Hybrid fluorometric flow analyzer for atmospheric ammonia measurement

Gaseous ammonia has long been known to play a key role in atmospheric and biogeochemical processes. It is by far the dominant atmospheric base, responsible for the neutralization of particulate atmospheric acidity, such that the major fraction of atmospheric fine particulate matter consists of sulfate, ammonium nitrate, or both. Paradoxically, ammonia deposition in soils and subsequent nitrification leads to acidification and may cause long-term imbalances of Ca, K, and Mg; ammonia is also partially converted to N2O, a greenhouse gas.

We developed a robust, highly sensitive instrument for the determination of ambient ammonia. The instrument uses two syringe pumps to handle three liquids. The flow configuration is a hybrid between traditional flow injection (FI) and sequential injection (SI) schemes. This hybrid flow analyzer spends ~ 87% of its time in the continuous flow FI mode, providing the traditional FI advantages of high baseline stability and sensitivity. The SI fluid handling operation in the remaining time makes for flexibility and robustness. Atmospheric ammonia is collected in deionized water by a porous membrane diffusion scrubber at 0.2 L/min with quantitative collection efficiency, derivatized on-line to 1-sulfonatoisoindole, and measured by fluorometry. In the typical range for ambient ammonia (0-20 ppbv), response is linear (r2 =0.9990) with a S/N = 3 limit of detection of 135 pptv (15 nM for 500 μL of injected NH4+(aq)) with an inexpensive light emitting diode photodiode-based detector. Automated operation in continuously repeated, 8-min cycles over 9 days shows excellent overall precision (n = 1544, pNH3 5 ppbv, RSD = 3%). Precision for liquid-phase injections is even better (n = 1520, [NH4+(aq)] = 2.5 μM, RSD = 2%). The response decreases by 3.6% from 20 to 80% relative humidity. 





Amornthammarong, N.; Jakmunee, J.; Li, J.; Dasgupta, P.K. Anal. Chem. 2006, 78, 1890-1896.