The detection of atmospheric NO3 radicals is still challenging owing to its low mixing ratios (approximate 1 to 300 pptv) in the troposphere. While long-path differential optical absorption ...spectroscopy (DOAS) has been a well-established NO3 detection approach for over 25 yr, newly sensitive techniques have been developed in the past decade. This publication outlines the results of the first comprehensive intercomparison of seven instruments developed for the spectroscopic detection of tropospheric NO3 . Four instruments were based on cavity ring-down spectroscopy (CRDS), two utilised open-path cavity-enhanced absorption spectroscopy (CEAS), and one applied "classical" long-path DOAS. The intercomparison campaign "NO3Comp" was held at the atmosphere simulation chamber SAPHIR in Jülich (Germany) in June 2007. Twelve experiments were performed in the well-mixed chamber for variable concentrations of NO3 , N2 O5 , NO2 , hydrocarbons, and water vapour, in the absence and in the presence of inorganic or organic aerosol. The overall precision of the cavity instruments varied between 0.5 and 5 pptv for integration times of 1 s to 5 min; that of the DOAS instrument was 9 pptv for an acquisition time of 1 min. The NO3 data of all instruments correlated excellently with the NOAA-CRDS instrument, which was selected as the common reference because of its superb sensitivity, high time resolution, and most comprehensive data coverage. The median of the coefficient of determination (r2 ) over all experiments of the campaign (60 correlations) is r2 = 0.981 (quartile 1 (Q1): 0.949; quartile 3 (Q3): 0.994; min/max: 0.540/0.999). The linear regression analysis of the campaign data set yielded very small intercepts (median: 1.1 pptv; Q1/Q3: -1.1/2.6 pptv; min/max: -14.1/28.0 pptv), and the slopes of the regression lines were close to unity (median: 1.01; Q1/Q3: 0.92/1.10; min/max: 0.72/1.36). The deviation of individual regression slopes from unity was always within the combined accuracies of each instrument pair. The very good correspondence between the NO3 measurements by all instruments for aerosol-free experiments indicates that the losses of NO3 in the inlet of the instruments were determined reliably by the participants for the corresponding conditions. In the presence of inorganic or organic aerosol, however, differences in the measured NO3 mixing ratios were detectable among the instruments. In individual experiments the discrepancies increased with time, pointing to additional NO3 radical losses by aerosol deposited onto the filters or on the inlet walls of the instruments. Instruments using DOAS analyses showed no significant effect of aerosol on the detection of NO3 . No hint of a cross interference of NO2 was found. The effect of non-Lambert-Beer behaviour of water vapour absorption lines on the accuracy of the NO3 detection by broadband techniques was small and well controlled. The NO3Comp campaign demonstrated the high quality, reliability and robustness of performance of current state-of-the-art instrumentation for NO3 detection.
This paper presents results from the first large‐scale in situ intercomparison of oxygenated volatile organic compound (OVOC) measurements. The intercomparison was conducted blind at the large (270 ...m3) simulation chamber, Simulation of Atmospheric Photochemistry in a Large Reaction Chamber (SAPHIR), in Jülich, Germany. Fifteen analytical instruments, representing a wide range of techniques, were challenged with measuring atmospherically relevant OVOC species and toluene (14 species, C1 to C7) in the approximate range of 0.5–10 ppbv under three different conditions: (1) OVOCs with no humidity or ozone, (2) OVOCs with humidity added (r.h. ≈ 50%), and (3) OVOCs with ozone (≈60 ppbv) and humidity (r.h. ≈ 50%). The SAPHIR chamber proved to be an excellent facility for conducting this experiment. Measurements from individual instruments were compared to mixing ratios calculated from the chamber volume and the known amount of OVOC injected into the chamber. Benzaldehyde and 1‐butanol, compounds with the lowest vapor pressure of those studied, presented the most overall difficulty because of a less than quantitative transfer through some of the participants' analytical systems. The performance of each individual instrument is evaluated with respect to reference values in terms of time series and correlation plots for each compound under the three measurement conditions. A few of the instruments performed very well, closely matching the reference values, and all techniques demonstrated the potential for quantitative OVOC measurements. However, this study showed that nonzero offsets are present for specific compounds in a number of instruments and overall improvements are necessary for the majority of the techniques evaluated here.
Formaldehyde of known, near-natural isotopic composition was photolyzed in the SAPHIR atmosphere simulation chamber under ambient conditions. The isotopic composition of the product H2 was used to ...determine the isotope effects in formaldehyde photolysis. The experiments are sensitive to the molecular photolysis channel, and the radical channel has only an indirect effect and cannot be effectively constrained. The molecular channel kinetic isotope effect KIEmol , the ratio of photolysis frequencies j(HCHO->CO+H2 )/j(HCDO->CO+HD) at surface pressure, is determined to be KIEmol =1.63−0.046+0.038 . This is similar to the kinetic isotope effect for the total removal of HCHO from a recent relative rate experiment (KIEtot =1.58±0.03), which indicates that the KIEs in the molecular and radical photolysis channels at surface pressure (≈100 kPa) may not be as different as described previously in the literature.
