H(4)CH(2)P((t)Bu)(2)]. cis, cis-1,2,3,4-Tetraphenyl-buta-1,3-diene is detected as a minor reaction product with Pd(LL')(PhCH-CHPh-CPh=CHPh)(+) (4) also being shown to play a role in the alkyne dimerisation step.