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Would urban air quality and climate improve if we replaced the fossil fuels by molecular hydrogen (H2) as an energy carrier? A quantitative answer to this question requires a thorough understanding of the current role of H2 in the Earth’s atmosphere. On its own, H2 does not impact climate, as for example carbon dioxide or methane. However, increasing levels of H2 in the stratosphere can lead to increased ozone loss due to the formation of polar stratospheric clouds. Additionally, the atmospheric lifetime of methane could increase because both H2 and methane are removed by photochemical oxidation with the hydroxyl radical. Consequently, the lifetime of the strong greenhouse gas methane could be prolonged. During the last two decades, more and more experimental data have become available to put tighter constraints on the different sources and sinks that contribute to the global H2 cycle. However, the main removal process, dry deposition due to microbial/enzymatic decomposition of H2 in the soils, still has a rather large uncertainty between 40-99 Tg/yr globally. This is a highly uncertain number compared to the estimated overall amount of 136-166 Tg present in the troposphere. The photochemical removal of H2 from the atmosphere is estimated at 14-24 Tg/yr. Together with the estimates for the burden and dry deposition, this implies a tropospheric lifetime of H2 between 1.1-3.1 years. The atmospheric H2 is replenished by emissions from the Earth’s surfaces due to fossil fuel burning (5-25 Tg/yr), biomass burning (7-21 Tg/yr) and nitrogen fixation processes in the oceans (1-11 Tg/yr) and soils (0-11 Tg/yr). H2 is photochemically produced from methane (15-21 Tg/yr) and non-methane hydrocarbons (10-25 Tg/yr) in the atmosphere. These uncertainties suggest that at present, the global hydrogen cycle is poorly understood. However, this statement would do little justice to the scientific quality of most studies so far. The main purpose of the research in this thesis is to show

In this study, we identify a biomass-burning signal in molecular hydrogen (H-2) over the Amazonian tropical rainforest. To quantify this signal, we measure the mixing ratios of H-2 and several other species as well as the H-2 isotopic composition in air samples that were collected in the BARCA (Balanco Atmosferico Regional de Carbono na Amazonia) aircraft campaign during the dry season. We derive a relative H-2 emission ratio with respect to carbon monoxide (CO) of 0.31 +/- 0.04 ppb ppb(-1) and an isotopic source signature of -280 +/- 41 parts per thousand in the air masses influenced by tropical biomass burning. In order to retrieve a clear source signal that is not influenced by the soil uptake of H-2, we exclude samples from the atmospheric boundary layer. This procedure is supported by data from a global chemistry transport model. The Delta H-2/Delta CO emission ratio is significantly lower than some earlier estimates for the tropical rainforest. In addition, our results confirm the lower values of the previously conflicting estimates of the H-2 isotopic source signature from biomass burning. These values for the emission ratio and isotopic source signatures of H-2 from tropical biomass burning can be used in future bottom-up and top-down approaches aiming to constrain the strength of the biomass-burning source for H-2. Hitherto, these two quantities relied only on combustion experiments or on statistical relations, since no direct signal had been obtained from in-situ observations.

Inverse modeling techniques used to quantify surface carbon fluxes commonly assume that the uncertainty of fossil fuel CO2 (FFCO2) emissions is negligible and that intra-annual variations can be neglected. To investigate these assumptions, we analyzed the differences between four fossil fuel emission inventories with spatial and temporal differences over Europe and their impact on the model simulated CO2 concentration. Large temporal flux variations characterize the hourly fields (~40 % and ~80 % for the seasonal and diurnal cycles, peak-to-peak) and annual country totals differ by 10 % on average and up to 40 % for some countries (i.e., the Netherlands). These emissions have been prescribed to seven different transport models, resulting in 28 different FFCO2 concentrations fields. The modeled FFCO2 concentration time series at surface sites using time-varying emissions show larger seasonal cycles (+2 ppm at the Hungarian tall tower (HUN)) and smaller diurnal cycles in summer (−1 ppm at HUN) than when using constant emissions. The concentration range spanned by all simulations varies between stations, and is generally larger in winter (up to ~10 ppm peak-to-peak at HUN) than in summer (~5 ppm). The contribution of transport model differences to the simulated concentration std-dev is 2–3 times larger than the contribution of emission differences only, at typical European sites used in global inversions. These contributions to the hourly (monthly) std-dev's amount to ~1.2 (0.8) ppm and ~0.4 (0.3) ppm for transport and emissions, respectively. First comparisons of the modeled concentrations with 14C-based fossil fuel CO2 observations show that the large transport differences still hamper a quantitative evaluation/validation of the emission inventories. Changes in the estimated monthly biosphere flux (Fbio) over Europe, using two inverse modeling approaches, are relatively small (less that 5 %) while changes in annual Fbio (up to ~0.15 % GtC yr−1) are only slightly smal

The isotopic composition of molecular hydrogen (H2) contains independent information for constraining the global H2 budget. To explore this, we have implemented hydrogen sources and sinks, including their isotopic composition, into the global chemistry transport model TM5. For the first time, a global model now includes a simplified but explicit isotope reaction scheme for the photochemical production of H2. We present a comparison of modelled results for the H2 mixing ratio and isotope composition with available measurements on the seasonal to inter annual time scales for the years 2001–2007. The base model results agree well with observations for H2 mixing ratios. For dD[H2], modelled values are slightly lower than measurements. A detailed sensitivity study is performed to identify the most important parameters for modelling the isotopic composition of H2. The results show that on the global scale, the discrepancy between model and measurements can be closed by adjusting the default values of the isotope effects in deposition, photochemistry and the stratosphere-troposphere exchange within the known range of uncertainty. However, the available isotope data do not provide sufficient information to uniquely constrain the global isotope budget. Therefore, additional studies focussing on the isotopic composition near the tropopause and on the isotope effects in the photochemistry and deposition are recommended.

