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Long term methane flux measurements have been mostly performed with plant or soil enclosure techniques on specific components of an ecosystem. New fast response methane analyzers make it possible to use the eddy covariance (EC) technique instead. The EC technique is advantageous because it allows continuous flux measurements integrating over a larger and more representative area including the complete ecosystem, and allows fluxes to be observed as environmental conditions change naturally without disturbance. We deployed the closed-path Fast Methane Analyser (FMA) from Los Gatos Research Ltd and demonstrate its performance for EC measurements at a Ponderosa pine plantation at the Blodgett Forest site in central California. CH4 concentrations measured at 10 Hz showed a relatively high noise level that was caused by a software related problem. Nevertheless, in the frequency range important for turbulent exchange, the cospectra of CH4 compare very well with all other scalar cospectra confirming the quality of the FMA measurements are good for the EC technique. The low-pass filtering characteristics of our closed-path system and the use of the Webb-Pearman-Leuning (WPL) corrections for a combination of open and closed-path sensors are discussed using a large ensemble of cospectra. The diurnal variation of the methane concentration was up to 60 ppbv with an average of 1843 ppbv. Concentrations increased from morning to late afternoon as upslope flow from the valley below carried polluted air to the site, and then decreased through the night as downslope flow carried cleaner air from aloft. The fluxes were consistently directed downward with a well defined diurnal pattern, averaging −35±40 ng m−2 s−1 during the daytime. The detection limit of the system was estimated at 22 ng m−2 s−1. The average CH4 deposition during the daytime was higher than the average value for warm temperate forests in a recent global inventory and the results from a process-based model study.

Monoterpenes, primarily emitted by terrestrial vegetation, can influence atmospheric ozone chemistry, and can form precursors for secondary organic aerosol. The short-term emissions of monoterpenes have been well studied and understood, but their long-term variability, which is particularly important for atmospheric chemistry, has not. This understanding is crucial for the understanding of future changes. In this study, two algorithms of terrestrial biogenic monoterpene emissions, the first one based on the short-term volatilization of monoterpenes, as commonly used for temperature-dependent emissions, and the second one based on long-term production of monoterpenes (linked to photosynthesis) combined with emissions from storage, were compared and evaluated with measurements from a Ponderosa pine plantation (Blodgett Forest, California). The measurements were used to parameterize the long-term storage of monoterpenes, which takes place in specific storage organs and which determines the temporal distribution of the emissions over the year. The difference in assumptions between the first (emission-based) method and the second (production-based) method, which causes a difference in upscaling from instantaneous to daily emissions, requires roughly a doubling of emission capacities to bridge the gap to production capacities. The sensitivities to changes in temperature and light were tested for the new methods, the temperature sensitivity was slightly higher than that of the short-term temperature dependent algorithm. Applied on a global scale, the first algorithm resulted in annual total emissions of 29.6 Tg C a−1, the second algorithm resulted in 31.8 Tg C a−1 when applying the correction factor 2 between emission capacities and production capacities. However, the exact magnitude of such a correction is spatially varying and hard to determine as a global average

Long term methane flux measurements have been mostly performed with plant or soil enclosure techniques on specific components of an ecosystem. New fast response methane analyzers make it possible to use the eddy covariance (EC) technique instead. The EC technique is advantageous because it allows continuous flux measurements integrating over a larger and more representative area including the complete ecosystem, and allows fluxes to be observed as environmental conditions change naturally without disturbance. We deployed the closed-path Fast Methane analyzer (FMA) from Los Gatos Research Ltd and demonstrate its performance for EC measurements at a Ponderosa pine plantation at the Blodgett Forest site in central California. The fluctuations of the CH4 concentration measured at 10 Hz appear to be small and their standard deviation is comparable to the magnitude of the signal noise (±5 ppbv). Consequently, the power spectra typically have a white noise signature at the high frequency end (a slope of +1). Nevertheless, in the frequency range important for turbulent exchange, the cospectra of CH4 compare very well with all other scalar cospectra confirming the quality of the FMA measurements are good for the EC technique. We furthermore evaluate the complications of combined open and closed-path measurements when applying the Webb-Pearman-Leuning (WPL) corrections (Webb et al., 1980) and the consequences of a phase lag between the water vapor and methane signal inside the closed path system. The results of diurnal variations of CH4 concentrations and fluxes are summarized and compared to the monthly results of process-based model calculations

