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We analyzed air samples collected on board a C-130 cargo aircraft over the western North Pacific from May 2012 to March 2020 for atmospheric δ(O2 / N2) and CO2 amount fraction. Observations were corrected for significant artificial fractionation of O2 and N2 caused by thermal diffusion during the air sample collection using the simultaneously measured δ(Ar / N2). The observed seasonal cycles of the δ(O2 / N2) and atmospheric potential oxygen (δ(APO)) varied nearly in opposite phase to the cycle of the CO2 amount fraction at all latitudes and altitudes. Seasonal amplitudes of δ(APO) decreased with latitude from 34 to 25∘ N, as well as with increasing altitude from the surface to 6 km by 50 %–70 %, while those of the CO2 amount fraction decreased by less than 20 %. By comparing the observed values with the simulated δ(APO) and CO2 amount fraction values generated by an atmospheric transport model, we found that the seasonal δ(APO) cycle in the middle troposphere was modified significantly by a combination of the northern and southern hemispheric seasonal cycles due to the interhemispheric mixing of air. The simulated δ(APO) underestimated the observed interannual variation in δ(APO) significantly, probably due to the interannual variation in the annual mean air–sea O2 flux. Interannual variation in δ(APO) driven by the net marine biological activities, obtained by subtracting the assumed solubility-driven component of δ(APO) from the total variation, indicated a clear influence on annual net sea–air marine biological O2 flux during El Niño and net air–sea flux during La Niña. By analyzing the observed secular trends of δ(O2 / N2) and the CO2 amount fraction, global average terrestrial biospheric and oceanic CO2 uptakes for the period 2012–2019 were estimated to be (1.8±0.9) and (2.8±0.6) Pg a−1 (C equivalents), respectively.

Continuous observations of the atmospheric O2 / N2 ratio and CO2 amount fractions have been carried out at Ryori (RYO), Japan since August 2017. In these observations, the O2 : CO2 exchange ratio (oxidative ratio (OR), −Δy(O2)Δy(CO2)−1) has frequently been lower than expected from short-term variations in emissions from terrestrial biospheric activities and combustion of liquid, gas, and solid fuels. This finding suggests a significant effect of CO2 emission from a cement plant located about 6 km northwest of RYO. To evaluate this effect quantitatively, we simulated CO2 amount fractions in the area around RYO by using a fine-scale atmospheric transport model that incorporated CO2 fluxes from terrestrial biospheric activities, fossil fuel combustion, and cement production. The simulated CO2 amount fractions were converted to O2 amount fractions by using the respective OR values for each of the incorporated CO2 fluxes, and then simulated OR values were calculated from the calculated O2 and CO2 amount fractions. To extract the contribution of CO2 emissions from the cement plant, we used y(CO2*) as an indicator variable, where y(CO2*) is a conservative variable for terrestrial biospheric activity and fossil fuel combustion obtained by simultaneous analyses of observed O2 / N2 ratios and CO2 amount fractions and simulated ORs. We confirmed that the observed and simulated OR values and also the y(CO2*) values and simulated CO2 amount fractions due only to cement production were generally consistent. These results suggest that combined measurements of O2 / N2 ratios and CO2 amount fractions will be useful for evaluating CO2 capture from flue gas at carbon capture and storage (CCS) plants, which, similar to a cement plant, change CO2 amount fractions without changing O2 values, although CCS plants differ from cement plants in the direction of CO2 exchange with the atmosphere.

Systematic measurements of the atmospheric Ar∕N2 ratio have been made at ground-based stations in Japan and Antarctica since 2012. Clear seasonal cycles of the Ar∕N2 ratio with summertime maxima were found at middle- to high-latitude stations, with seasonal amplitudes increasing with increasing latitude. Eight years of the observed Ar∕N2 ratio at Tsukuba (TKB) and Hateruma (HAT), Japan, showed interannual variations in phase with the observed variations in the global ocean heat content (OHC). We calculated secularly increasing trends of 0.75 ± 0.30 and 0.89 ± 0.60 per meg per year from the Ar∕N2 ratio observed at TKB and HAT, respectively, although these trend values are influenced by large interannual variations. In order to examine the possibility of the secular trend in the surface Ar∕N2 ratio being modified significantly by the gravitational separation in the stratosphere, two-dimensional model simulations were carried out by arbitrarily modifying the mass stream function in the model to simulate either a weakening or an enhancement of the Brewer–Dobson circulation (BDC). The secular trend of the Ar∕N2 ratio at TKB, corrected for gravitational separation under the assumption of weakening (enhancement) of BDC simulated by the 2-D model, was 0.60 ± 0.30 (0.88 ± 0.30) per meg per year. By using a conversion factor of 3.5 × 10−23 per meg per joule by assuming a one-box ocean with a temperature of 3.5 ∘C, average OHC increase rates of 17.1 ± 8.6 ZJ yr−1 and 25.1 ± 8.6 ZJ yr−1 for the period 2012–2019 were estimated from the corrected secular trends of the Ar∕N2 ratio for the weakened- and enhanced-BDC conditions, respectively. Both OHC increase rates from the uncorrected- and weakened-BDC secular trends of the Ar∕N2 ratio are consistent with 12.2 ± 1.2 ZJ yr−1 reported by ocean temperature measurements, while that from the enhanced-BDC is outside of the range of the uncertainties. Although the effect of the actual atmospheric circulation on the Ar∕N2 ratio is still unclear and longer-term observations are needed to reduce uncertainty of the secular trend of the surface Ar∕N2 ratio, the analytical results obtained in the present study imply that the surface Ar∕N2 ratio is an important tracer for detecting spatiotemporally integrated changes in OHC and BDC.

