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We present improved estimates of air–sea CO₂exchange over three latitude bands of the Southern Ocean using atmospheric CO₂measurements from global airborne campaigns and an atmospheric 4-box inverse model based on a mass-indexed isentropic coordinate (M_θe). These flux estimates show two features not clearly resolved in previous estimates based on inverting surface CO₂measurements: a weak winter-time outgassing in the polar region and a sharp phase transition of the seasonal flux cycles between polar/subpolar and subtropical regions. The estimates suggest much stronger summer-time uptake in the polar/subpolar regions than estimates derived through neural-network interpolation of pCO₂data obtained with profiling floats but somewhat weaker uptake than a recent study by Long et al. [Science374, 1275–1280 (2021)], who used the same airborne data and multiple atmospheric transport models (ATMs) to constrain surface fluxes. Our study also uses moist static energy (MSE) budgets from reanalyses to show that most ATMs tend to have excessive diabatic mixing (transport across moist isentrope, θ_e, or M_θesurfaces) at high southern latitudes in the austral summer, which leads to biases in estimates of air–sea CO₂exchange. Furthermore, we show that the MSE-based constraint is consistent with an independent constraint on atmospheric mixing based on combining airborne and surface CO₂observations. 

Abstract Seasonal change of atmospheric potential oxygen (APO ∼ O₂ + CO₂) is a tracer for air‐sea O₂flux with little sensitivity to the terrestrial exchange of O₂and CO₂. In this study, we present the tropospheric distribution and inventory of APO in each hemisphere with seasonal resolution, using O₂and CO₂measurements from discrete airborne campaigns between 2009 and 2018. The airborne data are represented on a mass‐weighted isentropic coordinate (M_θe) as an alternative to latitude, which reduces the noise from synoptic variability in the APO cycles. We find a larger seasonal amplitude of APO inventory in the Southern Hemisphere relative to the Northern Hemisphere, and a larger amplitude in high latitudes (lowM_θe) relative to low latitudes (highM_θe) within each hemisphere. With a box model, we invert the seasonal changes in APO inventory to yield estimates of air‐sea flux cycles at the hemispheric scale. We found a larger seasonal net outgassing of APO in the Southern Hemisphere (518 ± 52.6 Tmol) than in the Northern Hemisphere (342 ± 52.1 Tmol). Differences in APO phasing and amplitude between the hemispheres suggest distinct physical and biogeochemical mechanisms driving the air‐sea O₂fluxes, such as fall outgassing of photosynthetic O₂in the Northern Hemisphere, possibly associated with the formation of the seasonal subsurface shallow oxygen maximum. We compare our estimates with four model‐ and observation‐based products, identifying key limitations in these products or in the tools used to create them. 

The global ocean's oxygen content has declined significantly over the past several decades and is expected to continue decreasing under global warming, with far-reaching impacts on marine ecosystems and biogeochemical cycling. Determining the oxygen trend, its spatial pattern, and uncertainties from observations is fundamental to our understanding of the changing ocean environment. This study uses a suite of CMIP6 Earth system models to evaluate the biases and uncertainties in oxygen distribution and trends due to sampling sparseness. Model outputs are sub-sampled according to the spatial and temporal distribution of the historical shipboard measurements, and the data gaps are filled by a simple optimal interpolation method using Gaussian covariance with a constant e-folding length scale. Sub-sampled results are compared to full model output, revealing the biases in global and basin-wise oxygen content trends. The simple optimal interpolation underestimates the modeled global deoxygenation trends, capturing approximately two-thirds of the full model trends. The North Atlantic and subpolar North Pacific are relatively well sampled, and the simple optimal interpolation is capable of reconstructing more than 80% of the oxygen trend in the non-eddying CMIP models. In contrast, pronounced biases are found in the equatorial oceans and the Southern Ocean, where the sampling density is relatively low. The application of the simple optimal interpolation method to the historical dataset estimated the global oxygen loss to be 1.5% over the past 50 years. However, the ratio of the global oxygen trend between the sub-sampled and full model output has increased the estimated loss rate in the range of 1.7% to 3.1% over the past 50 years, which partially overlaps with previous studies. The approach taken in this study can provide a framework for the intercomparison of different statistical gap-filling methods to estimate oxygen content trends and their uncertainties due to sampling sparseness. 

