Global high‐precision atmospheric Δ14CO2 records covering the last two decades are presented, and evaluated in terms of changing (radio)carbon sources and sinks, using the coarse‐grid carbon cycle model GRACE. Dedicated simulations of global trends and interhemispheric differences with respect to atmospheric CO2 as well as δ13CO2 and Δ14CO2, are shown to be in good agreement with the available observations (1940–2008). While until the 1990s the decreasing trend of Δ14CO2 was governed by equilibration of the atmospheric bomb 14C perturbation with the oceans and terrestrial biosphere, the largest perturbation today are emissions of 14C‐free fossil fuel CO2. This source presently depletes global atmospheric Δ14CO2 by 12–14‰ yr−1, which is partially compensated by 14CO2 release from the biosphere, industrial 14C emissions and natural 14C production. Fossil fuel emissions also drive the changing north–south gradient, showing lower Δ14C in the northern hemisphere only since 2002. The fossil fuel‐induced north–south (and also troposphere–stratosphere) Δ14CO2 gradient today also drives the tropospheric Δ14CO2 seasonality through variations of air mass exchange between these atmospheric compartments. Neither the observed temporal trend nor the Δ14CO2 north–south gradient may constrain global fossil fuel CO2 emissions to better than 25%, due to large uncertainties in other components of the (radio)carbon cycle.

[1] This paper documents a global Bayesian variational inversion of CO 2 surface fluxes during the period . Weekly fluxes are estimated on a 3.75°× 2.5°(longitudelatitude) grid throughout the 21 years. The assimilated observations include 128 station records from three large data sets of surface CO 2 mixing ratio measurements. A Monte Carlo approach rigorously quantifies the theoretical uncertainty of the inverted fluxes at various space and time scales, which is particularly important for proper interpretation of the inverted fluxes. Fluxes are evaluated indirectly against two independent CO 2 vertical profile data sets constructed from aircraft measurements in the boundary layer and in the free troposphere. The skill of the inversion is evaluated by the improvement brought over a simple benchmark flux estimation based on the observed atmospheric growth rate. Our error analysis indicates that the carbon budget from the inversion should be more accurate than the a priori carbon budget by 20% to 60% for terrestrial fluxes aggregated at the scale of subcontinental regions in the Northern Hemisphere and over a year, but the inversion cannot clearly distinguish between the regional carbon budgets within a continent. On the basis of the independent observations, the inversion is seen to improve the fluxes compared to the benchmark: the atmospheric simulation of CO 2 with the Bayesian inversion method is better by about 1 ppm than the benchmark in the free troposphere, despite possible systematic transport errors. The inversion achieves this improvement by changing the regional fluxes over land at the seasonal and at the interannual time scales. Citation: Chevallier, F., et al. (2010), CO 2 surface fluxes at grid point scale estimated from a global 21 year reanalysis of atmospheric measurements,

Abstract. Within the project MUSICA (MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water), long-term tropospheric water vapour isotopologue data records are provided for ten globally distributed ground-based mid-infrared remote sensing stations of the NDACC (Network for the Detection of Atmospheric Composition Change). We present a new method allowing for an extensive and straightforward characterisation of the complex nature of such isotopologue remote sensing datasets. We demonstrate that the MUSICA humidity profiles are representative for most of the troposphere with a vertical resolution ranging from about 2 km (in the lower troposphere) to 8 km (in the upper troposphere) and with an estimated precision of better than 10 %. We find that the sensitivity with respect to the isotopologue composition is limited to the lower and middle troposphere, whereby we estimate a precision of about 30 ‰ for the ratio between the two isotopologues HD 16 O and H 16 2 O. The measurement noise, the applied atmospheric temperature profiles, the uncertainty in the spectral baseline, and the cross-dependence on humidity are the leading error sources. We introduce an a posteriori correction method of the cross-dependence on humidity, and we recommend applying it to isotopologue ratio remote sensing datasets in general. In addition, we present mid-infrared CO 2 retrievals and use them for demonstrating the MUSICA network-wide data consistency.In order to indicate the potential of long-term isotopologue remote sensing data if provided with a well-documented quality, we present a climatology and compare it to simulations of an isotope incorporated AGCM (Atmospheric General Circulation Model). We identify differences in the multiyear mean and seasonal cycles that significantly exceed the estimated errors, thereby indicating deficits in the modeled atmospheric water cycle.

