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Systematic observations of CO2 mole fraction, the isotopic ratio δ13C of CO2 and oxygen to nitrogen ratio (δ(O2/N2)) in the atmosphere have been carried out at Ny-Alesund, Svalbard since 1991, 1996 and 2001, respectively. The CO2 mole fraction shows a clear seasonal cycle superimposed on a secular increase with an average rate of 2.0 ppm yr−1 for the period 1996–2013. On the other hand, δ13C and δ(O2/N2) decrease secularly at an average rate of −0.020 ‰ yr−1 for 1996–2013, and −19.9 per meg yr−1 for 2001–2013, respectively. Based on the observed secular trends of the CO2 mole fraction and δ(O2/N2), the average CO2 uptake during 2001–2013 was estimated to be 1.6 ± 0.8 and 2.3 ± 0.5 GtC yr−1 for the terrestrial biosphere and the ocean, respectively. By using the observed CO2 and δ13C, the corresponding CO2 uptake of 1.3 ± 0.6 and 2.6 ± 0.5 GtC yr−1 were obtained for the same period. The estimates from the two methods are in good agreement with each other. The terrestrial biospheric CO2 uptake derived by the latter method showed large inter-annual variability in association with El Nino events. On the other hand, the oceanic uptake increased secularly with less inter-annual variability during 1996–2013.

Accepted: 2013-07-23, 資料番号: SA1004576000

Oxygen in the atmosphere undergoes variations and changes in response to biospheric activities, ocean–atmosphere exchange and fossil fuel combustion. Continuous in situ measurements of atmospheric δ(O2/N2) and CO2 mole fraction were started at Ny-Ålesund, Svalbard (78.93°N, 11.83°E, 40 m a.s.l.) in November 2012. Atmospheric potential oxygen (APO) calculated from the measured O2 and CO2 values during November 2012–January 2015 show a clear seasonal cycle with a peak-to-peak amplitude of approximately 50 per meg. The seasonal cycle of APO simulated using an atmospheric transport model, with prescribed oceanic O2, N2 and CO2 fluxes at monthly time intervals, is in excellent agreement with the observed APO. However, in spring and early summer, high values of APO are observed irregularly on a timescale of hours to days. By comparing backward trajectories of air parcels released from the site with distributions of marine net primary production (NPP), and tagged tracer experiments made using the atmospheric transport model for APO, it is found that these high APO fluctuations are primarily attributable to O2 emissions from the Greenland Sea, the Norwegian Sea and the Barents Sea, due to marine biological productivity. Marine net community production, estimated based on the sea-to-air O2 flux derived from observed APO fluctuations, agrees with NPP obtained from satellite observations within an order of magnitude. The results obtained in this study have still some uncertainties, but our continuous observations of atmospheric δ(O2/N2) and CO2 mole fraction at Ny-Ålesund can play an important role in detecting possible changes in the carbon cycle in the near future.

We have conducted systematic observations of the CH4 mole fraction and its carbon isotope ratio (δ13C) at Ny-Ålesund, Svalbard (78°55′N, 11°56′E) using air samples collected weekly since 1991 and 1996, respectively. The CH4 mole fraction showed long-term increase until 1999, stagnation between 2000 and 2006, followed by an increase after 2006. On the other hand, δ13C showed monotonous increase until 2006 and decrease after 2006. By comparing the rates of change in the CH4 mole fraction and δ13C under the assumption that the atmospheric CH4 lifetime is constant, it is suggested that the temporal pause of the CH4 mole fraction observed at Ny-Ålesund is attributed to reductions of CH4 release from the microbial and fossil fuel sectors. On the other hand, the increase in CH4 after 2006 could be ascribed to an increase in microbial CH4 release. The CH4 and δ13C data presented in this paper would be useful for clarifying their temporal variations in the Arctic atmosphere, as well as providing additional constraints on the global CH4 budget.

