The importance of transport model uncertainties for the estimation of CO2 sources and sinks using satellite measurements

This study presents a synthetic model intercomparison to investigate the importance of transport model errors for estimating the sources and sinks of CO2 using satellite measurements. The experiments were designed for testing the potential performance of the proposed CO2 lidar A-SCOPE, but also apply to other space borne missions that monitor total column CO2. The participating transport models IFS, LMDZ, TM3, and TM5 were run in forward and inverse mode using common a priori CO2 fluxes and initial concentrations. Forward simulations of column averaged CO2 (xCO2) mixing ratios vary between the models by s=0.5 ppm over the continents and s=0.27 ppm over the oceans. Despite the fact that the models agree on average on the sub-ppm level, these modest differences nevertheless lead to significant discrepancies in the inverted fluxes of 0.1 PgC/yr per 106 km2 over land and 0.03 PgC/yr per 106 km2 over the ocean. These transport model induced flux uncertainties exceed the target requirement that was formulated for the A-SCOPE mission of 0.02 PgC/yr per 106 km2, and could also limit the overall performance of other CO2 missions such as GOSAT. A variable, but overall encouraging agreement is found in comparison with FTS measurements at Park Falls, Darwin, Spitsbergen, and Bremen, although systematic differences are found exceeding the 0.5 ppm level. Because of this, our estimate of the impact of transport model uncerainty is likely to be conservative. It is concluded that to make use of the remote sensing technique for quantifying the sources and sinks of CO2 not only requires highly accurate satellite instruments, but also puts stringent requirements on the performance of atmospheric transport models. Improving the accuracy of these models should receive high priority, which calls for a closer collaboration between experts in atmospheric dynamics and tracer transpor

Corrigendum to "First direct observation of the atmospheric CO2 year-to-year increase from space" published in Atmos. Chem. Phys., 7, 4249─4256, 2007

No abstract available

Derivation of tropospheric methane from TCCON CH₄ and HF total column observations

The Total Carbon Column Observing Network (TCCON) is a global ground-based network of Fourier transform spectrometers that produce precise measurements of column-averaged dry-air mole fractions of atmospheric methane (CH₄). Temporal variability in the total column of CH₄ due to stratospheric dynamics obscures fluctuations and trends driven by tropospheric transport and local surface fluxes that are critical for understanding CH₄ sources and sinks. We reduce the contribution of stratospheric variability from the total column average by subtracting an estimate of the stratospheric CH₄ derived from simultaneous measurements of hydrogen fluoride (HF). HF provides a proxy for stratospheric CH₄ because it is strongly correlated to CH₄ in the stratosphere, has an accurately known tropospheric abundance (of zero), and is measured at most TCCON stations. The stratospheric partial column of CH₄ is calculated as a function of the zonal and annual trends in the relationship between CH₄ and HF in the stratosphere, which we determine from ACE-FTS satellite data. We also explicitly take into account the CH₄ column averaging kernel to estimate the contribution of stratospheric CH₄ to the total column. The resulting tropospheric CH₄ columns are consistent with in situ aircraft measurements and augment existing observations in the troposphere

First direct observation of the atmospheric CO2 year-to-year increase from space

The reliable prediction of future atmospheric CO₂ concentrations and associated global climate change requires an adequate understanding of the CO₂ sources and sinks. The sparseness of the existing surface measurement network limits current knowledge about the global distribution of CO₂ surface fluxes. The retrieval of CO₂ total vertical columns from satellite observations is predicted to improve this situation. Such an application however requires very high accuracy and precision. We report on retrievals of the column-averaged CO₂ dry air mole fraction, denoted XCO₂, from the near-infrared nadir spectral radiance and solar irradiance measurements of the SCIAMACHY satellite instrument between 2003 and 2005. We focus on northern hemispheric large scale CO₂ features such as the CO₂ seasonal cycle and show - for the first time - that the atmospheric annual increase of CO₂ can be directly observed using satellite measurements of the CO₂ total column. The satellite retrievals are compared with global XCO₂ obtained from NOAA's CO₂ assimilation system CarbonTracker taking into account the spatio-temporal sampling and altitude sensitivity of the satellite data. We show that the measured CO₂ year-to-year increase agrees within about 1 ppm/year with CarbonTracker. We also show that the latitude dependent amplitude of the northern hemispheric CO₂ seasonal cycle agrees with CarbonTracker within about 2 ppm with the retrieved amplitude being systematically larger. The analysis demonstrates that it is possible using satellite measurements of the CO₂ total column to retrieve information on the atmospheric CO₂ on the level of a few parts per million