We analyzed air samples collected onboard a cargo aircraft C-130 over the western North Pacific from May 2012 to March 2020 for atmospheric δ(O2/N2) and CO2 amount fraction. We corrected for significant artificial fractionation of O2 and N2 caused by thermal diffusion during the air sample collection by using the simultaneously-measured δ(Ar/N2). The observed seasonal cycles of the δ(O2/N2) and atmospheric potential oxygen (δ(APO)) varied nearly in opposite phase to that of the CO2 amount fraction at all latitudes and altitudes. Seasonal amplitudes of δ(APO) decreased with latitude from 34 to 25° N, as well as with increasing altitude from the surface to 6 km by 50–70 %, while those of CO2 amount fraction decreased by less than 20 %. By comparing the observed values with the simulated δ(APO) and CO2 amount fraction values generated by an atmospheric transport model, we found that the seasonal δ(APO) cycle in the middle troposphere was modified significantly by a superposition of the northern and southern hemispheric seasonal cycles due to the inter-hemispheric mixing of air. The simulated δ(APO) underestimated the observed interannual variation in δ(APO) significantly, probably due to the interannual variation in the annual mean air-sea O2 flux. Interannual variation in δ(APO) driven by the net marine biological activities, obtained by subtracting the assumed solubility-driven component of δ(APO) from the total variation, indicated a clear evidence of influence on annual sea-to-air (air-to-sea) marine biological O2 flux during El Niño (La Niña). By analyzing the observed secular trends of δ(O2/N2) and CO2 amount fraction, global average terrestrial biospheric and oceanic CO2 uptakes for the period 2012–2019 were estimated to be (1.8 ± 0.9) and (2.8 ± 0.6) Pg a−1 (C equivalents), respectively.

Three-dimensional (3D) quasi-residual mean flow is derived to diagnose 3D dynamical material transport associated with stationary planetary waves. The 3D quasi-residual mean vertical flow does not include the vertical flow due to tilting of the potential temperature caused by stationary waves, which is apparent but not seen in the mass-weighted isentropic mean state. Thus, the quasi-residual mean vertical flow is balanced with the term of diabatic heating rate. The 3D quasi-residual mean horizontal flow is balanced with the sum of the forcing due to transient wave activity flux divergence and the forcing associated with fluctuation of the potential vorticity due to stationary waves (defined as the effective Coriolis forcing). The zonal mean of the effective Coriolis forcing corresponds to the divergence of stationary wave activity flux. Thus, the zonal mean of derived 3D quasi-residual mean flow is exactly equal to the traditional residual mean flow. To demonstrate the usefulness of this quasi-residual mean flow, we analyze material transport of atmospheric sulfur hexafluoride (SF6) by using an atmospheric chemistry transport model. Comparison between the derived 3D quasi-residual mean flow and traditional residual mean flow shows that the zonal mean of advection of SF6 associated with the 3D quasi-residual mean flow derived is almost equal to that of the traditional residual mean flow. Next, it is confirmed that the horizontal structure of advection of SF6 associated with the 3D quasi-residual mean flow is balanced with the transport because of the nonlinear, nonconservative effects of disturbances. This relation is similar to the results for traditional residual mean flow in the zonal-mean state.

