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Using proton transfer reaction mass spectrometry equipped with a quadrupol mass analyser to quantify the biosphere-atmosphere exchange of volatile organic compounds (VOC), concentrations of different VOC are measured sequentially. Depending on how many VOC species are targeted and their respective integration times, each VOC is measured at repeat rates on the order of a few seconds. This represents an order of magnitude longer sample interval compared to the standard eddy covariance (EC) method (5–20 Hz sampling rates). Here we simulate the effect of disjunct sampling on EC flux estimates by decreasing the time resolution of CO2 and H2O concentrations measured at 20 Hz above a temperate mountain grassland in the Austrian Alps. Fluxes for one month are calculated with the standard EC method and compared to fluxes calculated based on the disjunct data (1, 3 and 5 s sampling rates) using the following approaches: i) imputation of missing concentrations based on the nearest neighbouring samples (iDECnn), ii) imputation by linear interpolation (iDECli), and iii) virtual disjunct EC (vDEC), i.e. flux calculation based solely on the disjunct concentrations. It is shown that the two imputation methods result in additional low-pass filtering, longer lag times (as determined with the maximum cross-correlation method) and a flux loss of 3–30% as compared to the standard EC method. A novel procedure, based on a transfer function approach, which specifically corrects for the effect of data treatment, was developed, resulting in improved correspondence (to within 2%). The vDEC method yields fluxes which approximate the true (20 Hz) fluxes to within 3–7% and it is this approach we recommend because it involves no additional empirical corrections. The only drawback of the vDEC method is the noisy nature of the cross-correlations, which poses problems with lag determination – practical approaches to overcome this limitation are discussed.  相似文献   
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Ozone (O3) fluxes above a temperate mountain grassland were measured by means of the eddy covariance (EC) method using a slow-response O3 analyser. The resultant flux loss was corrected for by a series of transfer functions which model the various sources of high- and, in particular, low-pass filtering. The resulting correction factors varied on average between 1.7 and 3.5 during night and daytime, respectively. A cospectral analysis confirmed the accuracy of this approach. O3 fluxes were characterised by a comparatively large random uncertainty, which during daytime typically amounted to 60%. EC O3 fluxes were compared against O3 flux measurements made concurrently with the flux-gradient (FG) method. The two methods generally agreed well, except for a period between sunrise and early afternoon, when the FG method was suspected of being affected by the presence of photochemical sources/sinks. O3 flux magnitudes and deposition velocities determined with the EC method compared nicely with the available literature from grassland studies. We conclude that our understanding of the causes and consequences of various sources of flux loss (associated with any EC system) has sufficiently matured so that also less-than-ideal instrumentation may be used in EC flux applications, albeit at the cost of relatively large empirical corrections.  相似文献   
3.
Experiments have been conducted to measure vehicle sulfate emissions, by vehicle type, at two tunnels on the Pennsylvania Turnpike. A satisfactory balance between estimated fuel sulfur consumption and observed emissions of sulfur compounds corrected for ambient-air contributions was obtained. This work started in 1974 before the introduction of catalyst-equipped automobiles and continued into 1976. The sulfate contributed by vehicles even in the tunnels was found to be generally modest relative to rural ambient sulfate levels. Average sulfate emission rates were found to be ~30 mg/km (50 mg/mi) from heavy-duty Diesel trucks, <15 mg/km from catalyst-equipped cars (probably in the range 4 to 7 mg/km), and probably <1 mg/km from non-catalyst cars. The overall SO2 —* SO4 -2 conversion of the vehicle emissions was 2 %.  相似文献   
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