Abstract. Monitoring, reporting, and verification (MRV) refers to the multistep process of monitoring the amount of greenhouse gas removed by a carbon dioxide removal (CDR) activity and reporting the results of the monitoring to a third party. The third party then verifies the reporting of the results. While MRV is usually conducted in pursuit of certification in a voluntary or regulated CDR market, this chapter focuses on key recommendations for MRV relevant to ocean alkalinity enhancement (OAE) research. Early stage MRV for OAE research may become the foundation on which markets are built. Therefore, such research carries a special obligation toward comprehensiveness, reproducibility, and transparency. Observational approaches during field trials should aim to quantify the delivery of alkalinity to seawater and monitor for secondary precipitation, biotic calcification, and other ecosystem changes that can feed back on sources or sinks of greenhouse gases where alkalinity is measurably elevated. Observations of resultant shifts in the partial pressure of CO2 (pCO2) and ocean pH can help determine the efficacy of OAE and are amenable to autonomous monitoring. However, because the ocean is turbulent and energetic and CO2 equilibration between the ocean and atmosphere can take several months or longer, added alkalinity will be diluted to perturbation levels undetectable above background variability on timescales relevant for MRV. Therefore, comprehensive quantification of carbon removal via OAE will be impossible through observational methods alone, and numerical simulations will be required. The development of fit-for-purpose models, carefully validated against observational data, will be a critical part of MRV for OAE. 

Abstract Estimates suggest that over 4 gigatons per year of carbon dioxide (Gt-CO₂year⁻¹) be removed from the atmosphere by 2050 to meet international climate goals. One strategy for carbon dioxide removal is seaweed farming; however its global potential remains highly uncertain. Here, we apply a dynamic seaweed growth model that includes growth-limiting mechanisms, such as nitrate supply, to estimate the global potential yield of four types of seaweed. We estimate that harvesting 1 Gt year⁻¹of seaweed carbon would require farming over 1 million km²of the most productive exclusive economic zones, located in the equatorial Pacific; the cultivation area would need to be tripled to attain an additional 1 Gt year⁻¹of harvested carbon, indicating dramatic reductions in carbon harvest efficiency beyond the most productive waters. Improving the accuracy of annual harvest yield estimates requires better understanding of biophysical constraints such as seaweed loss rates (e.g., infestation, disease, grazing, wave erosion). 

Abstract The California Current System (CCS) sustains economically valuable fisheries and is particularly vulnerable to ocean acidification, due to its natural upwelling of carbon-enriched waters that generate corrosive conditions for local ecosystems. Here we use a novel suite of retrospective, initialized ensemble forecasts with an Earth system model (ESM) to predict the evolution of surface pH anomalies in the CCS. We show that the forecast system skillfully predicts observed surface pH variations a year in advance over a naive forecasting method, with the potential for skillful prediction up to five years in advance. Skillful predictions of surface pH are mainly derived from the initialization of dissolved inorganic carbon anomalies that are subsequently transported into the CCS. Our results demonstrate the potential for ESMs to provide skillful predictions of ocean acidification on large scales in the CCS. Initialized ESMs could also provide boundary conditions to improve high-resolution regional forecasting systems. 

Abstract. While there is agreement that global warming over the 21st century is likely to influence the biological pump, Earth system models (ESMs) display significant divergence in their projections of future new production. This paper quantifies and interprets the sensitivity of projected changes in new production in an idealized global ocean biogeochemistry model. The model includes two tracers that explicitly represent nutrient transport, light- and nutrient-limited nutrient uptake by the ecosystem (new production), and export via sinking organic particles. Globally, new production declines with warming due to reduced surface nutrient availability, as expected. However, the magnitude, seasonality, and underlying dynamics of the nutrient uptake are sensitive to the light and nutrient dependencies of uptake, which we summarize in terms of a single biological timescale that is a linear combination of the partial derivatives of production with respect to light and nutrients. Although the relationships are nonlinear, this biological timescale is correlated with several measures of biogeochemical function: shorter timescales are associated with greater global annual new production and higher nutrient utilization. Shorter timescales are also associated with greater declines in global new production in a warmer climate and greater sensitivity to changes in nutrients than light. Future work is needed to characterize more complex ocean biogeochemical models in terms of similar timescale generalities to examine their climate change implications. 

The Southern Ocean plays an important role in determining atmospheric carbon dioxide (CO 2 ), yet estimates of air-sea CO 2 flux for the region diverge widely. In this study, we constrained Southern Ocean air-sea CO 2 exchange by relating fluxes to horizontal and vertical CO 2 gradients in atmospheric transport models and applying atmospheric observations of these gradients to estimate fluxes. Aircraft-based measurements of the vertical atmospheric CO 2 gradient provide robust flux constraints. We found an annual mean flux of –0.53 ± 0.23 petagrams of carbon per year (net uptake) south of 45°S during the period 2009–2018. This is consistent with the mean of atmospheric inversion estimates and surface-ocean partial pressure of CO 2 ( P co 2 )–based products, but our data indicate stronger annual mean uptake than suggested by recent interpretations of profiling float observations.