Halogen atoms from the reactions of sea-salt particles may play a significant role in the marine boundary layer. Reactions of sodium chloride, the major component of sea-salt particles, with nitrogen ...oxides generate chlorine atom precursors. However, recent studies suggest there is an additional source of chlorine in the marine troposphere. This study shows that molecular chlorine is generated from the photolysis of ozone in the presence of sea-salt particles above their deliquescence point; this process may also occur in the ocean surface layer. Given the global distribution of ozone, this process may provide a global source of chlorine.
Hydroperoxy radical (HO2 ) concentrations were measured during the formal blind intercomparison campaign HOxComp carried out in Jülich, Germany, in 2005. Three instruments detected HO2 via chemical ...conversion to hydroxyl radicals (OH) and subsequent detection of the sum of OH and HO2 by laser induced fluorescence (LIF). All instruments were based on the same detection and calibration scheme. Because measurements by a MIESR instrument failed during the campaign, no absolute reference measurement was available, so that the accuracy of individual instruments could not be addressed. Instruments sampled ambient air for three days and were attached to the atmosphere simulation chamber SAPHIR during the second part of the campaign. Six experiments of one day each were conducted in SAPHIR, where air masses are homogeneously mixed, in order to investigate the performance of instruments and to determine potential interferences of measurements under well-controlled conditions. Linear correlation coefficients (R2 ) between measurements of the LIF instruments are generally high and range from 0.82 to 0.98. However, the agreement between measurements is variable. The regression analysis of the entire data set of measurements in SAPHIR yields slopes between 0.69 to 1.26 and intercepts are smaller than typical atmospheric daytime concentrations (less than 1 pptv). The quality of fit parameters improves significantly, when data are grouped into data subsets of similar water vapor concentrations. Because measurements of LIF instruments were corrected for a well-characterized water dependence of their sensitivities, this indicates that an unknown factor related to water vapor affected measurements in SAPHIR. Measurements in ambient air are also well-correlated, but regression parameters differ from results obtained from SAPHIR experiments. This could have been caused by differences in HO2 concentrations in the sampled air at the slightly different locations of instruments.
Absolute reaction rate studies of NO3 radicals with 4 aldehydes were performed in the atmosphere simulation chamber SAPHIR at the Research Center Jülich. Rate coefficients (ethanal: 2.6 ± 0.5, ...propanal: 5.8 ± 1.0, butanal: 11.9 ± 1.4, benzaldehyde: 2.2 ± 0.6; in 10−15 cm3 s−1 at 300 K) were determined from measured concentration–time profiles of aldehydes and NO3 at near ambient conditions. The values for the aliphatic aldehydes are in good agreement with the most recent recommendations (IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry: Evaluated kinetic and photochemical data for atmospheric chemistry, 2005, available at http://www.iupac-kinetic.ch.cam.ac.uk). The measured concentration‐time profiles of precursor aldehydes, NO3, NO2, and of product aldehydes were compared to model calculations based on the MCM v3 (Jenkin et al., 2003; Saunders et al., 2003). Differences between measurements and model are attributed to a major interference of the GC system to peroxyacyl nitrates. In addition modifications to the rate constants in the MCM are suggested.
Measurements of the atmospheric mixing ratios of 10 nonmethane hydrocarbons (NMHC) and four halocarbons (methyl chloride, dichloromethane, trichloroethene, and tetrachloroethene) were conducted ...between January 1989 and July 1996 at Alert (Canadian Arctic, 82°27′N, 62°31′W). About 270 canister samples were analyzed covering the 7‐year period with an average frequency of about one sample every 9 days. The mixing ratios of these volatile organic compounds (VOC) exhibit considerable variability, which can partly be described by systematic seasonal dependencies. The highest mixing ratios were always observed during winter. During spring, the mixing ratios decrease for some compounds to values near the detection limit. The amplitudes of the seasonal variability, the time of the occurrence of the maxima, and the relative steepness of the temporal gradients show a systematic dependence on OH reactivity. The steepest relative decrease is less than 1% d−1 for methyl chloride, increasing to about 4% d−1 for highly reactive VOC. Similarly, the highest relative increase rates vary between 0.5% d−1 for VOC with low reactivity to 4% d−1 for reactive VOC. With the exception of ethyne, toluene, and methyl chloride the concentrations of all measured VOC decrease during the studied period, although this decrease is not always statistically significant. In general, the largest changes were found for the most reactive VOC, although the seemingly random overall variability observed for these compounds results in substantial uncertainties. For the less reactive VOC (ethane, benzene, and propane) the average relative annual decrease rate is in the range of a few percent per year. Dichloromethane and tetrachloroethene showed a decrease of 4 and 14% yr−1, respectively. The average decrease rate for the other alkanes is in the range of some 10% yr−1, indicating a substantial change of emission rates during this period. A likely explanation is a reduction in VOC emissions in the area of the former Soviet Union, most likely Siberia, as a consequence of the recent major economic changes in this region. The measurements were compared with the results of chemical transport models' simulations using the Emission Database for Global Atmospheric Research NMHC emission inventory. Although the model captures most of the main features of the shapes of the seasonal cycles of the NMHC, the results clearly show that model estimates are consistently too low compared to the observations. Most likely this is the consequence of an underestimate of the NMHC emission rates in the emission inventory.
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