Intercomparison of in situ measurements of ambient NH3: instrument performance and application under field conditions

Twigg, Marsailidh M.; Berkhout, Augustinus J.C.; Cowan, Nicholas; Crunaire, Sabine; Dammers, Enrico; Ebert, Volker; Gaudion, Vincent; Haaima, Marty; Häni, Christoph; John, Lewis; Jones, Matthew R.; Kamps, Bjorn; Kentisbeer, John; Kupper, Thomas; Leeson, Sarah R.; Leuenberger, Daiana; Lüttschwager, Nils O.B.; Makkonen, Ulla; Martin, Nicholas A.; Missler, David; Mounsor, Duncan; Neftel, Albrecht; Nelson, Chad; Nemitz, Eiko; Oudwater, Rutger; Pascale, Celine; Petit, Jean-Eudes; Pogany, Andrea; Redon, Nathalie; Sintermann, Jörg; Stephens, Amy; Sutton, Mark A.; Tang, Yuk S.; Zijlmans, Rens; Braban, Christine F.; Niederhauser, Bernhard. 2022 Intercomparison of in situ measurements of ambient NH3: instrument performance and application under field conditions. Atmospheric Measurement Techniques, 15 (22). 6755-6787.

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Ammonia (NH3) in the atmosphere affects both the environment and human health. It is therefore increasingly recognised by policy makers as an important air pollutant that needs to be mitigated, though it still remains unregulated in many countries. In order to understand the effectiveness of abatement strategies, routine NH3 monitoring is required. Current reference protocols first developed in the 1990s, use daily samplers with offline analysis but there have been a number of technologies developed since, which may be applicable for high time resolution routine monitoring of NH3 at ambient concentrations. The following study is a comprehensive field intercomparison held over an intensively managed grassland in South East Scotland using currently available methods that are reported to be suitable for routine monitoring of ambient NH3. In total 13 instruments took part in the field study, including commercially available technologies, research prototype instruments and legacy instruments. Assessments of the instruments’ precision at low concentrations (< 10 ppb) and at elevated concentrations (maximum reported concentration of 282 ppb) were undertaken. At elevated concentrations all instruments performed well on precision (r2 >0.75). At concentrations below 10 ppb however, precision decreased and instruments fell into two distinct groups with duplicate instruments split across the two groups. It was found that duplicate instruments performed differently as a result of differences in instrument setup, inlet design and operation of the instrument. New metrological standards were used to evaluate the accuracy in determining absolute concentrations in the field. A calibration-free CRDS Optical Gas Standard (OGS, PTB, DE) served as an instrumental reference standard, and instrument operation was assessed against metrological calibration gases from i) a permeation system (ReGaS1, METAS, CH) and ii) Primary Standard gas Mixtures (PSMs) prepared by gravimetry (NPL, UK). This study suggests that though the OGS gives good performance with respect to sensitivity and linearity against the reference gas standards, this in itself is not enough for the OGS to be a field reference standard because in field applications a closed path spectrometer has limitations due to losses to surfaces in sampling NH3, which are not currently taken into account by the OGS. Overall, the instruments compared with the metrological standards performed well but not every instrument could be compared to the reference gas standards due to incompatible inlet designs and limitations in the gas flow rates of the standards. This work provides evidence that though NH3 instrumentation have greatly progressed in measurement precision, there is still further work required to quantify the accuracy of these systems under field conditions. It is the recommendation of this study that the use of instruments for routine monitoring of NH3 needs to be set out in standard operating protocols for inlet set-up, calibration and routine maintenance, in order for datasets to be comparable.

Item Type: Publication - Article
Digital Object Identifier (DOI):
UKCEH and CEH Sections/Science Areas: Atmospheric Chemistry and Effects (Science Area 2017-)
ISSN: 1867-1381
Additional Information. Not used in RCUK Gateway to Research.: Open Access paper - full text available via Official URL link.
NORA Subject Terms: Atmospheric Sciences
Date made live: 27 Jan 2023 11:24 +0 (UTC)

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