Stratospheric profiles of the mean age of air estimated from cryogenic air samples acquired during the CUBE/Biak field campaign over Indonesia are investigated with the aid of an atmospheric chemistry transport model nudged to ERA-Interim meteorological fields. Application of the boundary impulse response (BIR) method and Lagrangian backward trajectories to the transport field simulated by a single model prove useful in interpreting the observational results, which include discrepancies between CO2- and SF6-derived mean ages. This may be because the BIR method takes unresolved diffusive processes into account while the Lagrangian method distinguishes the pathways the air parcels have taken before reaching the sample site. The capability to estimate the vertical profiles of the clock tracer concentrations and the water vapor “tape recorder” is another advantage of the Lagrangian method, confirming the reality of the trajectory calculations. The profile of CO2-mean age is reproduced reasonably well by trajectory-derived mean age, while BIR-derived mean age is much greater than CO2 age at 28 and 29 km, possibly due to high diffusivity in the transport model. On the other hand, SF6 age is reproducible only in the lower stratosphere, but far exceeds the trajectory-derived mean age above 25 km. As air parcels of mesospheric origin are missing in the Lagrangian age estimation, this discrepancy, together with the fact that the observed SF6 concentrations are much lower than the trajectory-derived values in this height region, is consistent with the idea that the stratospheric air samples are mixed with SF6-depleted mesospheric air, leading to overestimation of the mean age.

Systematic measurements of the atmospheric Ar/N2 ratio have been made at ground-based stations in Japan and Antarctica since 2012. Clear seasonal cycles of the Ar/N2 ratio with summertime maxima were found at middle to high latitude stations, with seasonal amplitudes increasing with increasing latitude. Eight years of the observed Ar/N2 ratio at Tsukuba and Hateruma, Japan showed not only secular increasing trends, but also interannual variations in phase with the observed variations in the global ocean heat content (OHC). The observed secular trend of the Ar/N2 ratio was 0.75±0.30 per meg yr-1. Sensitivity test by using a 2-dimensional model with the Brewer-Dobson circulation (BDC) scenarios indicated the possibility of the secular trend in the surface Ar/N2 ratio being modified significantly by the gravitational separation in the stratosphere. The secular trend of the Ar/N2 ratio, corrected for gravitational separation under the assumption of weakening of BDC simulated by the 2D model, was 0.60±0.30 per meg yr-1. By using a conversion factor of 3.5x10-23 per meg J-1 by assuming a 1-box ocean with a temperature of 3.5 °C, then an average OHC increase rate of 17.1±8.6 ZJ yr-1 for the period 2012–2019 was estimated from the corrected secular trend of the Ar/N2 ratio. This value is consistent with 12.2±1.2 ZJ yr-1 reported by ocean temperature measurements. The effect of the actual atmospheric circulation on the Ar/N2 ratio is still unclear, however the analytical results obtained in the present study imply that the surface Ar/N2 ratio is an important tracer for detecting spatiotemporally-integrated changes in OHC and BDC.

The powerful El Niño event of 2015–2016 – the third most intense since the 1950s – has exerted a large impact on the Earth’s natural climate system. The column-averaged CO2 dry-air mole fraction (XCO2) observations from satellites and ground-based networks are analyzed together with in situ observations for the period of September 2014 to October 2016. From the differences between satellite (OCO-2) observations and simulations using an atmospheric chemistry-transport model, we estimate that, relative to the mean annual fluxes for 2014, the most recent El Niño has contributed to an excess CO2 emission from the Earth’s surface (land + ocean) to the atmosphere in the range of 2.4 ± 0.2 PgC (1 Pg = 1015 g) over the period of July 2015 to June 2016. The excess CO2 flux is resulted primarily from reduction in vegetation uptake due to drought, and to a lesser degree from increased biomass burning. It is about the half of the CO2 flux anomaly (range: 4.4–6.7 PgC) estimated for the 1997/1998 El Niño. The annual total sink is estimated to be 3.9 ± 0.2 PgC for the assumed fossil fuel emission of 10.1 PgC. The major uncertainty in attribution arise from error in anthropogenic emission trends, satellite data and atmospheric transport.

Methane (CH4) plays important roles in atmospheric chemistry and short-term forcing of climate. A clear understanding of atmospheric CH4’s budget of emissions and losses is required to aid sustainable management of Earth’s future environment. We used an atmospheric chemistry-transport model (JAMSTEC’s ACTM) for simulating atmospheric CH4. A global inverse modeling system has been developed for estimating CH4 emissions from 53 land regions for 2002–2012 using measurements at 39 sites. An ensemble of 7 inversions is performed by varying a priori emissions. Global net CH4 emissions varied between 505–509 and 524–545 Tg yr–1 during 2002–2006 and 2008–2012, respectively (ranges based on 7 inversion cases), with a step like increase in 2007 in agreement with atmospheric measurements. The inversion system did not account for interannual variations in OH radicals reacting with CH4 in the atmosphere. Our results suggest that the recent update of the EDGAR inventory (version 4.2FT2010) overestimated the global total emissions by at least 25 Tg yr–1 in 2010. The increase in CH4 emission since 2004 originated in the tropical and southern hemisphere regions, coinciding with an increase in non-dairy cattle stocks by ~10 % from 2002 (with 1056 million heads) to 2012, leading to ~10 Tg yr–1 increase in emissions from enteric fermentation. All 7 ensemble cases robustly estimated the interannual variations in emissions, but poorly constrained the seasonal cycle amplitude or phase consistently for all regions due to the sparse observational network. Forward simulation results using both a priori and a posteriori emissions are compared with independent aircraft measurements for validation. Based on the results of the comparison, we reject the upper limit (545 Tg yr–1) of global total emissions as 14 Tg yr–1 too high during 2008–2012, which allows us to further conclude that the increase in CH4 emissions over the East Asia (mainly China) region was 7–8 Tg yr–1 between the 2002–2006 and 2008–2012 periods, contrary to 1–17 Tg yr–1 in the a priori emissions.

