Search

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.

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.

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 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.

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.

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.

Received 29 May 2012; revised 8 August 2012; accepted 16 August 2012; published 4 October 2012. [1] We investigate the upper tropospheric distribution of methane (CH4) at low latitudes based on the analysis of air samples collected from aboard passenger aircraft. The distribution of CH4 exhibits spatial and seasonal differences, such as the pronounced seasonal cycles over tropical Asia and elevated mixing ratios over central Africa. Over Africa, the correlations of methane, ethane, and acetylene with carbon monoxide indicate that these high mixing ratios originate from biomass burning as well as from biogenic sources. Upper tropospheric mixing ratios of CH4were modeled using a chemistry transport model. The simulation captures the large-scale features of the distributions along different flight routes, but discrepancies occur in some regions. Over Africa, where emissions are not well constrained, the model predicts a too steep interhemispheric gradient. During summer, efficient convective vertical transport and enhanced emissions give rise to a large-scale CH4 maximum in the upper troposphere over subtropical Asia. This seasonal (monsoonal) cycle is analyzed with a tagged tracer simulation. The model confirms that in this region convection links upper tropospheric mixing ratios to regional sources on the Indian subcontinent, subtropical East Asia, and Southeast Asia. This type of aircraft data can therefore provide information about surface fluxes.

Atmospheric N 2 O concentration was observed in the Pacific for the period 1991–2006, using commercial container ships sailing between Japan and North America and between Japan and Australia or New Zealand. The N 2 O concentration showed a secular increase and interannual variations at all sampling locations, but a seasonal cycle was detectable only at northern high latitudes. The annual mean N 2 O concentration showed little longitudinal variations (within ± 0.3 ppb) in the northern Pacific, but showed a clear north-south gradient of about 0.8 ppb, with higher values in the Northern Hemisphere. The annual mean N 2 O was also characterized by especially high values at 30°N due to strong local N 2 O emissions and by a steep latitudinal decrease from the equator to 20°S due to the suppression of interhemispheric exchange of air by the South Pacific Convergence Zone. The N 2 O growth rate showed an interannual variation with a period of about 3 yr (high-values in 1999 and 2000), with a delayed eastward and poleward phase propagation in the northern and western Pacific, respectively. The interannual variations of the N 2 O growth rate and soil water showed a good correlation, suggesting that the N 2 O emission from soils have an important causative role in the atmospheric N 2 O variation. DOI: 10.1111/j.1600-0889.2008.00406.x

[1] Measurements of atmospheric N2O spanning altitudes from the surface to 14 km, and latitudes from 67°S to 85°N, show high concentrations in the tropics and subtropics, with strong maxima in the middle and upper troposphere. The pattern varies significantly over time scales of a few weeks. Global simulations do not accurately capture observed distributions with latitude, altitude, or time. Inversion results indicate strong, episodic inputs of nitrous oxide from tropical regions (as large as 1 Tg N-N2O over 9 weeks) are necessary to produce observed vertical and latitudinal distributions. These findings highlight strong tropical sources of N2O with high temporal variability, and the necessity of using full vertical profile observations in deriving emissions from atmospheric measurements.

[1] The atmospheric N2O variations between the Earth's surface and the lower stratosphere, simulated by an atmospheric general circulation model–based chemistry transport model (ACTM), are compared with aircraft and satellite observations. We validate the newly developed ACTM simulations of N2O for loss rate and transport in the stratosphere using satellite observations from the Aura Microwave Limb Sounder (Aura-MLS), with optimized surface fluxes for reproducing N2O trends observed at the surface stations. Observations in the upper troposphere/lower stratosphere (UT/LS) obtained by the Japan AirLines commercial flights commuting between Narita (36°N), Japan, and Sydney (34°S), Australia, have been used to study the role of stratosphere-troposphere exchange (STE) on N2O variability near the tropopause. Low N2O concentration events in the UT region are shown to be captured statistically significantly by the ACTM simulation. This is attributed to successful reproduction of stratospheric air intrusion events and N2O vertical/horizontal gradients in the lower stratosphere. The meteorological fields and N2O concentrations reproduced in the ACTM are used to illustrate the mechanisms of STE and subsequent downward propagation of N2O-depleted stratospheric air in the troposphere. Aircraft observations of N2O vertical profile over Surgut (West Siberia, Russia; 61°N), Sendai-Fukuoka (Japan; 34°N–38°N), and Cape Grim (Tasmania, Australia; 41°S) have been used to estimate the relative contribution of surface fluxes, transport seasonality in the troposphere, and STE to N2O seasonal cycles at different altitude levels. Stratospheric N2O tracers are incorporated in the ACTM for quantitative estimation of the stratospheric influence on tropospheric N2O. The results suggest strong latitude dependency of the stratospheric contribution to the tropospheric N2O seasonal cycle. The periods of seasonal minimum in the upper troposphere, which are spring over Japan and summer over Surgut, are in good agreement between the ACTM and observation and indicate a different propagation path of the stratospheric signal between the two sites in the Northern Hemisphere. The stratospheric tracer simulations, when utilized with the observed seasonal cycle, also provide qualitative information on the seasonal variation in surface fluxes of N2O.

