Application of a GC-ECD for measurements of biosphere–atmosphere exchange fluxes of peroxyacetyl nitrate using the relaxed eddy accumulation and gradient method

Peroxyacetyl nitrate (PAN) may constitute a significant fraction of reactive nitrogen in the atmosphere. Current knowledge about the biosphere–atmosphere exchange of PAN is limited, and only few studies have investigated the deposition of PAN to terrestrial ecosystems. We developed a flux measurement system for the determination of biosphere–atmosphere exchange fluxes of PAN using both the hyperbolic relaxed eddy accumulation (HREA) method and the modified Bowen ratio (MBR) method. The system consists of a modified, commercially available gas chromatograph with electron capture detection (GC-ECD, Meteorologie Consult GmbH, Germany). Sampling was performed by trapping PAN onto two pre-concentration columns; during HREA operation one was used for updraft and one for downdraft events, and during MBR operation the two columns allowed simultaneous sampling at two measurement heights. The performance of the PAN flux measurement system was tested at a natural grassland site, using fast-response ozone (O₃) measurements as a proxy for both methods. The measured PAN fluxes were comparatively small (daytime PAN deposition was on average −0.07 nmol m⁻² s⁻¹) and, thus, prone to significant uncertainties. A major challenge in the design of the system was the resolution of the small PAN mixing ratio differences. Consequently, the study focuses on the performance of the analytical unit and a detailed analysis of errors contributing to the overall uncertainty. The error of the PAN mixing ratio differences ranged from 4 to 15 ppt during the MBR and between 18 and 26 ppt during the HREA operation, while during daytime measured PAN mixing ratios were of similar magnitude. Choosing optimal settings for both the MBR and HREA method, the study shows that the HREA method did not have a significant advantage towards the MBR method under well-mixed conditions as was expected

Net ecosystem CO₂ exchange measurements by the closed chamber method and the eddy covariance technique and their dependence on atmospheric conditions

Carbon dioxide flux measurements in ecosystem sciences are mostly conducted by eddy covariance technique or the closed chamber method. But there is a lack of detailed comparisons that assess present differences and uncertainties. To determine underlying processes, a 10-day, side-by-side measurement of the net ecosystem exchange with both techniques was evaluated with regard to various atmospheric conditions during the diurnal cycle. It was found that, depending on the particular atmospheric condition, the chamber carbon dioxide flux was either (i) equal to the carbon dioxide flux measured by the reference method eddy covariance, by day with well-developed atmospheric turbulence; (ii) higher, in the afternoon in times of oasis effect; (iii) lower, predominantly at night while large coherent structure fluxes or high wind velocities prevailed; or (iv) showed less variation in the flux pattern, at night while stable stratification was present. At night – when respiration forms the net ecosystem exchange – lower chamber carbon dioxide fluxes were found. In the afternoon – when the ecosystem is still a net carbon sink – the carbon dioxide fluxes measured by the chamber prevailed. These two complementary aspects resulted in an overestimation of the ecosystem sink capacity by the chamber of 40% in this study

Comparison of conventional Lagrangian stochastic footprint models against LES driven footprint estimates

In this study we introduce a comparison method for footprint model results by evaluating the performance of conventional Lagrangian stochastic (LS) footprint models that use parameterised flow field characteristics with results of a Lagrangian trajectory model embedded in a large eddy simulation (LES) framework. The two conventional models follow the particles backward and forward in time while the trajectories in LES only evolve forward in time. We assess their performance in two unstably stratified boundary layers at observation levels covering the whole depth of the atmospheric boundary layer. We present a concept for footprint model comparison that can be applied for 2-D footprints and demonstrate that comparison of only cross wind integrated footprints is not sufficient for purposes facilitating two dimensional footprint information. Because the flow field description among the three models is most realistic in LES we use those results as the reference in the comparison. We found that the agreement of the two conventional models against the LES is generally better for intermediate measurement heights and for the more unstable case, whereas the two conventional flux footprint models agree best under less unstable conditions. The model comparison in 2-D was found quite sensitive to the grid resolution

