Diurnal variation of CO2 concentration, Δ14C and δ13C in an urban forest: estimate of the anthropogenic and biogenic CO2 contributions

Diurnal variation in the atmospheric CO₂ concentration and the carbon isotopic composition (Δ¹⁴C and δ¹³C) was measured in a forest in an urban area on 9 February 1999. The carbon isotope approach used in the present study differentiated between the quantitative contributions from anthropogenic and biogenic CO₂ sources in the urban atmosphere. The anthropogenic (fossil fuel) and biogenic (soil respiration) contributions was estimated, and they ranged from 1 to 16% and from 2 to 8% of the total atmospheric CO₂. The diurnal variation of the anthropogenic CO₂ was the major cause of the total atmospheric CO₂ variation, while the biogenic CO₂ remained relatively constant throughout the day. Estimating the contribution of soil respired CO₂ provided the mean residence time of soil respired CO₂ within the forest atmosphere.     

A recent build-up of atmospheric CO2 over Europe. Part 1: observed signals and possible explanations

We analysed interannual and decadal changes in the atmospheric CO₂ concentration gradient (ΔCO₂) between Europe and the Atlantic Ocean over the period 1995–2007. Fourteen measurement stations are used, with Mace-Head being used to define background conditions. The variability of ΔCO₂ reflects fossil fuel emissions and natural sinks activity over Europe, as well as atmospheric transport variability. The mean ΔCO₂ increased by 1–2 ppm at Eastern European stations (∼30% growth), between 1990–1995 and 2000–2005. This built up of CO₂ over the continent is predominantly a winter signal. If the observed increase of ΔCO₂ is explained by changes in ecosystem fluxes, a loss of about 0.46 Pg C per year would be required during 2000–2005. Even if severe droughts have impacted Western Europe in 2003 and 2005, a sustained CO₂ loss of that magnitude is unlikely to be true. We sought alternative explanations for the observed CO₂ build-up into transport changes and into regional redistribution of fossil fuel CO₂ emissions. Boundary layer heights becoming shallower can only explain 32% of the variance of the signal. Regional changes of emissions may explain up to 27% of the build-up. More insights are given in the Aulagnier et al. companion paper.     

Reconciliation of excess 14C-constrained global CO2 piston velocity estimates

Oceanic excess radiocarbon data is widely used as a constraint for air–sea gas exchange. However, recent estimates of the global mean piston velocity  〈 k 〉  from Naegler et al., Krakauer et al., Sweeney et al. and Müller et al. differ substantially despite the fact that they all are based on excess radiocarbon data from the GLODAP data base. Here I show that these estimates of  〈 k 〉  can be reconciled if first, the changing oceanic radiocarbon inventory due to net uptake of CO₂ is taken into account; second, if realistic reconstructions of sea surface  Δ¹⁴C  are used and third, if  〈 k 〉  is consistently reported with or without normalization to a Schmidt number of 660. These corrections applied, unnormalized estimates of  〈 k 〉  from these studies range between 15.1 and 18.2 cm h⁻¹. However, none of these estimates can be regarded as the only correct value for  〈 k 〉  . I thus propose to use the 'average' of the corrected values of  〈 k 〉  presented here (16.5 ± 3.2 cm h⁻¹) as the best available estimate of the global mean unnormalized piston velocity  〈 k 〉  , resulting in a gross ocean-to-atmosphere CO₂ flux of 76 ± 15 PgC yr⁻¹ for the mid-1990s.     

The YAK-AEROSIB transcontinental aircraft campaigns: new insights on the transport of CO2, CO and O3 across Siberia

Two airborne campaigns were carried out to measure the tropospheric concentrations and variability of CO₂, CO and O₃ over Siberia. In order to quantify the influence of remote and regional natural and anthropogenic sources, we analysed a total of 52 vertical profiles of these species collected in April and September 2006, every ∼200 km and up to 7 km altitude. CO₂ and CO concentrations were high in April 2006 (respectively 385–390 ppm CO₂ and 160–200 ppb CO) compared to background values. CO concentrations up to 220 ppb were recorded above 3.5 km over eastern Siberia, with enhancements in 500–1000 m thick layers. The presence of CO enriched air masses resulted from a quick frontal uplift of a polluted air mass exposed to northern China anthropogenic emissions and to fire emissions in northern Mongolia. A dominant Asian origin for CO above 4 km (71.0%) contrasted with a dominant European origin below this altitude (70.9%) was deduced both from a transport model analysis, and from the contrasted ΔCO/ΔCO₂ ratio vertical distribution. In September 2006, a significant O₃ depletion (∼–30 ppb) was repeatedly observed in the boundary layer, as diagnosed from virtual potential temperature profiles and CO₂ gradients, compared to the free troposphere aloft, suggestive of a strong O₃ deposition over Siberian forests.     

