Investigation of parameters controlling the soil sink of atmospheric molecular hydrogen

Enclosure measurements have been performed on a bare mineral soil at an experimental field site near Heidelberg, Germany. From observed molecular hydrogen (H₂) mixing ratio changes in the enclosure, deposition velocities were calculated ranging from  8.4 × 10⁻³  to  8.2 × 10⁻² cm s⁻¹  and with an annual mean value of  3.1 × 10⁻² cm s⁻¹  . In the studied range of  2– 27 °C  , the uptake showed a significant temperature dependence. However, this turned out not to be the primary driving mechanism of the uptake flux. Soil moisture content, co-varying with temperature, was identified as the major parameter being responsible for the diffusive permeability of H₂ in the soil and the final rate of H₂ uptake. A simple Millington–Quirk diffusion model approach could largely explain this behaviour and yielded a diffusion path length of H₂ in the studied soil of only 0.2–1.8 cm, suggesting that total H₂ consumption occurs within the first few centimetres of the soil. The diffusion model, when applied to continuous measurements of soil moisture content, atmospheric pressure, temperature and the mixing ratio of H₂ in the atmosphere, could largely reproduce the measured deposition flux densities, assuming a mean thickness of the diffusion path length of 0.7 cm.     

Seasonal variation of the molecular hydrogen uptake by soils inferred from continuous atmospheric observations in Heidelberg, southwest Germany

The dominant sink of atmospheric molecular hydrogen (H₂) is its enzymatic destruction in soils. Quantitative estimates of the global sink strength, as derived from bottom-up process studies, are, however, still associated to large uncertainties. Here we present an alternative way to estimate atmosphere-to-soil flux densities, respectively deposition velocities of H₂, based on atmospheric H₂ and ²²²Rn observations in the boundary layer. Two and a half years of continuous measurements from a polluted site in the Rhine-Neckar area have been evaluated and night-time flux densities were calculated for situations of strong nocturnal boundary layer inversions using the Radon-Tracer Method. The influences from local anthropogenic combustion sources could be detected and successfully separated by parallel measurements of carbon monoxide. Inferred daily uptake fluxes in the Heidelberg catchment area range from 0.5 to 3 × 10⁻⁸ g H₂ m⁻² s⁻¹ with a mean value of (1.28 ± 0.31) × 10⁻⁸ g H₂ m⁻² s⁻¹. Uptake rates are about 25% larger during summer than during winter, when soil moisture is high, and diffusive transport of H₂ into the soil is inhibited. The mean deposition velocity is 3.0 ± 0.7 × 10⁻² cm s⁻¹_, which is very well in line with direct measurements on similar soil types in Europe and elsewhere.     

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.     

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.     

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.     

Evolution of boundary‐layer aerosol particles due to in‐cloud chemical reactions during the 2nd Lagrangian experiment of ACE‐2

The second Aerosol Characterisation Experiment (ACE‐2) was aimed at investigating the physical, chemical and radiative properties of aerosol and their evolution in the North Atlantic region. In the 2nd "Lagrangian" experiment, an air mass was tracked over a 30‐h period during conditions of extensive stratocumulus cover. Boundary‐layer measurements of the aerosol size distribution obtained with a passive cavity aerosol spectrometer probe (PCASP) during the experiment show a gradual growth in size of particles in the 0.1–0.2 μm diameter mode. Simultaneously, SO₂ concentrations were found to decrease sharply from 800 to 20 ppt. The fraction of sulphate in aerosol ionic mass increased from 0.68±0.07 to 0.82±0.09 for small particles (diameter below 1.7 μm) and from 0.21±0.04 to 0.34±0.03 for large particles (diameter above 1.7 μm). The measurements were compared with a multicyclic parcel model of gas phase diffusion into cloud droplets and aqueous phase chemical reactions. The model was able to broadly reproduce the observed transformation in the aerosol spectra and the timescale for the transformation of SO₂ to sulphate aerosol. The modelled SO₂ concentration in the boundary layer fell to below half its initial value over a 6.5‐h time period due to a combination of the entrainment of cleaner tropospheric air and cloud chemical reactions. NH₃ and HCl gas were also found to play an important rôle in cloud processing in the model.     

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.     

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).     

Feedback mechanisms and sensitivities of ocean carbon uptake under global warming

Global warming simulations are performed with a coupled climate model of reduced complexity to investigate global warming–marine carbon cycle feedbacks. The model is forced by emissions of CO₂ and other greenhouse agents from scenarios recently developed by the Intergovernmental Panel on Climate Change and by CO₂ stabilization profiles. The uptake of atmospheric CO₂ by the ocean is reduced between 7 to 10% by year 2100 compared to simulations without global warming. The reduction is of similar size in the Southern Ocean and in low‐latitude regions (32.5°S‐32.5°N) until 2100, whereas low‐latitude regions dominate on longer time scales. In the North Atlantic the CO₂ uptake is enhanced, unless the Atlantic thermohaline circulation completely collapses. At high latitudes, biologically mediated changes enhance ocean CO₂ uptake, whereas in low‐latitude regions the situation is reversed. Different implementations of the marine biosphere yield a range of 5 to 16% for the total reduction in oceanic CO₂ uptake until year 2100. Modeled oceanic O₂ inventories are significantly reduced in global warming simulations. This suggests that the terrestrial carbon sink deduced from atmospheric O₂/N₂ observations is potentially overestimated if the oceanic loss of O₂ to the atmosphere is not considered.     