Some aspects of the energy balance closure problem

International audienceAfter briefly discussing several reasons for the energy balance closure problem in the surface layer, the paper focuses on the influence of the low frequency part of the turbulence spectrum on the residual. Changes in the turbulent fluxes in this part of the turbulence spectrum were found to have a significant influence on the changes of the residual. Using the ogive method, it was found that the eddy-covariance method underestimates turbulent fluxes in the case of ogives converging for measuring times longer than the typical averaging interval of 30 min. Additionally, the eddy-covariance method underestimates turbulent fluxes for maximal ogive functions within the averaging interval, both mainly due to advection and non-steady state conditions. This has a considerable influence on the use of the eddy-covariance method

Characterisation of short-term extreme methane fluxes related to non-turbulent mixing above an Arctic permafrost ecosystem

Methane (CH4) emissions from biogenic sources, such as Arctic permafrost wetlands, are associated with large uncertainties because of the high variability of fluxes in both space and time. This variability poses a challenge to monitoring CH4 fluxes with the eddy covariance (EC) technique, because this approach requires stationary signals from spatially homogeneous sources. Episodic outbursts of CH4 emissions, i.e. triggered by spontaneous outgassing of bubbles or venting of methane-rich air from lower levels due to shifts in atmospheric conditions, are particularly challenging to quantify. Such events typically last for only a few minutes, which is much shorter than the common averaging interval for EC (30&thinsp;min). The steady-state assumption is jeopardised, which potentially leads to a non-negligible bias in the CH4 flux. Based on data from Chersky, NE Siberia, we tested and evaluated a flux calculation method based on wavelet analysis, which, in contrast to regular EC data processing, does not require steady-state conditions and is allowed to obtain fluxes over averaging periods as short as 1&thinsp;min. Statistics on meteorological conditions before, during, and after the detected events revealed that it is atmospheric mixing that triggered such events rather than CH4 emission from the soil. By investigating individual events in more detail, we identified a potential influence of various mesoscale processes like gravity waves, low-level jets, weather fronts passing the site, and cold-air advection from a nearby mountain ridge as the dominating processes. The occurrence of extreme CH4 flux events over the summer season followed a seasonal course with a maximum in early August, which is strongly correlated with the maximum soil temperature. Overall, our findings demonstrate that wavelet analysis is a powerful method for resolving highly variable flux events on the order of minutes, and can therefore support the evaluation of EC flux data quality under non-steady-state conditions.</p

The impact of free convection on late morning ozone decreases on an Alpine foreland mountain summit

Exceptional patterns in the diurnal course of ozone mixing ratio at a mountain top site (998 m a.s.l.) were observed during a field experiment (September 2005). They manifested themselves as strong and sudden decreases of ozone mixing ratio with a subsequent return to previous levels. The evaluation of corresponding long-term time series (2000–2005) revealed that such events occur mainly during summer, and affect the mountain top site on about 18% of the summer days. Combining (a) surface layer measurements at mountain summit and at the foot of the mountain, (b) in-situ (tethered balloon) and remote sensing (SODAR-RASS) measurements within the atmospheric boundary layer, the origin of these events of sudden ozone decrease could be attributed to free convection. The free convection was triggered by a rather frequently occurring wind speed minimum around the location of the mountain

Energy balance closure for the LITFASS-2003 experiment

In the first part, this paper synthesises the main results from a series of previous studies on the closure of the local energy balance at low-vegetation sites during the LITFASS-2003 experiment. A residual of up to 25% of the available energy has been found which cannot be fully explained either by the measurement uncertainty of the single components of the surface energy balance or by the length of the flux-averaging period. In the second part, secondary circulations due to heterogeneities in the surface characteristics (roughness, thermal and moisture properties) are discussed as a possible cause for the observed energy balance non-closure. This hypothesis seems to be supported from the fluxes derived from area-averaging measurement techniques (scintillometers, aircraft)