Determination of microbial versus root‐produced CO2 in an agricultural ecosystem by means of δ13CO2 measurements in soil air

The amounts of microbial and root‐respired CO₂ in a maize/winter wheat agricultural system in south western Germany were investigated by measurements of the CO₂ mixing ratio and the ¹³C/¹²C ratio in soil air. CO₂ fluxes at the soil surface for the period of investigation (1993–1995) were also determined. Root respired CO₂ shows a strong correlation with the plant mass above ground surface of the respective vegetation (R²≥0.88); the maximum CO₂ release from roots was in August for the maize (2.0±0.5 mmol m⁻² h⁻¹) and in June for winter wheat (1.5±0.5 mmol m⁻² h⁻¹). Maximum CO₂ production by roots correlate well with the maximum amount of plant root matter. Integrating the CO₂ production over the whole growing season and normalizing to the dry root matter yields, the CO₂ production per gram dry organic root matter (DORM) of maize was found to be 0.14±0.03 gC (g DORM)⁻¹. At the sites investigated, root‐produced CO₂ contributed (16±4)% for maize, and (24±4)% for winter wheat, respectively, to the total annual CO₂ production in the soil (450±50 gC m⁻² for maize, 210±30 gC m⁻² for winter wheat).     

The H2/CO ratio of emissions from combustion sources: comparison of top-down with bottom-up measurements in southwest Germany

The hydrogen-to-carbon monoxide (H₂/CO) emission ratio of anthropogenic combustion sources was determined from more than two years of quasi-continuous atmospheric observations in Heidelberg (49°24' N, 8°42' E), located in the polluted Rhein-Neckar region. Evaluating concurrent mixing ratio changes of H₂ and CO during morning rush hours yielded mean molar H₂/CO ratios of 0.40 ± 0.06, while respective results inferred from synoptic pollution events gave a mean value of 0.31 ± 0.05 mole H₂/mole CO. After correction for the influence of the H₂ soil sink on the measured ratios, mean values of 0.46 ± 0.07 resp. 0.48 ± 0.07 mole H₂/mole CO were obtained, which are in excellent agreement with direct source studies of traffic emissions in the Heidelberg/Mannheim region (0.448 ± 0.003 mole H₂/mole CO). Including results from other European studies, our best estimate of the mean H₂/CO emission ratio from anthropogenic combustion sources (mainly traffic) ranges from 0.45 to 0.48 mole H₂/mole CO, which is about 20% smaller than the value of 0.59 mole H₂/mole CO which is frequently used as the basis to calculate global H₂ emissions from anthropogenic combustion sources.     

Assessment of the soil CO2 gradient method for soil CO2 efflux measurements: comparison of six models in the calculation of the relative gas diffusion coefficient

This paper uses a refined soil gradient method to estimate soil CO₂ efflux. Six different models are used to determine the relative gas diffusion coefficient (ξ). A weighted harmonic averaging is used to estimate the soil CO₂ diffusion coefficient, yielding a better estimate of soil CO₂ efflux. The resulting soil CO₂ efflux results are then compared to the soil CO₂ efflux measured with a soil chamber. Depending on the choice of ξ model used, the estimated soil CO₂ efflux using the gradient method reasonably approximates the efflux obtained using the soil chamber method. In addition, the estimated soil CO₂ efflux obtained by this improved method is well described by an exponential function of soil temperature at a depth of 0.05 m with the temperature sensitivity ( Q ₁₀) of 1.81 and a linear function of soil moisture at a depth of 0.12 m, in general agreement with previous findings. These results suggest that the gradient method is a practical cost-effective means to measure soil CO₂ emissions. Results from the present study suggest that the gradient method can be used successfully to measure soil CO₂ efflux provided that proper attention is paid to the judicious use of the proper diffusion coefficient.     