Constraints for the photolysis rate and the equilibrium constant of ClO-dimer from airborne and balloon-borne measurements of chlorine compounds

We analyze measurements of ClO across the terminator taken by the Airborne Submillimeter Radiometer (ASUR) in the activated vortices of the Arctic winters of 1995/1996, 1996/1997, and 1999/2000 to evaluate the plausibility of various determinations of the ClO-dimer photolysis cross section and the rate constant controlling the thermal equilibrium between ClO-dimer and ClO. We use measured ClO during sunlit conditions to estimate total active chlorine (ClOx). As the measurements suggest nearly full chlorine activation in winter 1999/2000, we compare ClOx estimates based on various photolysis frequencies of ClO-dimer with total available inorganic chlorine (Cly), estimated from an N2O-Cly correlation established by a balloon-borne MkIV interferometer measurement. Only ClO-dimer cross sections leading to the fastest photolysis frequencies in the literature (including the latest evaluation by the Jet Propulsion Laboratory) give ClOx mixing ratios that overlap with the estimated range of available Cly. Slower photolysis rates lead to ClOx values that are higher than available Cly. We use the ClOx calculated from sunlit ClO measurements to estimate ClO in darkness based on different equilibrium constants, and compare it with ASUR ClO measurements before sunrise at high solar zenith angles. Calculations with equilibrium constants published in recent evaluations of the Jet Propulsion Laboratory give good agreement with observed ClO mixing ratios. Equilibrium constants leading to a higher ClO/ClOx ratio in darkness yield ClO values that tend to exceed observed abundances. Perturbing the rates for the ClO + BrO reaction in a manner that increases OClO formation and decreases BrCl formation leads to lower ClO values calculated for twilight conditions after sunset, resulting in better agreement with ASUR measurements

Nitrous oxide and methane in two tropical estuaries in a peat-dominated region of northwestern Borneo

Estuaries are sources of nitrous oxide (N2O) and methane (CH4) to the atmosphere. However, our present knowledge of N2O and CH4 emissions from estuaries in the tropics is very limited because data are scarce. In this study, we present first measurements of dissolved N2O and CH4 from two estuaries in a peat-dominated region of northwestern Borneo. Two campaigns (during the dry season in June 2013 and during the wet season in March 2014) were conducted in the estuaries of the Lupar and Saribas rivers. Median N2O concentrations ranged between 7.2 and 12.3 nmol L−1 and were higher in the marine end-member (13.0 ± 7.0 nmol L−1). CH4 concentrations were low in the coastal ocean (3.6 ± 0.2 nmol L−1) and higher in the estuaries (medians between 10.6 and 64.0 nmol L−1). The respiration of abundant organic matter and presumably anthropogenic input caused slight eutrophication, which did not lead to hypoxia or enhanced N2O concentrations, however. Generally, N2O concentrations were not related to dissolved inorganic nitrogen concentrations. Thus, the use of an emission factor for the calculation of N2O emissions from the inorganic nitrogen load leads to an overestimation of the flux from the Lupar and Saribas estuaries. N2O was negatively correlated with salinity during the dry season, which suggests a riverine source. In contrast, N2O concentrations during the wet season were not correlated with salinity but locally enhanced within the estuaries, implying that there were additional estuarine sources during the wet (i.e., monsoon) season. Estuarine CH4 distributions were not driven by freshwater input but rather by tidal variations. Both N2O and CH4 concentrations were more variable during the wet season. We infer that the wet season dominates the variability of the N2O and CH4 concentrations and subsequent emissions from tropical estuaries. Thus, we speculate that any changes in the Southeast Asian monsoon system will lead to changes in the N2O and CH4 emissions from these systems. We also suggest that the ongoing cultivation of peat soil in Borneo is likely to increase N2O emissions from these estuaries, while the effect on CH4 remains uncertain

