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Abstract. Phytoplankton calcifiers contribute to global carbon cycling through their dual formation of calcium carbonate and particulate organic carbon (POC). The carbonate might provide an efficient export pathway for the associated POC to the deep ocean, reducing the particles' exposure to biological degradation in the upper ocean and increasing the particle settling rate. Previous work has suggested ballasting of POC by carbonate might increase in a warming climate, in spite of increasing carbonate dissolution rates, because calcifiers benefit from the widespread nutrient limitation arising from stratification. We compare the biogeochemical responses of three models containing (1) a single mixed phytoplankton class, (2) additional explicit small phytoplankton and calcifiers, and (3) additional explicit small phytoplankton and calcifiers with a prognostic carbonate ballast model, to two rapid changes in atmospheric CO2. The first CO2 scenario represents a rapid (151-year) transition from a stable icehouse climate (283.9 ppm) into a greenhouse climate (1263 ppm); the second represents a symmetric rapid transition from a stable greenhouse climate into an icehouse climate. We identify a slope change in the global net primary production response with a transition point at about 3.5 ∘C global mean sea surface temperature change in all models, driven by a combination of physical and biological changes. We also find that in both warming and cooling scenarios, the application of a prognostic carbonate ballast model moderates changes in carbon export production, suboxic volume, and nitrate sources and sinks, reducing the long-term model response to about one-third that of the calcifier model without ballast. Explicit small phytoplankton and calcifiers, and carbonate ballasting, increase the physical separation of nitrate sources and sinks through a combination of phytoplankton competition and lengthened remineralization profile, resulting in a significantly higher global nitrate inventory in this model compared to the single phytoplankton type model (15 % and 32 % higher for icehouse and greenhouse climates). Higher nitrate inventory alleviates nitrate limitation, increasing phytoplankton sensitivity to changes in physical limitation factors (light and temperature). This larger sensitivity to physical forcing produces stronger shifts in ocean phosphate storage between icehouse and greenhouse climates. The greenhouse climate is found to hold phosphate and nitrate deeper in the ocean, despite a shorter remineralization length scale than the icehouse climate, because of the longer residence times of the deep water masses. We conclude the global biogeochemical impact of calcifiers extends beyond their role in global carbon cycling, and that the ecological composition of the global ocean can affect how ocean biogeochemistry responds to climate forcing.

Abstract. Nitrous oxide (N2O) is a long-lived potent greenhouse gas and stratospheric ozone-depleting substance that has been accumulating in the atmosphere since the preindustrial period. The mole fraction of atmospheric N2O has increased by nearly 25 % from 270 ppb (parts per billion) in 1750 to 336 ppb in 2022, with the fastest annual growth rate since 1980 of more than 1.3 ppb yr−1 in both 2020 and 2021. According to the Sixth Assessment Report of the Intergovernmental Panel on Climate Change (IPCC AR6), the relative contribution of N2O to the total enhanced effective radiative forcing of greenhouse gases was 6.4 % for 1750–2022. As a core component of our global greenhouse gas assessments coordinated by the Global Carbon Project (GCP), our global N2O budget incorporates both natural and anthropogenic sources and sinks and accounts for the interactions between nitrogen additions and the biogeochemical processes that control N2O emissions. We use bottom-up (BU: inventory, statistical extrapolation of flux measurements, and process-based land and ocean modeling) and top-down (TD: atmospheric measurement-based inversion) approaches. We provide a comprehensive quantification of global N2O sources and sinks in 21 natural and anthropogenic categories in 18 regions between 1980 and 2020. We estimate that total annual anthropogenic N2O emissions have increased 40 % (or 1.9 Tg N yr−1) in the past 4 decades (1980–2020). Direct agricultural emissions in 2020 (3.9 Tg N yr−1, best estimate) represent the large majority of anthropogenic emissions, followed by other direct anthropogenic sources, including fossil fuel and industry, waste and wastewater, and biomass burning (2.1 Tg N yr−1), and indirect anthropogenic sources (1.3 Tg N yr−1) . For the year 2020, our best estimate of total BU emissions for natural and anthropogenic sources was 18.5 (lower–upper bounds: 10.6–27.0) Tg N yr−1, close to our TD estimate of 17.0 (16.6–17.4) Tg N yr−1. For the 2010–2019 period, the annual BU decadal-average emissions for both natural and anthropogenic sources were 18.2 (10.6–25.9) Tg N yr−1 and TD emissions were 17.4 (15.8–19.20) Tg N yr−1. The once top emitter Europe has reduced its emissions by 31 % since the 1980s, while those of emerging economies have grown, making China the top emitter since the 2010s. The observed atmospheric N2O concentrations in recent years have exceeded projected levels under all scenarios in the Coupled Model Intercomparison Project Phase 6 (CMIP6), underscoring the importance of reducing anthropogenic N2O emissions. To evaluate mitigation efforts and contribute to the Global Stocktake of the United Nations Framework Convention on Climate Change, we propose the establishment of a global network for monitoring and modeling N2O from the surface through to the stratosphere. The data presented in this work can be downloaded from https://doi.org/10.18160/RQ8P-2Z4R (Tian et al., 2023).