The rising abundance of greenhouse gases in the atmosphere has been associated with a change in the stratospheric circulation and a decrease in the mean age of stratospheric air. Balloon-borne measurements of trace gases over 30 years suggest that, in contrast to model predictions, there have been no significant trends (at a 90% confidence limit) in the age of stratospheric air. The rising abundances of greenhouse gases in the atmosphere is associated with an increase in radiative forcing that leads to warming of the troposphere, the lower portion of the Earth’s atmosphere, and cooling of the stratosphere above1. A secondary effect of increasing levels of greenhouse gases is a possible change in the stratospheric circulation2,3, which could significantly affect chlorofluorocarbon lifetimes4, ozone levels5,6 and the climate system more generally7. Model simulations have shown that the mean age of stratospheric air8 is a good indicator of the strength of the residual circulation9, and that this mean age is expected to decrease with rising levels of greenhouse gases in the atmosphere10. Here we use balloon-borne measurements of stratospheric trace gases over the past 30 years to derive the mean age of air from sulphur hexafluoride (SF6) and CO2 mixing ratios. In contrast to the models, these observations do not show a decrease in mean age with time. If models are to make valid predictions of future stratospheric ozone levels, and of the coupling between ozone and climate change, a correct description of stratospheric transport and possible changes in the transport pathways are necessary.

Stratospheric and upper tropospheric air samples were collected during 1994–2004 over Sanriku, Japan and in 1997 over Kiruna, Sweden. Using these archived air samples, we determined the triple oxygen-isotope composition of stratospheric CO2 and the N2O mixing ratio. The maximum Δ17OCO2 value of +12.2‰, resembling that observed previously in the mesosphere at 60 km height, was found in the middle stratosphere over Kiruna at 25.6 km height, suggesting that upper stratospheric and mesospheric air descended to the middle stratosphere through strong downward advection. A least-squares regression analysis of our observations on a δ18OCO2−δ17OCO2 plot (r2>0.95) shows a slope of 1.63±pm0.10, which is similar to the reported value of 1.71±0.06, thereby confirming the linearity of three isotope correlation with the slope of 1.6–1.7 in the mid-latitude lower and middle stratosphere. The slope decrease with increasing altitude and a curvy trend in three-isotope correlation reported from previous studies were not statistically significant. Using negative linear correlations of Δ17OCO2 and δ18OCO2 with the N2O mixing ratio, we quantified triple oxygen-isotope fluxes of CO2 to the troposphere as +48‰ GtC/yr (Δ17OCO2) and +38‰ GtC/yr (δ18OCO2) with ~30% uncertainty. Comparing recent model results and observations, underestimation of the three isotope slope and the maximum Δ17OCO2 value in the model were clarified, suggesting a smaller O2 photolysis contribution than that of the model. Simultaneous observations of δ18OCO2, δ17OCO2, and N2O mixing ratios can elucidate triple oxygen isotopes in CO2 and clarify complex interactions among physical, chemical, and photochemical processes occurring in the middle atmosphere.

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.

A method for measuring the concentration of methyl chloride (CH 3 Cl) in air trapped in an ice core was developed. The method combines the air extraction by milling the ice core samples under vacuum and the analysis of the extracted air with a cryogenic preconcentration/gas chromatograph/mass spectrometry system. The method was applied to air from Antarctic ice core samples estimated to have been formed in the pre-industrial and/or early industrial periods. The overall precision of the method deduced from duplicate ice core analyses was estimated to be better than ±20 pptv. The measured CH 3 Cl concentration of 528 ± 26 pptv was similar to the present-day concentration in the remote atmosphere as well as the CH 3 Cl concentration over the past 300 years obtained from Antarctic firn air and ice core analyses.