This study assessed historical changes in emissions of nitrous oxide (N2O), a potent greenhouse gas and stratospheric ozone-depleting substance, from the soils of East Asia to the atmosphere. A process-based terrestrial ecosystem model (VISIT) was used to simulate the nitrogen cycle and associated N2O emissions as a function of climate, land use, atmospheric deposition, and agricultural inputs from 1901 to 2016. The mean regional N2O emission rate in the 2000s was estimated to be 2.03 Tg N2O year−1 (1.29 Tg N year−1; approximately one-third from natural ecosystems and two-thirds from croplands), more than triple the rate in 1901. A sensitivity analysis suggested that the increase of N2O emissions was primarily attributable to the increase of agricultural inputs from fertilizer and manure. The simulated N2O emissions showed a clear seasonal cycle and interannual variability, primarily in response to meteorological conditions and nitrogen inputs. The spatial pattern of the simulated N2O emissions revealed hot spots in agricultural areas of China, South Korea, and Japan. The average N2O emission factor (emission per unit nitrogen input) was estimated to be 1.38%, a value comparable to previous estimates. These biogeochemical modeling results will facilitate identifying ways to mitigate global warming and manage agricultural practices in this region.

Forests of the Western Himalaya, India, are impacted by the summer monsoon and winter seasonal rainfall events and associated changes in the meteorology. Here, we assess the scale interactions between observed forest ecosystem fluxes and meteorological parameters, particularly rainfall seasonality and extremes. The scale interactions were investigated using daily observed fluxes and meteorological parameters of 1080 days of 2014–2016 from a Pinus roxburghii dominated forest and using wavelet spectral analysis method. The mixed forest of this study was a sink of CO2 having the average NEE −3.21 gC m−2 day−1 for the period of observations. Result of the wavelet coherence analysis from observed data indicated a statistically significant correlation (> 0.7 at 95 % confidence level) between daily average NEE and daily total rainfall having band periods of 70–120 days, 35–64 days and 60–90 days of monsoon periods of 2014–16, respectively, where rainfall leading to NEE. Impact of heavy rainfall events of monsoon periods over NEE of the forest patch was found to have average band periods of 4 days; whereas, the winter time heavy rainfall events were having average band periods of 15 days with very high local correlation (> 0.7 at 95 % confidence level) inferring that ecosystem exchange rate was mirroring rainfall events. Although CASA-GFDE3 model simulated daily NEE values of 2014–15 were found have a low fraction of explained variance (= 0.08) with respect to observations, modeled NEE-rainfall relationship of 2014 was found to corroborate well with the observed pattern; however for 2015, the phase relationship between modeled NEE and rainfall around band period of 100 days was opposite to the flux tower observations. Subsequently, heavy rainfall events and daily average air temperatures were also found to be coherent during monsoon period having wavelet coherences > 0.8 indicating a cause and effect relationship between both parameters, and rainfall events were mirroring temperature variations. Therefore, it is anticipated that the Pinus roxburghii dominated forest productivity of Western Himalaya, India, are expected to increase even with the increment of heavy rainfall events in the near 20 future.

Atmospheric methane (CH4) increased from ~900 ppb (parts per billion, or nanomoles per mole of dry air) in 1900 to ~1800 ppb in 2010 at a rate unprecedented in any observational records. However, the contributions of the various methane sources and sinks to the CH4 increase are poorly understood. Here we use initial emissions from bottom-up inventories for anthropogenic sources, emissions from wetlands and rice paddies simulated by a~terrestrial biogeochemical model, and an atmospheric general circulation model (AGCM)-based chemistry-transport model (i.e. ACTM) to simulate atmospheric CH4 concentrations for 1910–2010. The ACTM simulations are compared with the CH4 concentration records reconstructed from Antarctic and Arctic ice cores and firn air samples, and from direct measurements since the 1980s at multiple sites around the globe. The differences between ACTM simulations and observed CH4 concentrations are minimized to optimize the global total emissions using a mass balance calculation. During 1910–2010, the global total CH4 emission doubled from ~290 to ~580 Tg yr−1. Compared to optimized emission, the bottom-up emission data set underestimates the rate of change of global total CH4 emissions by ~30% during the high growth period of 1940–1990, while it overestimates by ~380% during the low growth period of 1990–2010. Further, using the CH4 stable carbon isotopic data (δ13C), we attribute the emission increase during 1940–1990 primarily to enhancement of biomass burning. The total lifetime of CH4 shortened from 9.4 yr during 1910–1919 to 9 yr during 2000–2009 by the combined effect of the increasing abundance of atomic chlorine radicals (Cl) and increases in average air temperature. We show that changes of CH4 loss rate due to increased tropospheric air temperature and CH4 loss due to Cl in the stratosphere are important sources of uncertainty to more accurately estimate the global CH4 budget from δ13C observations.

