A modified method for the quantitative determination of atmospheric perfluoroalkylcycloalkanes (PFCs) using thermal desorption coupled with gas chromatography and detection by negative ion chemical ionization–mass spectrometry was developed. Using an optimized analytical system, a commercially available Al2O3 porous layer open tubular (PLOT) capillary column (30 m × 0.25 mm) deactivated with Na2SO4 was used for separation of PFCs. Improvements in the separation of PFCs, the corresponding identification and the limit of detection of PFCs using this method and column are presented. The method was successfully applied to determine the atmospheric background concentrations of a range of PFCs from a number of samples collected at a rural site in Germany. The results of this study suggest that the method outlined using the Al2O3-PLOT-S capillary column has good sensitivity and selectivity, and that it can be deployed in a routine laboratory process for the analysis of PFCs in the future research work. In addition, the ability of this column to separate the isomers of one of the lower boiling PFCs (perfluorodimethylcyclobutane) and its ability to resolve perfluoroethylcyclohexane offer the opportunity for single-column analysis for multiple PFCs.
Abstract.A perfluorocarbon tracer system (PERTRAS), specifically designed for Lagrangian aircraft experiments, has been developed by the Deutsches Zentrum für Luft-und Raumfahrt (German Aerospace Center, DLR). It consists of three main parts: a tracer release unit (RU), an adsorption tube sampler (ATS), and a tracer analytical system. The RU was designed for airborne tracer release experiments; meanwhile, it can be used on various platforms for different experimental purposes (here research vessel). PERTRAS was for the first time applied in the field campaign Stratospheric ozone: Halogen Impacts in a Varying Atmosphere (SHIVA) in November 2011. An amount of 8.8 kg perfluoromethylcyclopentane (PMCP) was released aboard the research vessel Sonne (RV Sonne) near the operational site of this campaign, Miri, Malaysia, on 21 November. The tracer samples collected using the ATS onboard the DLR research aircraft Falcon were analyzed in the laboratory using a thermal desorber-gas chromatography-mass spectrometry (TD-GC-MS) system. Guided by forecasts calculated with the Lagrangian model Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT), 64 tracer samples were collected onboard the Falcon approximately 5 and 25 h after the release, mostly with a time resolution of 1 min. Enhanced PMCP concentrations relative to ambient PMCP background values (mean: 6.62 fmol mol −1 ) were detected during three intersects of the fresh tracer plume (age 5 h), with a maximum value of 301.33 fmol mol −1 . This indicates that the fresh tracer plume was successfully intercepted at the forecast position. During the second flight, 25 h after the release, the center of tracer plume was not detected by the sampling system due to a faster advection of the plume than forecast. The newly developed PERTRAS system has been successfully deployed for the first time. The instrumental setup and comparisons between the measurements and HYSPLIT simulations are presented in this study.
Abstract. A perfluorocarbon tracer system (PERTRAS), specifically designed for Lagrangian aircraft experiments, has been developed by the Deutsches Zentrum für Luft- und Raumfahrt (German Aerospace Center, DLR). It consists of three main parts: a tracer release unit (RU), an adsorption tube sampler (ATS) and a tracer analytical system. The RU was designed for airborne tracer release experiments; meanwhile, it can be used on various platforms for different experimental purpose (here research vessel). PERTRAS was for the first time applied in the field campaign Stratospheric ozone: halogen Impacts in a Varying Atmosphere (SHIVA) in November 2011. An amount of 8.8 kg perfluoromethylcyclopentane (PMCP) was released aboard the research vessel Sonne (RV Sonne) near the operational site of this campaign, Miri, Malaysia, on 21 November. The tracer samples collected using the ATS on board the DLR research aircraft Falcon were analyzed in the laboratory using a thermal desorber/gas chromatography/mass spectrometry (TD/GC/MS) system. Guided by forecasts calculated with the Lagrangian model, Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT), 64 tracer samples were collected onboard the Falcon approximately 5 and 25 h after the release, respectively, mostly with a time resolution of 1 min. Enhanced PMCP concentrations relative to ambient PMCP background values (mean: 6.62 fmol mol−1) were detected during three intersects of the fresh tracer plume (age 5 h), with a maximum value of 301.33 fmol mol−1. This indicates that the fresh tracer plume was successfully intercepted at the forecasted position. During the second flight, 25 h after the release, the center of tracer plume was not detected by the sampling system due to a faster advection of the plume than forecasted. The newly developed PERTRAS system has been successfully deployed for the first time. The instrumental set-up and comparisons between the measurements and HYSPLIT simulations are presented in this study.
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