Abstract. Over the last decade, advanced statistical inference and machine learning have been used to fill the gaps in sparse surface ocean CO2 measurements (Rödenbeck et al. 2015). The estimates from these methods have been used to constrain seasonal, interannual and decadal variability in sea-air CO2 fluxes and the drivers of these changes (Landschützer et al. 2015, 2016, Gregor et al. 2018). However, it is also becoming clear that these methods are converging towards a common bias and RMSE boundary: the wall, which suggests that pCO2 estimates are now limited by both data gaps and scale-sensitive observations. Here, we analyse this problem by introducing a new gap-filling method, an ensemble of six machine learning models (CSIR-ML6 version 2019a), where each model is constructed with a two-step clustering-regression approach. The ensemble is then statistically compared to well-established methods. The ensemble, CSIR-ML6, has an RMSE of 17.16 µatm and bias of 0.89 µatm when compared to a test-dataset kept separate from training procedures. However, when validating our estimates with independent datasets, we find that our method improves only incrementally on other gap-filling methods. We investigate the differences between the methods to understand the extent of the limitations of gap-filling estimates of pCO2. We show that disagreement between methods in the South Atlantic, southeastern Pacific and parts of the Southern Ocean are too large to interpret the interannual variability with confidence. We conclude that improvements in surface ocean pCO2 estimates will likely be incremental with the optimisation of gap-filling methods by (1) the inclusion of additional clustering and regression variables (e.g. eddy kinetic energy), (2) increasing the sampling resolution. Larger improvements will only be realised with an increase in CO2 observational coverage, particularly in today's poorly sampled areas.
FORMATION OF DIFFUSION BARRIERS IN THE COPPER METALLIZATION SYSTEM IN THE GAP FILLING METHOD