N2O is currently the third most important anthropogenic greenhouse gas in terms of radiative forcing and its atmospheric mole fraction is rising steadily. To quantify the growth rate and its causes over the past decades, we performed a multi-site reconstruction of the atmospheric N2O mole fraction and isotopic composition using new and previously published firn air data collected from Greenland and Antarctica in combination with a firn diffusion and densification model. The multi-site reconstruction showed that while the global mean N2O mole fraction increased from (290 ± 1) nmol mol−1 in 1940 to (322 ± 1) nmol mol−1 in 2008, the isotopic composition of atmospheric N2O decreased by (−2.2 ± 0.2) ‰ for δ15Nav, (−1.0 ± 0.3) ‰ for δ18O, (−1.3 ± 0.6) ‰ for δ15Nα, and (−2.8 ± 0.6) ‰ for δ15Nβ over the same period. The detailed temporal evolution of the mole fraction and isotopic composition derived from the firn air model was then used in a two-box atmospheric model (comprising a stratospheric box and a tropospheric box) to infer changes in the isotopic source signature over time. The precise value of the source strength depends on the choice of the N2O lifetime, which we choose to fix at 123 years. The average isotopic composition over the investigated period is δ15Nav = (−7.6 ± 0.8) ‰ (vs. air-N2), δ18O = (32.2 ± 0.2) ‰ (vs. Vienna Standard Mean Ocean Water – VSMOW) for δ18O, δ15Nα = (−3.0 ± 1.9) ‰ and δ15Nβ = (−11.7 ± 2.3) ‰. δ15Nav, and δ15Nβ show some temporal variability, while for the other signatures the error bars of the reconstruction are too large to retrieve reliable temporal changes. Possible processes that may explain trends in 15N are discussed. The 15N site preference ( = δ15Nα − δ15Nβ) provides evidence of a shift in emissions from denitrification to nitrification, although the uncertainty envelopes are large.

We present a comprehensive estimate of nitrous oxide (N2O) emissions using observations and models from 1995 to 2008. High-frequency records of tropospheric N2O are available from measurements at Cape Grim, Tasmania; Cape Matatula, American Samoa; Ragged Point, Barbados; Mace Head, Ireland; and at Trinidad Head, California using the Advanced Global Atmospheric Gases Experiment (AGAGE) instrumentation and calibrations. The Global Monitoring Division of the National Oceanic and Atmospheric Administration/Earth System Research Laboratory (NOAA/ESRL) has also collected discrete air samples in flasks and in situ measurements from remote sites across the globe and analyzed them for a suite of species including N2O. In addition to these major networks, we include in situ and aircraft measurements from the National Institute of Environmental Studies (NIES) and flask measurements from the Tohoku University and Commonwealth Scientific and Industrial Research Organization (CSIRO) networks. All measurements show increasing atmospheric mole fractions of N2O, with a varying growth rate of 0.1–0.7% per year, resulting in a 7.4% increase in the background atmospheric mole fraction between 1979 and 2011. Using existing emission inventories as well as bottom-up process modeling results, we first create globally gridded a priori N2O emissions over the 37 years since 1975. We then use the three-dimensional chemical transport model, Model for Ozone and Related Chemical Tracers version 4 (MOZART v4), and a Bayesian inverse method to estimate global as well as regional annual emissions for five source sectors from 13 regions in the world. This is the first time that all of these measurements from multiple networks have been combined to determine emissions. Our inversion indicates that global and regional N2O emissions have an increasing trend between 1995 and 2008. Despite large uncertainties, a significant increase is seen from the Asian agricultural sector in recent years, most likely due to an increase in the use of nitrogenous fertilizers, as has been suggested by previous studies.