Anthropogenic and biogenic winter sources of Arctic CO2—a model study

Long‐range transport of anthropogenic and biogenic CO₂ to a remote site in the Arctic is studied. A limited area, off‐line, Eulerian atmospheric transport model is used, and the results are compared to the observed CO₂ concentration at the "Ny‐Alesund International Arctic Research and Monitoring Facility". Inventories of anthropogenic CO₂ emissions and estimates of biogenic CO₂ emissions are used to investigate the respective impact of these emissions on Arctic CO₂ variations during 4 winter months. A direct comparison of the modelled and observed concentrations reveals remarkably good timing in the modelled variations as compared to the observed variations for most of the time. The correlation of observed versus modelled CO₂ concentration is significant at the 95% confidence level. The biogenic and the anthropogenic CO₂ emissions are shown to have approximately equal influence on Arctic CO₂ variations during winter. Europe is found to be the dominant source of anthropogenic CO₂ at the monitoring station, while Siberia and Northern America have little influence on Arctic CO₂, during the months studied. These results contradict Engardt and Holmén whose results indicate that the lower‐Ob region in western Siberia has a large impact on Arctic CO₂.     

Simulating effects of land use changes on carbon fluxes: past contributions to atmospheric CO2 increases and future commitments due to losses of terrestrial sink capacity

The impact of land use on the global carbon cycle and climate is assessed. The Bern carbon cycle-climate model was used with land use maps from HYDE3.0 for 1700 to 2000 A.D. and from post-SRES scenarios for this century. Cropland and pasture expansion each cause about half of the simulated net carbon emissions of 188 Gt C over the industrial period and 1.1 Gt C yr⁻¹ in the 1990s, implying a residual terrestrial sink of 113 Gt C and of 1.8 Gt C yr⁻¹, respectively. Direct CO₂ emissions due to land conversion as simulated in book-keeping models dominate carbon fluxes due to land use in the past. They are, however, mitigated by 25% through the feedback of increased atmospheric CO₂ stimulating uptake. CO₂ stimulated sinks are largely lost when natural lands are converted. Past land use change has eliminated potential future carbon sinks equivalent to emissions of 80–150 Gt C over this century. They represent a commitment of past land use change, which accounts for 70% of the future land use flux in the scenarios considered. Pre-industrial land use emissions are estimated to 45 Gt C at most, implying a maximum change in Holocene atmospheric CO₂ of 3 ppm. This is not compatible with the hypothesis that early anthropogenic CO₂ emissions prevented a new glacial period.     

Vertical profiles and storage fluxes of CO2, heat and water in a tropical rainforest at Pasoh, Peninsular Malaysia

Ambient CO₂ concentration, air temperature and relative humidity were measured intermittently for a 3-year period from the floor to the canopy top of a tropical rainforest in Pasoh, Peninsular Malaysia. Mean diurnal CO₂ storage flux ( S _c; μmol m⁻² s⁻¹) and sensible and latent heat storage fluxes ( Q _a and Q _w; W m⁻²) ranged from −12.7 to 3.2 μmol m⁻² s⁻¹, −15 to 27 W m⁻² and −10 to 20 W m⁻², respectively. Small differences in diurnal changes were observed in S _c and Q _a between the driest and wettest periods. Compared with the ranges of mean diurnal CO₂ eddy flux (−14.7 to 4.9 μmol m⁻² s⁻¹), sensible eddy flux (−12 to 169 W m⁻²) and latent eddy flux (0 to 250 W m⁻²), the contribution of CO₂ storage flux was especially large. Comparison with summertime data from a temperate Japanese cypress forest suggested a higher contribution of S _c in the tropical rainforest, probably mainly due to the difference in nighttime friction velocity at the sites. On the other hand, differences in Q _a and Q _w were smaller than the difference in S _c, probably because of the smaller nighttime sinks/sources of heat and water vapour.     

In situ produced 14C by cosmic ray muons in ablating Antarctic ice

Samples of a core (52 m) of ablating Antarctic ice were analysed for ¹⁴CO and ¹⁴CO₂ by accelerator mass spectrometry. The data were compared with a ¹⁴C in situ production model that includes muon capture in addition to oxygen spallation by neutrons. The analysis reveals significant in situ ¹⁴C at depths below 10 m, which we attribute to ¹⁴C production by cosmic ray muons. The age of the ice was determined as 9.3±0.4 ¹⁴C ka BP.     