We use an atmospheric general circulation model (AGCM) driven Chemistry-Transport Model (ACTM) to simulate the evolution of sulfur hexafluoride (SF6) in the atmosphere. 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. Monthly-mean, 2-box model exchange times (τex) are calculated from both the observed and simulated SF6time series at the 6 observing sites and show favorable agreement, suggesting that the model 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 SF6synoptic variability at the site level and provides insight into the seasonality of τex.

[1] Temporal and latitudinal variations of vertical profiles of N2O isotopomers were observed in the stratosphere over Japan (39°N, 142°E), Sweden (68°N, 20°E), and Antarctica (69°N, 40°E) during the period between 1990 and 2001. Samples were collected with a balloon-borne cryogenic sampler and analyzed by mass spectrometry in the laboratory. Observed enrichment factors for heavier isotopomers (15N14N16O, 14N15N16O, and 14N14N18O) relative to 14N14N16O were nearly constant in the lower stratosphere (less than ∼22 km) but increased at higher altitudes (∼22–35 km) while showing seasonal and latitudinal differences. Enrichment factors during the photolysis and photo-oxidation of N2O were also obtained in laboratory experiments and compared with those observed. We found that in the higher-altitude region (1) fractionation of the isotopomers is mainly determined by photolysis, but is also affected by physical processes, (2) subsidence of air masses in the winter polar vortex induces the intrusion of an upper stratospheric air mass depleted in N2O, and (3) decay of the vortex in the local spring leads to rapid horizontal advection of midlatitude air masses. At lower altitudes, isotopomer ratios are determined by photolysis, photo-oxidation, and the mixing of air masses within the stratosphere or between the stratosphere and the troposphere. Secular trend of isotopomer profiles was not detectable over Japan during 11 years. Assuming that the lower stratospheric air over midlatitudes is exchanged with the troposphere, isotopomer ratios of the N2O “back-flux” from the stratosphere were estimated. These values can be used in the isotopomeric mass balance model to constrain the global N2O budget.

We present observations of CH 4 concentrations from the lower to upper troposphere (LT and UT) over Japan during 1988–2010 based on aircraft measurements from the Tohoku University (TU). The analysis is aided by simulation results using an atmospheric chemistry transport model (i.e. ACTM). Tropospheric CH 4 over Japan shows interannual and seasonal variations that are dependent on altitudes, primarily reflecting differences in air mass origins at different altitudes. The long-term trend and interannual variation of CH 4 in the LT are consistent with previous reports of measurements at surface baseline stations in the northern hemisphere. However, those in the UT show slightly different features from those in the LT. In the UT, CH 4 concentrations show a seasonal maximum in August due to efficient transport of air masses influenced by continental CH 4 sources, while LT CH 4 reaches its seasonal minimum during summer due to enhanced chemical loss. Vertical profiles of the CH 4 concentrations also vary with season, reflecting the seasonal cycles at the respective altitudes. In summer, transport of CH 4 -rich air from Asian regions elevates UT CH 4 levels, forming a uniform vertical profile above the mid-troposphere. On the other hand, CH 4 decreases nearly monotonically with altitude in winter–spring. The ACTM simulations with different emission scenarios reproduce general features of the tropospheric CH 4 variations over Japan. Tagged tracer simulations using the ACTM indicate substantial contributions of CH 4 sources in South Asia and East Asia to the summertime high CH 4 values observed in the UT. This suggests that our observations over Japan are highly sensitive to CH 4 emission signals particularly from Asia. Keywords: methane, aircraft observation, long-term variation, seasonality, vertical profile, Asian outflow, atmospheric chemistry transport model (Published: 22 May 2014) Citation: Tellus B 2014, 66 , 23837, http://dx.doi.org/10.3402/tellusb.v66.23837 To access the supplementary material to this article, please see Supplementary files under Article Tools online.