Observations of methyl chloroform combined with an atmospheric transport model predict a Northern to Southern Hemisphere hydroxyl ratio of slightly less than 1, whereas commonly used atmospheric chemistry models predict ratios 15–45% higher. The hydroxyl radical is an important atmospheric oxidant, but our knowledge of its global distribution remains imprecise, with estimates for the ratio of Northern Hemisphere to Southern Hemisphere hydroxyl radical concentration varying from 0.85 to 1.4. These authors use a three-dimensional chemistry-transport model that has been well validated for interhemispheric transport using sulphur hexafluoride measurements, to obtain an interhemispheric hydroxyl radical ratio of 0.97±0.12. This information can help improve our understanding of the fate of atmospheric pollutants and greenhouse gases. The hydroxyl radical (OH) is a key oxidant involved in the removal of air pollutants and greenhouse gases from the atmosphere1,2,3. The ratio of Northern Hemispheric to Southern Hemispheric (NH/SH) OH concentration is important for our understanding of emission estimates of atmospheric species such as nitrogen oxides and methane4,5,6. It remains poorly constrained, however, with a range of estimates from 0.85 to 1.4 (refs 4, 7,8,9,10). Here we determine the NH/SH ratio of OH with the help of methyl chloroform data (a proxy for OH concentrations) and an atmospheric transport model that accurately describes interhemispheric transport and modelled emissions. We find that for the years 2004–2011 the model predicts an annual mean NH–SH gradient of methyl chloroform that is a tight linear function of the modelled NH/SH ratio in annual mean OH. We estimate a NH/SH OH ratio of 0.97 ± 0.12 during this time period by optimizing global total emissions and mean OH abundance to fit methyl chloroform data from two surface-measurement networks and aircraft campaigns11,12,13. Our findings suggest that top-down emission estimates of reactive species such as nitrogen oxides in key emitting countries in the NH that are based on a NH/SH OH ratio larger than 1 may be overestimated.

[1] Decadal time series and short-term temporal variations in mixing ratio of atmospheric nitrous oxide (N2O) and abundance of its isotopomers (14N15N16O and 15N14N16O) and isotopologue (14N14N18O) relative to 14N14N16O have been observed for the first time in the Northern Hemisphere at Hateruma Island (HAT), Japan during 1999–2010 by monthly air sampling. Results show that the bulk nitrogen isotope ratio δ15Nbulk decreased at the rate of −0.023 ± 0.006‰ yr−1, although the N2O mixing ratio increased at the rate of about 0.7 nmol mol−1 yr−1 (ppb yr−1) during the period. Isotope budget calculation with the δ15Nbulk trend supports the earlier estimates showing that the isotopically light sources such as agriculture and industry contribute to the increase of atmospheric N2O. However, the rate of decrease of δ15Nbulk is slightly smaller in magnitude than the rates obtained virtually for the 20th century from firn air in polar regions and surface air in the Southern Hemisphere (Tasmania and Antarctica), which suggests greater contribution of 15 N-enriched N2O sources in recent years or in the extra-polar Northern Hemisphere. In contrast, the oxygen isotope ratio (δ18O) and intramolecular 15N site preference (SP, difference between isotope ratios at central and terminal nitrogen atoms) of N2O showed no significant trends, contrary to previous reports. Results show that no significant seasonal variation exists in δ15Nbulk, δ18O, and SP of N2O at HAT in the past decade within the limits of our sampling frequency and analytical precision.

We present the mixing ratio, δ13C and δD of atmospheric CH4 using commercial aircraft in the upper troposphere (UT) over the Western Pacific for the period December 2005–September 2010. The observed results were compared with those obtained using commercial container ships in the lower troposphere (LT) over the same region. In the Northern Hemisphere (NH), the UT CH4 mixing ratio shows high values in the boreal summer–autumn, when the LT CH4 mixing ratio reaches a seasonal minimum. From tagged tracer experiments made using an atmospheric chemistry transport model, we found that such high CH4 values are due to rapid transport of air masses influenced by CH4 sources in South Asia and East Asia. The observed isotopic ratio data imply that these areas have CH4 sources with relatively low δ13C and δD signatures such as biogenic sources. Latitudinal distributions of the annual average UT and LT CH4 mixing ratio intersect each other in the tropics; the mixing ratio value is lower in the UT than in the LT in the NH and the situation is reversed in the Southern Hemisphere (SH), due mainly to the NH air intrusion into the SH through the UT. Such intersection of the latitudinal distributions is observable in δD but not in δ13C, implying an additional contribution from reaction of CH4 with active chlorine in the marine boundary layer. δ13C and δD show low values in the NH and high values in the SH both in the UT and in the LT. We also observed an increase in the CH4 mixing ratio and decreases in δ13C and &delta