We have used an AGCM (atmospheric general circulation model)-based Chemistry Transport Model (ACTM) for the simulation of methane (CH 4 ) in the height range of earth's surface to about 90 km. The model simulations are compared with measurements at hourly, daily, monthly and interannual time scales by filtering or averaging all the timeseries appropriately. From this model-observation comparison, we conclude that the recent (1990)(1991)(1992)(1993)(1994)(1995)(1996)(1997)(1998)(1999)(2000)(2001)(2002)(2003)(2004)(2005)(2006) trends in growth rate and seasonal cycle at most measurement sites can be fairly successfully modeled by using existing knowledge of CH 4 flux trends and seasonality. A large part of the interannual variability (IAV) in CH 4 growth rate is apparently controlled by IAV in atmospheric dynamics at the tropical sites and forest fires in the high latitude sites. The flux amplitudes are optimized with respect to the available hydroxyl radical (OH) distribution and model transport for successful reproduction of latitudinal and longitudinal distribution of observed CH 4 mixing ratio at the earth's surface. Estimated atmospheric CH 4 lifetime in this setup is 8.6 years. We found a small impact (less than 0.5 ppb integrated over 1 year) of OH diurnal variation, due to temperature dependence of reaction rate coe‰cient, on CH 4 simulation compared to the transport related variability (order of G15 ppb at interannual timescales). Model-observation comparisons of seasonal cycles, synoptic variations and diurnal cycles are shown to be useful for validating regional flux distribution patterns and strengths. Our results, based on two emission scenarios, suggest reduced emissions from temperate and tropical Asia region (by 13, 5, 3 Tg-CH 4 for India, China and Indonesia, respectively), and compensating increase (by 9, 9, 3 Tg-CH 4 for Russia, United States and Canada, respectively) in the boreal Northern Hemisphere (NH) are required for improved model-observation agreement.

Abstract. An analysis of the 22-yr ozone (O3) series (1988–2009) at the subtropical high mountain Izaña~station (IZO; 2373 m a.s.l.), representative of free troposphere (FT) conditions, is presented. Diurnal and seasonal O3 variations as well as the O3 trend (0.19 ± 0.05 % yr−1 or 0.09 ppbv yr−1), are assessed. A climatology of O3 transport pathways using backward trajectories shows that higher O3 values are associated with air masses travelling above 4 km altitude from North America and North Atlantic Ocean, while low O3 is transported from the Saharan continental boundary layer (CBL). O3 data have been compared with PM10, 210Pb, 7Be, potential vorticity (PV) and carbon monoxide (CO). A clear negative logarithmic relationship was observed between PM10 and surface O3 for all seasons. A similar relationship was found between O3 and 210Pb. The highest daily O3 values (90th percentile) are observed in spring and in the first half of summer time. A positive correlation between O3 and PV, and between O3 and 7Be is found throughout the year, indicating that relatively high surface O3 values at IZO originate from the middle and upper troposphere. We find a good correlation between O3 and CO in winter, supporting the hypothesis of long-range transport of photochemically generated O3 from North America. Aged air masses, in combination with sporadic inputs from the upper troposphere, are observed in spring, summer and autumn. In summer time high O3 values seem to be the result of stratosphere-to-troposphere (STT) exchange processes in regions neighbouring the Canary Islands. Since 1995–1996, the North Atlantic Oscillation has changed from a predominantly high positive phase to alternating between negative, neutral or positive phases. This change results in an increased flow of the westerlies in the mid-latitude and subtropical North Atlantic, thus favouring the transport of O3 and its precursors from North America, and a higher frequency of storms over North Atlantic, with a likely higher incidence of STT processes in mid-latitudes. These processes lead to an increase of tropospheric O3 in the subtropical North Atlantic region after 1996 that has been reflected in surface O3 records at IZO.