Spring initiation and autumn cessation of boreal coniferous forest CO2 exchange assessed by meteorological and biological variables

We studied the commencement and finishing of the growing season using different air temperature indices, the surface albedo, the chlorophyll fluorescence (Fv/Fm) and the carbon dioxide (CO₂) tropospheric concentration, together with eddy covariance measurements of CO₂ flux. We used CO₂ flux data from four boreal coniferous forest sites covering a wide latitudinal range, and CO₂ concentration measurements from Sammaltunturi in Pallas. The CO₂ gas exchange was taken as the primary determinant for the growing season to which other methods were compared.
Indices based on the cumulative temperature sum and the variation in daily mean temperature were successfully used for approximating the start and cessation of the growing season. The beginning of snow melt was a successful predictor of the onset of the growing season. The chlorophyll fluorescence parameter Fv/Fm and the CO₂ concentration were good indicators of both the commencement and cessation of the growing season. By a derivative estimation method for the CO₂ concentration, we were also able to capture the larger-scale spring recovery. The trends of the CO₂ concentration and temperature indices at Pallas/Sammaltunturi were studied over an 11-yr time period, and a significant tendency towards an earlier spring was observed. This tendency was not observed at the other sites.     

Climate effects on atmospheric carbon dioxide over the last century

The buildup of atmospheric CO₂ since 1958 is surprisingly well explained by the simple premise that 57% of the industrial emissions (fossil fuel burning and cement manufacture) has remained airborne. This premise accounts well for the rise both before and after 1980 despite a decrease in the growth rate of fossil fuel CO₂ emissions, which occurred at that time, and by itself should have caused the airborne fraction to decrease. In contrast, the buildup prior to 1958 was not simply proportional to cumulative fossil fuel emissions, and notably included a period during the 1940s when CO₂ growth stalled despite continued fossil fuel emissions. Here we show that the constancy of the airborne fraction since 1958 can be in part explained by decadal variations in global land air temperature, which caused a warming-induced release of CO₂ from the land biosphere to the atmosphere. We also show that the 1940s plateau may be related to these decadal temperature variations. Furthermore, we show that there is a close connection between the phenomenology producing CO₂ variability on multidecadal and El Niño timescales.     

Model analysis of the influence of gas diffusivity in soil on CO and H2 uptake

CO and H₂ uptake by soil was studied as a diffusion process. A diffusion model was used to determine how the surface fluxes (net deposition velocities) were controlled by in‐situ microbial uptake rates and soil gas diffusivity calculated from the 3‐phase system (solid, liquid, gas) in the soil. Analytical solutions of the diffusion model assuming vertical uniformity of soil properties showed that physical properties such as air‐filled porosity and soil gas diffusivity were more important in the uptake process than in the emission process. To incorporate the distribution of in‐situ microbial uptake, we used a 2‐layer model incorporating "a microbiologically inactive layer and an active layer" as suggested from experimental results. By numerical simulation using the 2‐layer model, we estimated the effect of several factors on deposition velocities. The variations in soil gas diffusivity due to physical properties, i.e., soil moisture and air‐filled porosity, as well as to the depth of the inactive layer and in‐situ microbial uptake, were found to be important in controlling deposition velocities. This result shows that the diffusion process in soil is critically important for CO and H₂ uptake by soil, at least in soils with higher in‐situ uptake rates and/or with large variation in soil moisture. Similar uptake rates and the difference in deposition velocity between CO and H₂ may be attributable to differences in CO and H₂ molecular diffusivity. The inactive layer is resistant to diffusion and creates uptake limits in CO and H₂ by soil. The coupling of high temperature and a thick inactive layer, common in arid soils, markedly lowers net CO deposition velocity. The temperature for maximum uptake of CO changes with depth of the inactive layer.     

Is the recent build-up of atmospheric CO2 over Europe reproduced by models. Part 2: an overview with the atmospheric mesoscale transport model CHIMERE

In this issue, Ramonet et al. revealed a positive trend in European, atmospheric CO₂ concentrations relative to a marine, North Atlantic reference baseline, for the years 2001–2006. The observed build up mainly occurred during the cold season where it reaches a 0.8 ppm yr⁻¹ at low-altitude stations to a 0.3 ppm yr⁻¹ at mid-altitude stations. We explore the cause of this build-up using the mesoscale model CHIMERE. We first model the observed trends, using interannually varying fluxes and transport, then suppress the interannual variability in fluxes or aspects of transport to elucidate the cause. The run with no interannual variability in fluxes still matches observed trends suggesting that transport is the major cause. Separate runs varying either boundary layer height or winds show that changes in boundary layer height explain the trends at low-altitude stations within the continents while changes in wind regimes drive changes elsewhere.     