We present a comparison of an atmospheric general circulation model (AGCM)-based chemistry-transport model (ACTM) simulation with total column measurements of CO2, CH4 and N2O from the Total Carbon Column Observing Network (TCCON). The model is able to capture observed trends, seasonal cycles and inter hemispheric gradients at most sampled locations for all three species. The model-observation agreements are best for CO2, because the simulation uses fossil fuel inventories and an inverse model estimate of non-fossil fuel fluxes. The ACTM captures much of the observed seasonal variability in CO2 and N2O total columns (~81 % variance, R>0.9 between ACTM and TCCON for 19 out of 22 cases). These results suggest that the transport processes in troposphere and stratosphere are well represented in ACTM. Thus the poor correlation between simulated and observed CH4 total columns, particularly at tropical and extra-tropical sites, have been attributed to the uncertainties in surface emissions and loss by hydroxyl radicals. While the upward-looking total column measurements of CO2 contains surface flux signals at various spatial and temporal scales, the N2O measurements are strongly affected by the concentration variations in the upper troposphere and stratosphere.

We have carried out monthly flask sampling using aircraft, in the altitude range of 0-7 km, over the boreal wetlands in Surgut (61°N, 73°E; since 1993) and a pine forest near Novosibirsk (55°N, 83°E; since 1997), both located in the West Siberian Lowland (WSL). The temporal variation of methane (CH4) concentrations at all altitudes at both sites exhibited an increasing trend with stagnation during 2000-2006 as observed globally from ground-based networks. In addition to a winter maximum as seen at other remote sites in northern mid to high latitudes, another seasonal maximum was also observed in summer, particularly in the lower altitudes over the WSL, which could be attributed to emissions from the wetlands. Our measurements suggest that the vertical gradient at Surgut has been decreasing; the mean CH4 difference between 5.5 km and 1.0 km changed from 64±5 ppb during 1995-1999 to 37±3 ppb during 2009-2013 (mean ± standard error). No clear decline in the CH4 vertical gradient appeared at Novosibirsk. Simulations using an atmospheric chemistry-transport model captured the observed decrease in the vertical CH4 gradient at Surgut when CH4 emissions from Europe decreased but increased from the regions south of Siberia, e.g., East and South Asia. At Novosibirsk, the influence of the European emissions was relatively small. Our results also suggest that the regional emissions around the WSL did not change significantly over the period of our observations.

A terrestrial ecosystem model, called the Vegetation Integrative Simulator for Trace gases model (VISIT), which fully integrates biogeochemical carbon and nitrogen cycles, was developed to simulate atmosphere–ecosystem exchanges of greenhouse gases (CO2, CH4, and N2O), and to determine the global warming potential (GWP) taking into account the radiative forcing effect of each gas. The model was then applied to a cool-temperate deciduous broad-leaved forest in Takayama, central Japan (36°08′N, 137°25′E, 1420 m above sea level). Simulations were conducted at a daily time step from 1948 to 2008, using time-series meteorological and nitrogen deposition data. VISIT accurately captured the carbon and nitrogen cycles of this typical Japanese forest, as validated by tower and chamber flux measurements. During the last 10 years of the simulation, the model estimated that the forest was a net greenhouse gas sink, having a GWP equivalent of 1025.7 g CO2 m−2 y−1, most of which (1016.9 g CO2 m−2 y−1) was accounted for by net CO2 sequestration into forest biomass regrowth. CH4 oxidation by the forest soil made a small contribution to the net sink (11.9 g CO2-eq. m−2 y−1), whereas N2O emissions were a very small source (3.2 g CO2-eq. m−2 y−1), as expected for a volcanic soil in a humid climate. Analysis of the sensitivity of GWP to changes in temperature, precipitation, and nitrogen deposition indicated that warming temperatures would decrease the size of the sink, mainly as a result of increased CO2 release due to increased ecosystem respiration.

We use an atmospheric general circulation model (AGCM) driven chemistry-transport model (ACTM) to simulate the evolution of sulfur hexafluoride (SF6) in the troposphere. The model results are compared with continuous measurements at 6 sites over 71° N–90° S. These comparisons demonstrate that the ACTM simulations lie within the measurement uncertainty over the analysis period (1999–2006) and capture salient features of synoptic, seasonal and interannual SF6 variability. To understand transport timescales of SF6 within the troposphere, transport times of air parcels from the surface to different regions of the troposphere ("age") are estimated from a simulation of an idealized tracer. The age estimation error and its sensitivity to the selection of reanalysis meteorology for ACTM nudging or the tracer transport by deep cumulus convection as represented in the model are discussed. Monthly-mean, 2-box model exchange times (τex) are calculated from both the observed and simulated SF6 time series at the 6 observing sites and show favorable agreement, suggesting that the ACTM adequately represents large-scale interhemispheric transport. The simulated SF6 variability is further investigated through decomposition of the mixing ratio time-tendency into advective, convective, and vertical diffusive components. The transport component analysis illustrates the role of each process in SF6 synoptic variability at the site level and provides insight into the seasonality of τex.

