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Outgassing of carbon dioxide (CO 2 ) from river surface waters, estimated using partial pressure of dissolved CO 2 , has recently been considered an important component of the global carbon budget. However, little is still known about the high-frequency dynamics of CO 2 emissions in small-order rivers and streams. To analyse such highly dynamic systems, we propose a time-varying functional principal components analysis (FPCA) for non-stationary functional time series (FTS). This time-varying FPCA is performed in the frequency domain to investigate how the variability and auto-covariance structures in a FTS change over time. This methodology, and the associated proposed inference, enables investigation of the changes over time in the variability structure of the diurnal profiles of the partial pressure of CO 2 and identification of the drivers of those changes. By means of a simulation study, the performance of the time-varying dynamic FPCs is investigated under different scenarios of complete and incomplete FTS. Although the time-varying dynamic FPCA has been applied here to study the daily processes of consuming and producing CO 2 in a small catchment of the river Dee in Scotland, this methodology can be applied more generally to any dynamic time series.Supplementary materials accompanying this paper appear online. [ABSTRACT FROM AUTHOR]

The Orbiting Carbon Observatory-2 (OCO-2) collects infrared spectra from which atmospheric properties are retrieved. OCO-2 operational data processing uses optimal estimation (OE), a state-of-the-art approach to inference of atmospheric properties from satellite measurements. One of the main advantages of the OE approach is computational efficiency, but it only characterizes the first two moments of the posterior distribution of interest. Here we obtain samples from the posterior using a Markov Chain Monte Carlo (MCMC) algorithm and compare this empirical estimate of the true posterior to the OE results. We focus on 600 simulated soundings that represent the variability of physical conditions encountered by OCO-2 between November 2014 and January 2016. We treat the two retrieval methods as ensemble and density probabilistic forecasts, where the MCMC yields an ensemble from the posterior and the OE retrieval result provide the first two moments of a normal distribution. To compare these methods, we apply both univariate and multivariate diagnostic tools and proper scoring rules. The general impression from our study is that when compared to MCMC, the OE retrieval performs reasonably well for the main quantity of interest, the column-averaged CO2 concentration XCO2, but not for the full state vector X which includes a profile of CO2 concentrations over 20 pressure levels, as well as several other atmospheric properties.Supplementary materials accompanying this paper appear on-line. [ABSTRACT FROM AUTHOR]