Excess 210Po in the coastal atmosphere

Many researchers have reported the widespread occurrence of excess ²¹⁰ Po in the global atmosphere and suggested probable sources such as resuspension of top soils, stratospheric aerosols, sea spray of the surface micro‐layer, volcanic emission, and bio‐volatile ²¹⁰Po species from the productive ocean. We have observed excess ²¹⁰Po on aerosols in the coastal atmosphere of the Chesapeake and Delaware Bays. On‐board measurements in the Chesapeake Bay atmosphere show that the increase of this excess ²¹⁰Po is dependent upon wind speed. Simultaneously measured activity ratios of ⁷Be/²¹⁰Pb and ²¹⁰Pb/²²²Rn argue against either higher altitude air or continental soils as the source of this excess. We hypothesize that the excess ²¹⁰Po originates mainly from surface waters either by the sea‐spray of the surface microlayer, or more likely, by gas exchange. We conclude gas exchange as the mechanism since the polonium excess increases linearly with wind speed over a threshold of 3 m s⁻¹(mean) similar to other gases (i.e., CO₂, SF₆ , and DMS). In addition, higher ²¹⁰Po excess with lower ²²²Rn is observed in on‐shore marine air at Lewes, DE. This suggests sea‐air exchange of volatile Po along with other bio‐volatile species (i.e., DMS, DMSe, and MMHg) in the coastal productive ocean during high wind speeds.     

Projections of SO2, NOx and carbonaceous aerosols emissions in Asia

Estimates of Asian emissions of air pollutants and carbonaceous aerosols and their mid-term projections have been changing significantly in the last years. The remote sensing community has shown that increase in NO _x in Central East Asia is much stronger than any of the emission inventories or projections indicated so far. A number of studies reviewing older estimates appeared. Here, we review the key contributions and compare them to the most recent results of the GAINS model application for Asia and to the SRES projections used in the IPPC work. The recent projections indicate that the growth of emissions of SO₂ in Asia should slow down significantly towards 2010 or even stabilize at the current level. For NO _x , however, further growth is projected although it will be most likely slower that in the last decade, owing to introduction of measures in transport. Emissions of carbonaceous aerosols (black carbon and organic carbon) are expected to decline after 2010, largely due to reduced use of biofuels in residential sector and efficiency improvements. The estimates of these emissions are burdened with significantly larger uncertainties than SO₂ and NO _x ; even for the year 2000 the differences in estimates between studies are up to a factor of 2.     

Sulfur (32S, 33S, 34S, 36S) and oxygen (16O,17O,18O) isotopic ratios of primary sulfate produced from combustion processes

The recent discovery of an anomalous enrichment in ¹⁷O isotope in atmospheric sulfate has opened a new way to investigate the oxidation pathways of sulfur in the atmosphere. From laboratory investigations, it has been suggested that the wet oxidation of sulfur in rain droplets was responsible for the excess ¹⁷O. In order to confirm this theory, sulfur and oxygen isotope ratios of different primary sulfates produced during fossil fuel combustion have been investigated and are reported. None of these samples exhibits any anomalous oxygen or sulfur isotopic content, as compared to urban sulfate aerosols. These results, in agreement with the laboratory investigations, reinforce the idea of an aqueous origin for the oxygen-17 anomaly found in tropospheric sulfates.     

Tropospheric carbon dioxide concentrations at a northern boreal site in Finland: basic variations and source areas

Diurnal and annual variations of CO₂, O_3, SO₂, black carbon and condensation nuclei and their source areas were studied by utilizing air parcel trajectories and tropospheric concentration measurements at a boreal GAW site in Pallas, Finland. The average growth trend of CO₂ was about 2.5 ppm yr⁻¹ according to a 4-yr measurement period starting in October 1996. The annual cycle of CO₂ showed concentration difference of about 19 ppm between the summer minimum and winter maximum. The diurnal cycle was most pronounced during July and August. The variation between daily minimum and maximum was about 5 ppm. There was a diurnal cycle in aerosol concentrations during spring and summer. Diurnal variation in ozone concentrations was weak. According to trajectory analysis the site was equally affected by continental and marine air masses. During summer the contribution of continental air increased, although the southernmost influences decreased. During daytime in summer the source areas of CO₂ were mainly located in the northern parts of the Central Europe, while during winter the sources were more evenly distributed. Ozone showed similar source areas during summer, while during winter, unlike CO₂, high concentrations were observed in air arriving from the sea. Sulfur dioxide sources were more northern (Kola peninsula and further east) and CO₂ sources west-weighted in comparison to sources of black carbon. Source areas of black carbon were similar to source areas of aerosols during winter. Aerosol source area distributions showed signs of marine sources during spring and summer.