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.     

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.     

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.     

Vertical profiles of biospheric and fossil fuel-derived CO2 and fossil fuel CO2 : CO ratios from airborne measurements of Δ14C, CO2 and CO above Colorado, USA

Measurements of  Δ¹⁴C  in atmospheric CO₂ are an effective method of separating CO₂ additions from fossil fuel and biospheric sources or sinks of CO₂. We illustrate this technique with vertical profiles of CO₂ and  Δ¹⁴C  analysed in whole air flask samples collected above Colorado, USA in May and July 2004. Comparison of lower tropospheric composition to cleaner air at higher altitudes (>5 km) revealed considerable additions from respiration in the morning in both urban and rural locations. Afternoon concentrations were mainly governed by fossil fuel emissions and boundary layer depth, also showing net biospheric CO₂ uptake in some cases. We estimate local industrial CO₂:CO emission ratios using in situ measurements of CO concentration. Ratios are found to vary by 100% and average 57 mole CO₂:1 mole CO, higher than expected from emissions inventories. Uncertainty in CO₂ from different sources was ±1.1 to ±4.1 ppm for addition or uptake of −4.6 to 55.8 ppm, limited by  Δ¹⁴C  measurement precision and uncertainty in background  Δ¹⁴C  and CO₂ levels.     

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).     

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.     

Isotopic composition and origin of polar precipitation in present and glacial climate simulations

The Hamburg atmospheric general circulation model (AGCM) ECHAM‐4 is used to identify the main source regions of precipitation falling on Greenland and Antarctica. Both water isotopes H₂¹⁸O and HDO are explicitly built into the water cycle of the AGCM, and in addition the capability to trace water from different source regions was added to the model. Present and LGM climate simulations show that water from the most important source regions has an isotopic signature similar to the mean isotope values of the total precipitation amount. But water from other source regions (with very different isotopic signatures) contributes an additional, non‐negligible part of the total precipitation amount on both Greenland and Antarctica. Analyses of the temperature‐isotope‐relations for both polar regions reveal a solely bias of the glacial isotope signal on Greenland, which is caused by a strong change in the seasonal deposition of precipitation originating from nearby polar seas and the northern Atlantic. Although the performed simulations under LGM boundary conditions show a decrease of the δ ¹⁸O values in precipitation in agreement with ice core measurements, the AGCM fails to reproduce the observed simultaneous decrease of the deuterium excess signal.     

Seasonal and global NOx production by lightning estimated from the Optical Transient Detector (OTD)

The Optical Transient Detector (OTD) lightning data for the 12‐month period of 1996 are used to estimate the seasonal and global distributions of lightning‐produced NO _x . The relatively small viewing footprint and the low detection efficiency of the OTD sensor and other difficulties require extrapolations of the OTD data to the actual global flash distributions. Furthermore, available measurements for the ratios of intracloud (IC) to cloud‐to‐ground (CG) flashes have been used to partition lightning counts for IC versus CG flashes from the OTD observations. The resulting lightning distributions are then used to calculate the global and seasonal production of NO _x , assuming a NO production rate of 6.2×10²⁵ molecules for each CG flash and 8.7×10²⁴ molecules for each IC flash. Consequently, we find that CG flashes produce more NO _x than IC flashes despite fewer CG flashes by a factor of 3 or more. NO _x production by lightning varies seasonally in accordance with the global lightning distribution, with the maximum production occurring in the Northern Hemisphere in the local summer. The latitudinal distribution of NO _x production exhibits a strong seasonal variation outside the tropics with the production occurring mainly in the summer hemisphere, whereas in the tropics the production is high throughout the year. The annual contribution to NO _x production by lightning is higher in the Northern Hemisphere than that in the Southern Hemisphere.     