We have used an AGCM (atmospheric general circulation model)-based Chemistry Transport Model (ACTM) for the simulation of methane (CH4) 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 (1990-2006) trends in growth rate and seasonal cycle at most measurement sites can be fairly successfully modeled by using existing knowledge of CH4 flux trends and seasonality. A large part of the interannual variability (IAV) in CH4 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 CH4 mixing ratio at the earth’s surface. Estimated atmospheric CH4 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 coefficient, on CH4 simulation compared to the transport related variability (order of ±15 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-CH4 for India, China and Indonesia, respectively), and compensating increase (by 9, 9, 3 Tg-CH4 for Russia, United States and Canada, respectively) in the boreal Northern Hemisphere (NH) are required for improved model-observation agreement.

This paper presents the development of an atmospheric N2O isotopocule model based on a chemistry-coupled atmospheric general circulation model (ACTM). We also describe a simple method to optimize the model and present its use in estimating the isotopic signatures of surface sources at the hemispheric scale. Data obtained from ground-based observations, measurements of firn air, and balloon and aircraft flights were used to optimize the long-term trends, interhemispheric gradients, and photolytic fractionation, respectively, in the model. This optimization successfully reproduced realistic spatial and temporal variations of atmospheric N2O isotopocules throughout the atmosphere from the surface to the stratosphere. The very small gradients associated with vertical profiles through the troposphere and the latitudinal and vertical distributions within each hemisphere were also reasonably simulated. The results of the isotopic characterization of the global total sources were generally consistent with previous one-box model estimates, indicating that the observed atmospheric trend is the dominant factor controlling the source isotopic signature. However, hemispheric estimates were different from those generated by a previous two-box model study, mainly due to the model accounting for the interhemispheric transport and latitudinal and vertical distributions of tropospheric N2O isotopocules. Comparisons of time series of atmospheric N2O isotopocule ratios between our model and observational data from several laboratories revealed the need for a more systematic and elaborate intercalibration of the standard scales used in N2O isotopic measurements in order to capture a more complete and precise picture of the temporal and spatial variations in atmospheric N2O isotopocule ratios. This study highlights the possibility that inverse estimation of surface N2O fluxes, including the isotopic information as additional constraints, could be realized.

N[subscript 2]O surface fluxes were estimated for 1999 to 2009 using a time-dependent Bayesian inversion technique. Observations were drawn from 5 different networks, incorporating 59 surface sites and a number of ship-based measurement series. To avoid biases in the inverted fluxes, the data were adjusted to a common scale and scale offsets were included in the optimization problem. The fluxes were calculated at the same resolution as the transport model (3.75° longitude × 2.5° latitude) and at monthly time resolution. Over the 11-year period, the global total N[subscript 2]O source varied from 17.5 to 20.1 Tg a[superscript −1] N. Tropical and subtropical land regions were found to consistently have the highest N[subscript 2]O emissions, in particular in South Asia (20 ± 3% of global total), South America (13 ± 4%) and Africa (19 ± 3%), while emissions from temperate regions were smaller: Europe (6 ± 1%) and North America (7 ± 2%). A significant multi-annual trend in N[subscript 2]O emissions (0.045 Tg a[superscript −2] N) from South Asia was found and confirms inventory estimates of this trend. Considerable interannual variability in the global N[subscript 2]O source was observed (0.8 Tg a[superscript −1] N, 1 standard deviation, SD) and was largely driven by variability in tropical and subtropical soil fluxes, in particular in South America (0.3 Tg a[superscript −1] N, 1 SD) and Africa (0.3 Tg a[superscript −1] N, 1 SD). Notable variability was also found for N[subscript 2]O fluxes in the tropical and southern oceans (0.15 and 0.2 Tg a[superscript −1] N, 1 SD, respectively). Interannual variability in the N[subscript 2]O source shows some correlation with the El Niño–Southern Oscillation (ENSO), where El Niño conditions are associated with lower N[subscript 2]O fluxes from soils and from the ocean and vice versa for La Niña conditions.

Aircraft measurements of the tropospheric N2O concentration were made over Japan during the period from October 1991 to June 1999. The observed values of the N2O concentration showed clear evidence of the secular increase, with mean rates of 0.50 to 0.64 ppbv/yr for selected height intervals of 0–2, 2–4, 4–6, 6–8 km and 8 km-tropopause. Although the seasonality of the N2O concentration was hardly observable throughout the troposphere, interannual variations with periods of about 2 years were clearly found. The average N2O concentrations over the observation period for the above 5 height intervals were almost identical with each other, showing no appreciable vertical gradient of the concentration. This suggests that N2O emissions from the ground surface around Japan are very weak and the emitted N2O is mixed well in the troposphere.