C. Zellweger

Summertime NO y speciation at the Jungfraujoch, 3580 m above sea level, Switzerland

During summer 1997, speciated reactive nitrogen (NO, NO2, peroxyacetyl nitrate (PAN), HNO3, and particulate nitrate) was measured in conjunction with total reactive nitrogen (NOy) at the high-alpine research station Jungfraujoch (JFJ), 3580 m above sea level (asl). The individually measured NOy components averaged to 82% of total NOy. PAN was the most abundant reactive nitrogen compound and composed on average 36% of NOy, followed by NOx, (22%), particulate nitrate (17%), and HNO3 (7%). The NOx/NOy ratio averaged 0.25, but significantly lower values (0.15–0.20) were observed in the presence of high NOy mixing ratios. A classification of the data by synoptic weather conditions indicated that thermally driven vertical transport has a strong impact on the mixing ratios measured at the JFJ during summer. A strong diurnal cycle with maximum mixing ratios in the late afternoon was observed for convective days with north-westerly advection at 500 hPa. In contrast, during a period of convective days with a wind speed below 7.5 m s−1 at 500 hPa, no obvious diurnal cycle was observed. Under these meteorological conditions the convective boundary layer can be significantly higher over the Alps (i.e., around 4 km asl) than over the surrounding lowlands. Subsequent advection may finally result in the export of reactive nitrogen reservoir compounds to the free troposphere and hence influence global atmospheric chemistry.

Two high-speed, portable GC systems designed for the measurement of non-methane hydrocarbons and PAN: results from the Jungfraujoch High Altitude Observatory.

Near real-time measurements of light non-methane hydrocarbons (NMHCs) and peroxyacetyl nitrate (PAN) have been performed in the free troposphere using two fast gas chromatography (GC) instruments designed for use on aircraft. A GC-helium ionisation detector (HID) system measured 15 C(2)-C(5) hydrocarbons with 5 min time resolution and a dual channel GC-Electron Capture Detector (ECD) measured PAN with 90 s resolution. Both instruments had low parts per trillion by volume (pptV) detection limits and ran continuously at the remote Jungfraujoch (JFJ) research station in the Swiss Alps (46.55[degree]N, 7.98[degree]E), 3580 m above mean sea level (AMSL), during February/March 2003. Carbon monoxide, ozone, nitrogen oxide and nitrogen dioxide and all odd nitrogen species (NO(y)) were also measured continuously. Hydrocarbons and CO were strongly correlated in all air-masses whilst PAN exhibited both positive and negative correlations with respect to O(3), dependent on age and origin of the air-mass sampled. PAN was found to contribute [similar]20% to the NO(y) sampled on average. The experiment, as well as providing interesting datasets from this remote location, also demonstrated that when optimised, GC techniques have the potential to measure at a time resolution significantly greater than is traditionally considered, with high sensitivity and low uncertainty.

Real-time analysis of δ13C- and δD-CH4 in ambient air with laser spectroscopy: method development and first intercomparison results

In situ and simultaneous measurement of the three most abundant isotopologues of methane using midinfrared laser absorption spectroscopy is demonstrated. A field-deployable, autonomous platform is realized by coupling a compact quantum cascade laser absorption spectrometer (QCLAS) to a preconcentration unit, called trace gas extractor (TREX). This unit enhances CH4 mole fractions by a factor of up to 500 above ambient levels and quantitatively separates interfering trace gases such as N2O and CO2. The analytical precision of the QCLAS isotope measurement on the preconcentrated (750 ppm, parts-per-million, μmole mole) methane is 0.1 and 0.5 ‰ for δCand δDCH4 at 10 min averaging time. Based on repeated measurements of compressed air during a 2-week intercomparison campaign, the repeatability of the TREX–QCLAS was determined to be 0.19 and 1.9 ‰ for δC and δD-CH4, respectively. In this intercomparison campaign the new in situ technique is compared to isotoperatio mass spectrometry (IRMS) based on glass flask and bag sampling and real time CH4 isotope analysis by two commercially available laser spectrometers. Both laser-based analyzers were limited to methane mole fraction and δC-CH4 analysis, and only one of them, a cavity ring down spectrometer, was capable to deliver meaningful data for the isotopic composition. After correcting for scale offsets, the average difference between TREX–QCLAS data and bag/flask sampling–IRMS values are within the extended WMO compatibility goals of 0.2 and 5 ‰ for δCand δD-CH4, respectively. This also displays the potential to improve the interlaboratory compatibility based on the analysis of a reference air sample with accurately determined isotopic composition.

Abrupt reversal in emissions and atmospheric abundance of HCFC-133a (CF3CH2Cl)

Hydrochlorofluorocarbon HCFC-133a (CF3CH2Cl) is an anthropogenic compound whose consumption for emissive use is restricted under the Montreal Protocol. A recent study showed rapidly increasing atmospheric abundances and emissions. We report that, following this rise, the at- mospheric abundance and emissions have declined sharply in the past three years. We find a Northern Hemisphere HCFC-133a increase from 0.13 ppt (dry air mole fraction in parts-per-trillion) in 2000 to 0.50 ppt in 2012–mid-2013 followed by an abrupt reversal to 0.44 ppt by early 2015. Global emissions derived from these observations peaked at 3.1 kt in 2011, followed by a rapid decline of 0.5 kt yr−2 to 1.5 kt yr−1 in 2014. Sporadic HCFC-133a pollution events are detected in Europe from our high-resolution HCFC-133a records at three European stations, and in Asia from sam- ples collected in Taiwan. European emissions are estimated to be <0.1 kt yr−1 although emission hotspots were identi- fied in France.

Final report, ongoing key comparison BIPM.QM-K1: Ozone at ambient level, comparison with EMPA (June 2012)

As part of the ongoing key comparison BIPM.QM-K1, a comparison has been performed between the ozone national standard of the National Institute of Standards and Technology (NIST) and the common reference standard of the key comparison, maintained by the Bureau International des Poids et Mesures (BIPM). The instruments have been compared over a nominal ozone amount-of-substance fraction range of 0 nmol/mol to 500 nmol/mol.