Employing a mass spectrometry method, a high precision measurement system was developed for analysis of the atmospheric O2/N2 ratio. Sample air and reference air were introduced into the mass spectrometer through thermally-insulated thin fused silica capillaries from an inlet system. Interference by CO generated in the ion source of the mass spectrometer from CO2 in the sample air, and the O2/N2 ratio biased due to pressure imbalance between the sample air and the reference air during their introduction into the mass spectrometer were experimentally corrected. Deterioration of sampled air during storage in flasks, as well as air sampling procedures, was also examined. The precision of our measurement system was estimated to be 5.4 per meg for the O2/N2 ratio, which corresponds to 1.1 ppmv of the atmospheric O2 concentration. Our standard air with 6 different O2/N2 ratios were prepared by drying the atmosphere and then stored in 47 L high-pressure cylinders; their O2/N2 ratios were confirmed to be stable within 20.0 per meg over the last 2 years. This system has been used for actual measurements of the atmospheric O2/N2 ratio since May 1999. Preliminary results of the measurements made in the suburbs of Sendai, Japan showed clear evidence for the seasonal cycle and the secular trend of the atmospheric O2/N2 ratio, which are opposite in phase with those of the CO2 concentration.

Methyl chloride (CH3Cl), the most abundant halocarbon in the atmosphere, has received much attention as a natural source of chlorine atoms in the stratosphere1,2. The annual global flux of CH3Cl has been estimated to be around 3.5 Tg on the grounds that this must balance the loss through reaction with OH radicals (which gives a lifetime for atmospheric CH3Cl of 1.5 yr)3,4,5. The most likely main source of methyl chloride has been thought to be oceanic emission2,6,7,8, with biomass burning the second largest source9. But recent seawater measurements10 indicate that oceanic fluxes cannot account for more than 12% of the estimated global flux of CH3Cl, raising the question of where the remainder comes from. Here we report evidence of significant CH3Cl emission from warm coastal land, particularly from tropical islands. This conclusion is based on a global monitoring study and spot measurements, which show enhancement of atmospheric CH3Cl in the tropics, a close correlation between CH3Cl concentrations and those of biogenic compounds emitted by terrestrial plants, and OH-linked seasonality of CH3Cl concentrations in middle and high latitudes. A strong, equatorially located source of this nature would explain why the distribution of CH3Cl is uniform between the Northern and Southern hemispheres, despite their differences in ocean and land area.

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

A deep ice core drilled at Dome Fuji, East Antarctica was analyzed for the CO 2 concentration using a wet extraction method in order to reconstruct its atmospheric variations over the past 320 kyr, which includes three full glacial–interglacial climatic cycles, with a mean time resolution of about 1.1 kyr. The CO 2 concentration values derived for the past 65 kyr are very close to those obtained from other Antarctic ice cores using dry extraction methods, although the wet extraction method is generally thought to be inappropriate for the determination of the CO 2 concentration. The comparison between the CO 2 and Ca 2+ concentrations deduced from the Dome Fuji core suggests that calcium carbonate emitted from lands was mostly neutralized in the atmosphere before reaching the central part of Antarctica, or that only a small part of calcium carbonate was involved in CO 2 production during the wet extraction process. The CO 2 concentration for the past 320 kyr deduced from the Dome Fuji core varies between 190 and 300 ppmv, showing clear glacial–interglacial variations similar to the result of the Vostok ice core. However, for some periods, the concentration values of the Dome Fuji core are higher by up to 20 ppmv than those of the Vostok core. There is no clear indication that such differences are related to variations of chemical components of Ca 2+ , microparticle and acidity of the Dome Fuji core. DOI: 10.1034/j.1600-0889.2003.00050.x

The Milankovitch theory of climate change proposes that glacial interglacial cycles are driven by changes in summer insolation at high northern latitudes(1). The timing of climate change in the Southern Hemisphere at glacial-interglacial transitions (which are known as terminations) relative to variations in summer insolation in the Northern Hemisphere is an important test of this hypothesis. So far, it has only been possible to apply this test to the most recent termination(2,3), because the dating uncertainty associated with older terminations is too large to allow phase relationships to be determined. Here we present a new chronology of Antarctic climate change over the past 360,000 years that is based on the ratio of oxygen to nitrogen molecules in air trapped in the Dome Fuji and Vostok ice cores(4,5). This ratio is a proxy for local summer insolation(5), and thus allows the chronology to be constructed by orbital tuning without the need to assume a lag between a climate record and an orbital parameter. The accuracy of the chronology allows us to examine the phase relationships between climate records from the ice cores(6-9) and changes in insolation. Our results indicate that orbital-scale Antarctic climate change lags Northern Hemisphere insolation by a few millennia, and that the increases in Antarctic temperature and atmospheric carbon dioxide concentration during the last four terminations occurred within the rising phase of Northern Hemisphere summer insolation. These results support the Milankovitch theory that Northern Hemisphere summer insolation triggered the last four deglaciations(3,10,11).

