Journal of Physical Chemistry A, Vol.120, No.9, 1347-1357, 2016
New Approaches to Measuring Sticky Molecules: Improvement of Instrumental Response Times Using Active Passivation
A novel method has been developed to improve sampling system response times for nominally "sticky" molecules such as HNO3 and NH3. The method reported here makes use of active, continuous passivation; where the instrument interfaces are continuously exposed to 0.01-1 ppm of fluorinated acidic or basic surfactants. To reduce HNO3 response times, perfluoroheptanoic acid and perfluorobutanesulfonic acid vapors are evaluated as passivation species. 1H,1H-perfluorooctylamine is used to improve NH3 response times. The resulting time responses using the perfluorpalkanoic acids are on the order of 0.4-0.7 s for a 75% quantitative recovery of HNO3, and 1-5 s for 90% recovery. Similar response time improvements are seen in detection of NH3 using perfluorooctylamine (<1 s for a 75% recovery, similar to 2 s for 90% recovery). This generally applicable methodology significantly improves the capability of eddy covariance flux and real-time plume-based measurements of highly polar molecules that have historically :been hampered by slow response times due to adsorption on sampling system surfaces. The utility of this approach is demonstrated by field measurements of HNO3 eddy covariance fluxes in a central U.S. prairie.