Long-term tropospheric formaldehyde concentrations deduced from ground-based fourier transform solar infrared measurements

International audienceLong-term total column measurements of formaldehyde (HCHO) covering a 12 year period from 1992 to 2004 are reported from spectra recorded with a high-resolution Fourier Transform Spectrometer (FTS) using the sun as a light source at a Southern Hemisphere site (Lauder, New Zealand). The ambient HCHO concentrations at this rural location are often at background levels (15 molecules cm?2, the maximum occurring in the summer. A simple box model of CH4 oxidation reproduces the seasonal cycle, but significantly underestimates the maximum HCHO ground concentrations deduced from the column observations, particularly in summer. This implies the existence of a significant source of HCHO that cannot be explained by oxidation of CH4 alone. The ground-based FTS column data compares well with collocated HCHO column measurements from the Global Ozone Monitoring Experiment (GOME) satellite instrument (r2=0.65, mean bias=10%, n=48)

Trend in ice moistening the stratosphere – constraints from isotope data of water and methane

Water plays a major role in the chemistry and radiative budget of the stratosphere. Air enters the stratosphere predominantly in the tropics, where the very low temperatures around the tropopause constrain water vapour mixing ratios to a few parts per million. Observations of stratospheric water vapour show a large positive long-term trend, which can not be explained by change in tropopause temperatures. Trends in the partitioning between vapour and ice of water entering the stratosphere have been suggested to resolve this conundrum. We present measurements of stratospheric H_(2)O, HDO, CH_4 and CH_(3)D in the period 1991–2007 to evaluate this hypothesis. Because of fractionation processes during phase changes, the hydrogen isotopic composition of H_(2)O is a sensitive indicator of changes in the partitioning of vapour and ice. We find that the seasonal variations of H_(2)O are mirrored in the variation of the ratio of HDO to H_(2)O with a slope of the correlation consistent with water entering the stratosphere mainly as vapour. The variability in the fractionation over the entire observation period is well explained by variations in H_(2)O. The isotopic data allow concluding that the trend in ice arising from particulate water is no more than (0.01±0.13) ppmv/decade in the observation period. Our observations suggest that between 1991 and 2007 the contribution from changes in particulate water transported through the tropopause plays only a minor role in altering in the amount of water entering the stratosphere

Towards understanding the variability in biospheric CO2 fluxes:Using FTIR spectrometry and a chemical transport model to investigate the sources and sinks of carbonyl sulfide and its link to CO2

Understanding carbon dioxide (CO2) biospheric processes is of great importance because the terrestrial exchange drives the seasonal and interannual variability of CO2 in the atmosphere. Atmospheric inversions based on CO2 concentration measurements alone can only determine net biosphere fluxes, but not differentiate between photosynthesis (uptake) and respiration (production). Carbonyl sulfide (OCS) could provide an important additional constraint: it is also taken up by plants during photosynthesis but not emitted during respiration, and therefore is a potential means to differentiate between these processes. Solar absorption Fourier Transform InfraRed (FTIR) spectrometry allows for the retrievals of the atmospheric concentrations of both CO2 and OCS from measured solar absorption spectra. Here, we investigate co-located and quasi-simultaneous FTIR measurements of OCS and CO2 performed at five selected sites located in the Northern Hemisphere. These measurements are compared to simulations of OCS and CO2 using a chemical transport model (GEOS-Chem). The coupled biospheric fluxes of OCS and CO2 from the simple biosphere model (SiB) are used in the study. The CO2 simulation with SiB fluxes agrees with the measurements well, while the OCS simulation reproduced a weaker drawdown than FTIR measurements at selected sites, and a smaller latitudinal gradient in the Northern Hemisphere during growing season when comparing with HIPPO (HIAPER Pole-to-Pole Observations) data spanning both hemispheres. An offset in the timing of the seasonal cycle minimum between SiB simulation and measurements is also seen. Using OCS as a photosynthesis proxy can help to understand how the biospheric processes are reproduced in models and to further understand the carbon cycle in the real world