Satellite retrievals of methane (CH4) using the Atmospheric Infrared Sounder (AIRS) on the EOS/Aqua platform from 2003–2007 show a strong, plume-like enhancement of CH4 in the middle to upper troposphere over South Asia during July, August and September, with the maximum occurring in early September. Simulations using the global tracer model version 3 (TM3) also show similar seasonal enhancement of CH4 in the same region. The model results also suggest that this enhancement is associated with transport processes and local surface emissions, thus the observations of tropospheric CH4 during the monsoon season may be used to constrain the models for a better estimation of Asian CH4 sources. Further comparisons between the AIRS retrievals and the model simulations suggest a possible overestimate of emissions from rice paddies in Southeast Asia in the scenario with the global emissions from rice of 60 Tg yr‑1. Moreover, the observed tropospheric CH4 enhancement from AIRS provides evidence for the strong transport of atmospheric pollutants from the lower to the upper troposphere in Asia during the monsoon season. The observed rapid disappearance of the local CH4 maximum in September may provide valuable information for studying the dissipation of the Tibetan anticyclone and the withdrawal of monsoon

We use a 1-D cloud model with explicit microphysics and a binned representation of the aerosol size distribution to investigate the influence of entrainment of cloud condensation nuclei (CCN) on the microphysical development of warm cumulus clouds. For a more realistic representation of cloud drop spectral width, the model separates droplets that grow on aerosol that is initially present in the cloud from droplets growing on entrained aerosol. Model results are compared with observations of trade wind cumulus microphysics from the Rain in Cumulus over the Ocean experiment (RICO, 2004–2005). The results indicate that CCN are entrained throughout the entire cloud depth, and inside the cloud part of these may be activated. Compared to a simulation where entrainment of ambient CCN is neglected this leads to higher cloud droplet number concentrations (CDNC) and a continuous presence of droplets in the range smaller than 5μm that is consistent with the observations. Cloud dynamics are sensitive to the entrainment parameter as well as to the applied initial vertical velocity, as expressed by the liquid water content and cloud top height. However, simulated cloud drop spectra remain relatively unaffected for the specific conditions during RICO.

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

We report measurements of ambient atmospheric mixing ratios for methyl chavicol and determine its biogenic emission rate. Methyl chavicol, a biogenic oxygenated aromatic compound, is abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. Methyl chavicol was detected simultaneously by three in-situ instruments – a gas chromatograph with mass spectrometer detector (GC-MS), a proton transfer reaction mass spectrometer (PTR-MS), and a thermal desorption aerosol GC-MS (TAG) – and found to be abundant within and above Blodgett Forest. Methyl chavicol atmospheric mixing ratios are strongly correlated with 2-methyl-3-buten- 2-ol (MBO), a light- and temperature-dependent biogenic emission from the ponderosa pine trees at Blodgett Forest. Scaling from this correlation, methyl chavicol emissions account for 4–68% of the carbon mass emitted as MBO in the daytime, depending on the season. From this relationship, we estimate a daytime basal emission rate of 0.72– 10.2μgCg−1 h−1, depending on needle age and seasonality. We also present the first observations of its oxidation products (4-methoxybenzaldehyde and 4-methyoxy benzene acetaldehyde) in the ambient atmosphere. Methyl chavicol is a major essential oil component of many plant species. This work suggests that methyl chavicol plays a significant role in the atmospheric chemistry of Blodgett Forest, and potentially other sites, and should be included explicitly in both biogenic volatile organic carbon emission and atmospheric chemistry models.