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.     

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.     

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.     

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.     

Clear‐sky closure studies of lower tropospheric aerosol and water vapor during ACE‐2 using airborne sunphotometer, airborne in‐situ, space‐borne, and ground‐based measurements

We report on clear‐sky column closure experiments (CLEARCOLUMN) performed in the Canary Islands during the second Aerosol Characterization Experiment (ACE‐2) in June/July 1997. We present CLEARCOLUMN results obtained by combining airborne sunphotometer and in‐situ (optical particle counter, nephelometer, and absorption photometer) measurements taken aboard the Pelican aircraft, space‐borne NOAA/AVHRR data and ground‐based lidar and sunphotometer measurements. During both days discussed here, vertical profiles flown in cloud‐free air masses revealed 3 distinctly different layers: a marine boundary layer (MBL) with varying pollution levels, an elevated dust layer, and a very clean layer between the MBL and the dust layer. A key result of this study is the achievement of closure between extinction or layer aerosol optical depth (AOD) computed from continuous in‐situ aerosol size‐distributions and composition and those measured with the airborne sunphotometer. In the dust, the agreement in layer AOD (λ=380–1060 nm) is 3–8%. In the MBL there is a tendency for the in‐situ results to be slightly lower than the sunphotometer measurements (10–17% at λ=525 nm), but these differences are within the combined error bars of the measurements and computations.     

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.     

Future changes of the atmospheric composition and the impact of climate change

The development of the future atmospheric chemical composition is investigated with respect to NO _y and O₃ by means of the off‐line coupled dynamic‐chemical general circulation model ECHAM3/CHEM. Two time slice experiments have been performed for the years 1992 and 2015, which include changes in sea surface temperatures, greenhouse gas concentrations, emissions of CFCs, NO _x and other species, i.e., the 2015 simulation accounts for changes in chemically relevant emissions and for a climate change and its impact on air chemistry. The 2015 simulation clearly shows a global increase in ozone except for large areas of the lower stratosphere, where no significant changes or even decreases in the ozone concentration are found. For a better understanding of the importance of (A) emissions like NO _x and CFCs, (B) future changes of air temperature and water vapour concentration, and (C) other dynamical parameters, like precipitation and changes in the circulation, diabatic circulation, stratosphere‐troposphere‐exchange, the simulation of the future atmosphere has been performed stepwise. This method requires a climate‐chemistry model without interactive coupling of chemical species. Model results show that the direct effect of emissions (A) plays a major rôle for the composition of the future atmosphere, but they also clearly show that climate change (B and C) has a significant impact and strongly reduces the NO _y and ozone concentration in the lower stratosphere.     

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.     

Atmospheric concentrations and deposition of oxidised sulfur and nitrogen species at Petaling Jaya, Malaysia, 1993–1998

Wet‐only rainwater composition, acid‐precursor gas mixing ratios and aerosol loading were determined from weekly‐averaged samples at Petaling Jaya, Malaysia, over the five year period from March 1993 to March 1998. Annual deposition fluxes of acidic sulfur and nitrogen species estimated from these data show this site to be heavily impacted by acidic deposition, with total oxidised sulfur plus nitrogen deposition in the range 277–480 meq m⁻² yr⁻¹. Average contributions were 56% as sulfur species, 44% as nitrogen species, with wet deposition in this region of high rainfall accounting for 67% of total deposition. Thus total acid deposition fluxes were equivalent to levels that provided motivation for emissions reduction programs in both Europe and North America. The possibility of adverse environmental effects in Malaysia caused by acid deposition therefore merits serious consideration and assessment.     

Broadband extinction method to determine atmospheric aerosol optical properties

The equivalent wavelength ( λ _E), at which the aerosol optical depth (AOD) is equal to broadband AOD (BAOD), can change in a wide range from 0.619 μm to 1.575 μm in the usual aerosol conditions. By using the least squares technique and some empirical corrections, a parameterized relationship of λ _E with BAOD, Ångström wavelength exponent ( α ), solar zenith angle ( θ ₀) and H₂O amount is developed. Using this relationship, and based on the strong sensitivity of BAOD on θ ₀ when θ ₀>70°, the broadband extinction method to derive the spectral AOD and α is further proposed. As shown in comparative simulations to retrieve AOD by the present, Molineaux et al. and Gueymard methods, the present method has the best accuracy in most simulations using Junge, MODTRAN, log‐normal and Deirmendjian aerosol models. A key question of the pyrheliometer method to determine wavelength-dependent AODs is the effect of uncertainty in the aerosol size istribution. It is found that the AOD solution around λ _E is less sensitive to the uncertainty. The wavelength exponent α is derived using an assumption of the stable atmospheric turbidity. If the pyrheliometer data from θ ₀=85° to 70° are used and the change of the turbidity is ±10%, the error of solution α is usually within ±0.32. If the variation of the turbidity is random, the mean value of a lot of the measurements of α would be very reasonable.     

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.