The isotopic composition of molecular hydrogen (H2) produced by photochemical oxidation of methane (CH4) and Volatile Organic Compounds (VOCs) is a key quantity in the global isotope budget of (H2). The many individual reaction steps involved complicate its investigation. Here we present a simplified structure-activity approach to assign isotope effects to the individual elementary reaction steps in the oxidation sequence of CH4 and some other VOCs. The approach builds on and extends the work by Gerst and Quay (2001) and Feilberg et al. (2007b). The description is generalized and allows the application, in principle, also to other compounds. The idea is that the C-H and C-D bonds – seen as reactive sites – have similar relative reaction probabilities in isotopically substituted, but otherwise identical molecules. The limitations of this approach are discussed for the reaction CH4+Cl. The same approach is applied to VOCs, which are important precursors of H2 that need to be included into models. Unfortunately, quantitative information on VOC isotope effects and source isotope signatures is very limited and the isotope scheme at this time is limited to a strongly parameterized statistical approach, which neglects kinetic isotope effects. Using these concepts we implement a full hydrogen isotope scheme in a chemical box model and carry out a sensitivity study to identify those reaction steps and conditions that are most critical for the isotope composition of the final H2 product. The reaction scheme is directly applicable in global chemistry models, which can thus include the isotope pathway of H2 produced from CH4 and VOCs in a consistent way

The isotopic composition of molecular hydrogen (H2) produced by photochemical oxidation of methane (CH4) and Volatile Organic Compounds (VOCs) is a key quantity in the global isotope budget of (H2). The many individual reaction steps involved complicate its investigation. Here we present a simplified structure-activity approach to assign isotope effects to the individual elementary reaction steps in the oxidation sequence of CH4 and some other VOCs. The approach builds on and extends the work by Gerst and Quay (2001) and Feilberg et al. (2007b). The description is generalized and allows the application, in principle, also to other compounds. The idea is that the C-H and C-D bonds – seen as reactive sites – have similar relative reaction probabilities in isotopically substituted, but otherwise identical molecules. The limitations of this approach are discussed for the reaction CH4+Cl. The same approach is applied to VOCs, which are important precursors of H2 that need to be included into models. Unfortunately, quantitative information on VOC isotope effects and source isotope signatures is very limited and the isotope scheme at this time is limited to a strongly parameterized statistical approach, which neglects kinetic isotope effects. Using these concepts we implement a full hydrogen isotope scheme in a chemical box model and carry out a sensitivity study to identify those reaction steps and conditions that are most critical for the isotope composition of the final H2 product. The reaction scheme is directly applicable in global chemistry models, which can thus include the isotope pathway of H2 produced from CH4 and VOCs in a consistent way

Droplet growth rates of droplets suspended in methane gas and supersaturated water and/or n-nonane vapor are experimentally determined. The experiments are performed by applying the nucleation pulse principle using a modified shock tube. The droplets are optically detected using a combination of constant angle Mie scattering and light extinction measurements. From the analysis of the droplet growth rates in the binary systems the diffusion coefficients of water in methane and n-nonane in methane have been determined at two different conditions, being 11 bar and 242 K, and 44 bar and 247 K. The droplet growth rates in the ternary system have been determined at the same two conditions. From the analysis of these experiments it is evident that supersaturated water vapor does not condense onto n-nonane droplets while supersaturated n-nonane vapor does condense onto water droplets. This can be related to the wetting properties of liquid water on liquid n-nonane and vice versa.

A droplet growth model is formulated that describes the growth of homogeneous multi-component droplets suspended in a dilute gas–vapor mixture. The droplet is suspended in a real carrier gas, in which the vapors are diluted. The model is applicable for all Knudsen numbers. It is shown that the model can easily be extended to describe the growth of layered droplets. The model calculations are compared to the results of droplet growth experiments of supersaturated water and/or supersaturated n-nonane in methane. The model performs well for all the cases, except for the case when supersaturated n-nonane vapor is added to supersaturated water vapor in methane gas. In the latter case it is proposed that the discrepancies originate from the incomplete wetting of n-nonane on liquid water at the given conditions.

Droplet growth rates of droplets suspended in methane gas and supersaturated water and/or n-nonane vapor are experimentally determined. The experiments are performed by applying the nucleation pulse principle using a modified shock tube. The droplets are optically detected using a combination of constant angle Mie scattering and light extinction measurements. From the analysis of the droplet growth rates in the binary systems the diffusion coefficients of water in methane and n-nonane in methane have been determined at two different conditions, being 11 bar and 242 K, and 44 bar and 247 K. The droplet growth rates in the ternary system have been determined at the same two conditions. From the analysis of these experiments it is evident that supersaturated water vapor does not condense onto n-nonane droplets while supersaturated n-nonane vapor does condense onto water droplets. This can be related to the wetting properties of liquid water on liquid n-nonane and vice versa.

A droplet growth model is formulated that describes the growth of homogeneous multi-component droplets suspended in a dilute gas–vapor mixture. The droplet is suspended in a real carrier gas, in which the vapors are diluted. The model is applicable for all Knudsen numbers. It is shown that the model can easily be extended to describe the growth of layered droplets. The model calculations are compared to the results of droplet growth experiments of supersaturated water and/or supersaturated n-nonane in methane. The model performs well for all the cases, except for the case when supersaturated n-nonane vapor is added to supersaturated water vapor in methane gas. In the latter case it is proposed that the discrepancies originate from the incomplete wetting of n-nonane on liquid water at the given conditions.