Analysis of regional budgets of sulfur species modeled for the COSAM exercise

The COSAM intercomparison exercise (comparison of large‐scale sulfur models) was organized to compare and evaluate the performance of global sulfur cycle models. Eleven models participated, and from these models the simulated surface concentrations, vertical profiles and budget terms were submitted. This study focuses on simulated budget terms for the sources and sinks of SO₂ and sulfate in three polluted regions in the Northern Hemisphere, i.e., eastern North America, Europe, and Southeast Asia. Qualitatively, features of the sulfur cycle are modeled quite consistently between models, such as the relative importance of dry deposition as a removal mechanism for SO₂, the importance of aqueous phase oxidation over gas phase oxidation for SO₂, and the importance of wet over dry deposition for removal of sulfate aerosol. Quantitatively, however, models may show large differences, especially for cloud‐related processes, i.e., aqueous phase oxidation of SO₂ and sulfate wet deposition. In some cases a specific behavior can be related to the treatment of oxidants for aqueous phase SO₂ oxidation, or the vertical resolution applied in models. Generally, however, the differences between models appear to be related to simulated cloud (micro‐)physics and distributions, whereas differences in vertical transport efficiencies related to convection play an additional rôle. The estimated sulfur column burdens, lifetimes and export budgets vary between models by about a factor of 2 or 3. It can be expected that uncertainties in related effects which are derived from global sulfur model calculations, such as direct and indirect climate forcing estimates by sulfate aerosol, are at least of similar magnitude.     

Boron isotope variations in the atmosphere

We report here the first measurements of boron isotope ratios in the maritime atmosphere together with those of precipitation. The δ¹¹B values of atmospheric condensates in the western North Pacific and Japanese coast and snow in Tokyo range from −12.8 to +5.1‰ and from −0.4 to +0.4‰, respectively, which are significantly lower than those of rainwater (+18.9 to +34.7‰) collected mostly over the North Pacific. Since the ¹¹B/¹⁰B ratios of the atmosphere are lower than those of volcanic emissions (δ¹¹B=+2.3 to +21.4‰), we must seek sources for atmospheric boron other than volcanism. We postulate that the sea may be an important supplier for atmospheric boron under some dynamic conditions and that boron isotope fractionation during evaporation from seawater and removal from the atmosphere may account for the large variations of ¹¹B/¹⁰B ratios observed in the atmosphere and precipitation.     

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.     

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.     

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.     

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.     

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.     

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.     

A pseudo-Lagrangian study of the sulfur budget in the remote Arctic marine boundary layer

The atmospheric sulfur cycle of the remote Arctic marine boundary layer is studied using trajectories and measurements of sulfur compounds from the International Arctic Ocean Expedition 1991, along with a pseudo-Lagrangian approach and an analytical model. The dimethyl sulfide [DMS(g)] turnover time was  h. Only  % of DMS(g) followed reaction paths to sulfur dioxide [SO₂(g)], sub-micrometre aerosol non-seasalt sulfate (nss-SO₄²⁻) or methane sulfonate (MSA). During the first 3 d of transport over the pack ice, fog deposition and drizzle resulted in short turnover times;  h for SO₂(g),  h for MSA and  h for nss-SO₄²⁻. Therefore, DMS(g) will, owing to its origin along or south of the ice edge and longer turnover time, survive the original sub-micrometre sulfur aerosol mass and gradually replace it with new biogenic sulfur aerosol mass. The advection of DMS(g) along with heat and moisture will influence the clouds and fogs over the Arctic pack ice through the formation of cloud condensation nuclei (CCN). If the pack ice cover were to decrease owing to a climate change, the total Arctic Ocean DMS production would change, and potentially there could be an ice–DMS–cloud–albedo climate feedback effect, but it would be accompanied by changes in the fog aerosol sink.     

Sulfur budget above the Eastern Mediterranean: relative contribution of anthropogenic and biogenic sources

To access the relative contribution of anthropogenic and biogenic sulfur sources to the sulfur budget in the Eastern Mediterranean, an area characterized by very high nss-     levels, measurements of both wet and dry deposition of sulfur were performed at a remote area on the island of Crete (Finokalia) during a 3-yr period (1996–1999). The estimation of dry deposition is based on both gaseous sulfur dioxide (SO₂) and particulate phase non-sea-salt sulfate (nss-     ) and methane sulfonate (MSA) measurements. During the dry period, deposition of SO₂ from long-range transport is the main component of anthropogenic sulfur deposition in the area. The results of the wet and dry deposition obtained at Finokalia have been compared with DMS emission from seawater obtained during two yearly surveys (1997–1998) in the Cretan Sea. Our results indicate that the contribution from biogenic sources to the sulfur budget in the Eastern Mediterranean, although negligible during winter, can account for up to 26% during summer.