[1] Vertical profiles of nitrous oxide and methane at high latitudes (57–72°N; 64–89°S) were observed by the Improved Limb Atmospheric Spectrometer (ILAS) solar occultation sensor aboard Advanced Earth Observing Satellite. These measurements were made continuously from November 1996 through June 1997 with some additional periods in September–October 1996. A validation study of the nitrous oxide and methane data processed with the Version 5.20 ILAS retrieval algorithm is presented in this paper. Comparisons are made with (1) nitrous oxide and methane obtained by the ILAS validation balloon campaigns at Kiruna, Sweden, and at Fairbanks, Alaska, in the Arctic; (2) nitrous oxide and methane by the Photochemistry of Ozone Loss in the Arctic Region in Summer aircraft campaign in the Arctic; (3) nitrous oxide by the ground-based spectroscopic measurements and by the aircraft-based remote sensing measurements in the Arctic; and (4) methane by satellite measurements of the Version 19 Halogen Occultation Experiment in the Arctic and Antarctic. Comparisons of ILAS nitrous oxide and methane with Upper Atmosphere Research Satellite Reference Atmosphere data are also made. The results of the comparisons and additional ILAS internal consistency analyses are as follows: (1) the uncertainty of ILAS nitrous oxide is better than 10% over 10–30 km in altitude, and is larger than 50% over 30–40 km, which is comparable to the expected total errors of the ILAS measurements; (2) the uncertainty of ILAS methane is better than 10% over 10–50 km, except for 15–30 km in winter with positive biases exceeding 20%, which is smaller than or comparable to the expected total errors of the ILAS measurements (the quality of ILAS methane in the polar lower stratosphere is better in summer than in winter). In summary, the characteristics of ILAS measurements, i.e., high sampling frequency in polar latitudes with high vertical resolution, along with the good quality of ILAS Version 5.20 nitrous oxide for 10–40 km and the good quality of ILAS Version 5.20 methane for 10–50 km except for 15–30 km in winter, make the ILAS nitrous oxide and methane data set valuable for scientific study of various polar stratospheric phenomena.

Using discrete air sampling, values of δ 13 C and δ 18 O in atmospheric CO 2 , as well as its concentration, were measured in a forest in the central part of the main island of Japan during the period from June 1994 to June 1996 to examine the biospheric contribution to their temporal variations. δ 13 C shows a prominent diurnal variation with high values in the daytime and low values in the nighttime, especially during the warm season. δ 13 C also vary seasonally, showing a maximum in summer and a minimum in spring. The diurnal and seasonal variations of δ 13 C are opposite in phase with those of the CO 2 concentration. The rate of change in δ 13 C with respect to the CO 2 concentration is found to be approximately -0.05‰/ppmv. This suggests that the diurnal and seasonal variations of the CO 2 concentration are produced primarily by diurnally- and seasonally-dependent photosynthetic-respiratory processes of the biosphere near the observation site, respectively. In the warm season, δ 18 O also increases in the daytime and decreased in the nighttime, which is similar to the diurnal variation of δ 13 C, but opposite to that of the CO 2 concentration. The diurnal δ 18 O variation is thought to be caused by the release of isotopically heavy CO 2 during photosynthesis, and light CO 2 during respiration. However, an interpretation of the seasonal δ 18 O variation is found to be much more difficult than those of δ 13 C and the CO 2 concentration. This is likely due to complicated combinations of different seasonally varying fluxes of biospheric CO 2 into the atmosphere, as well as to various weather-dependent factors governing the δ 18 O composition in CO 2 . DOI: 10.1034/j.1600-0889.49.issue4.3.x