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.     

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.     

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.     

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.     

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.     

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.     

Effect of emission changes in Southeast Asia on global hydroxyl and methane lifetime

We performed model studies on how anthropogenic emission changes in Southeast Asia (region between 60–150°E and 10°S–50°N) in the period 1980–2020 could contribute to changes in hydroxyl and methane lifetime on a global scale. From 1980 to 2000, we calculate small global OH and methane lifetime changes due to compensating effects by emission changes in Southeast Asia and emission changes in the rest of the world. There is no guarantee that this offset will persist in the future. Southeast Asia is going through rapid economic development and emission increases there may be a major driver for changes. The development of Asian emissions after year 2000 is under much debate and for this period we apply several emission scenarios. For most emission scenarios the simulated Southeast Asian induced changes in global hydroxyl and methane lifetime after year 2000 are moderate. However, an upper estimate assuming very high increases in NO _x emissions results in substantial increases of hydroxyl and corresponding reductions in global methane lifetime. Interestingly, for the high NO _x emission case our results fit very well with recent satellite observations on trends of NO₂ over central eastern China.     

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.     

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).     

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.     

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.     

Aircraft observation of carbon dioxide at 8–13 km altitude over the western Pacific from 1993 to 1999

Abstract The spatial and temporal variations of atmospheric CO₂ at 8–13 km from April 1993 to April 1999 were observed by measuring CO₂ mixing ratios in samples collected biweekly from a commercial airliner between Australia and Japan. The CO₂ growth rate showed a considerable interannual variation, with a maximum of about 3 ppm yr⁻¹ during late 1997. This variation is related to the El Niño/Southern Oscillation (ENSO) events. A year-to-year change related to the ENSO events was also found in the latitudinal distribution pattern of the CO₂ annual mean between 30°N and 30°S. The averaged CO₂ seasonal cycle in the Northern Hemisphere gradually decayed toward the equator, and a relatively complicated variation with a double seasonal maximum appeared in the Southern Hemisphere. A significant yearly change of the seasonal cycle pattern was observed in the Southern Hemisphere. The impact of a tropical biomass-burning injection on the upper tropospheric CO₂ was estimated on the basis of the CO data from the same airliner observation.     

基于观测的污染气体区域排放特征

利用2006年9月—2007年8月河北省固城生态与农业气象试验基地 (固城站) 反应性气体观测数据获得了CO与NO_x,CO与SO₂,SO₂与NO_x体积分数比的变化特征,并将观测得到的体积分数比与从INTEX-B等排放源资料得到的排放比进行比较研究。当风向来自北方向 (北京) 时,固城站的CO和NO_x体积分数显著高于其他方向,而来自南方向 (保定、石家庄) 时,SO₂体积分数显著高于其他方向。固城站观测到的CO与SO₂,CO与NO_x体积分数比分别为43.7和31.6,较排放比高出2~12倍。分析表明:排放源清单对CO排放低估了大约2倍以上,生物质燃料燃烧,尤其是收获季节大规模秸秆燃烧排放可能是重要的且被低估了的源。从观测数据估计得到秸秆燃烧期比平时CO大约多排放了90%±30%,忽略秸秆燃烧期额外排放对CO排放强度估计有重要影响。未来排放源清单编制和使用需要更加关注我国农业区秸秆燃烧排放对排放强度的影响。     

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.     

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.     

Variations of atmospheric nitrous oxide concentration in the northern and western Pacific

Atmospheric N₂O 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 N₂O 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 N₂O 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 N₂O was also characterized by especially high values at 30°N due to strong local N₂O 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 N₂O 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 N₂O growth rate and soil water showed a good correlation, suggesting that the N₂O emission from soils have an important causative role in the atmospheric N₂O variation.     

京津冀典型工业城市沙河市大气污染特征及来源分析

近些年京津冀地区秋、冬季大气重污染事件频发,工业生产与居民燃煤是大气灰霾污染的重要原因。河北省沙河市是京津冀地区以玻璃制造和加工为主的典型工业城市,本研究选取该城市为研究对象,主要利用2017年1月至12月国控站点的大气环境监测和气象数据,采用扩散模型、潜在源分析等手段,分析了沙河市主要污染物的时空分布特征和污染来源。主要结论有:（1）沙河市首要污染物具有明显季节特征,春季、夏季、秋冬季分别以PM₁₀、O₃、PM_2.5污染为主,季节贡献率分别为43.3%、72.3%、61.5%。（2）受城市大气边界层和排放的共同影响,PM₁₀、PM_2.5、SO₂、NO₂和CO浓度均有剧烈的季节—日变化特征。（3）冬季东北风时PM_2.5、NO₂、SO₂均展现出高浓度和高相关性特征,表明站点可能受东北方向玻璃企业排放影响。同时,站点可能也受城中村散煤燃烧影响。（4）沙河市冬季PM_2.5浓度为143 μg m-3。冬季的一次重污染中硫氧化率SOR、氮氧化率NOR的最高值分别达0.67、0.39,气态污染物的二次转化剧烈,高湿度利于二次粒子的生成。重污染中C(NO₃-)/C(SO₄2-)均值为1.89,推测沙河市NO₂主要来自大型运输车辆和企业的共同排放。（5）本地源是沙河市PM_2.5的主要潜在源区,周边几个重工业城市也有一定贡献。因此本研究建议沙河市PM_2.5的治理除需加强本地污染源的削减和控制外,区域联防联控也十分重要。     

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.     

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.     

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.