Aircraft observations of the lower troposphere above a megacity: Alkyl nitrate and ozone chemistry

Eleonora Aruffo, Piero Di Carlo, Cesare Dari-Salisburgo, Fabio Biancofiore, Franco Giammaria, Marcella Busilacchio, James Lee, Sarah Moller, James Hopkins, Shalini Punjabi, Stéphane Bauguitte, Debbie O'Sullivan, Carl Percival, Michael Le Breton, Jennifer Muller, Rod Jones, Grant Forster, Claire Reeves, Dwayne Heard, Hannah WalkerTrevor Ingham, Stewart Vaughan, Daniel Stone

Research output: Contribution to journalArticlepeer-review

12 Citations (Scopus)


Within the framework of the RONOCO (ROle of Nighttime chemistry in controlling the Oxidising Capacity of the atmOsphere) campaign a daytime flight over the metropolitan area of London were carried out to study the nitrogen oxide chemistry and its role in the production and loss of ozone (O) and alkyl and multifunctional nitrate (σANs). The FAAM BAe-146 aircraft, used for these observations, was equipped with instruments to measure the most relevant compounds that control the lower troposphere chemistry, including O, NO, NO, NO, NO, HNO, peroxy nitrates (σPNs), σANs, OH, and HO. In the London's flight a strong ozone titration process was observed when flying above Reading (downwind of London) and when intercepting the London plume. The coupled cycles of NO and HO can have different terminations forming σPNs, σANs, HNO or peroxides (HO, ROOH) altering the O production. In the observations reported here, we found that a strong ozone titration (δO=-16ppb), due to a rapid increase of NO (δNO=27ppb), corresponds also to a high increase of σANs concentrations (δσANs=3ppb), and quite stable concentrations of HNO and σPNs. Unexpectedly, compared with other megacities, the production of σANs is similar to that of O (O+NO), suggesting that in the London plume, at least during these observations, the formation of σANs effectively removes active NO and hence reduces the amount of O production. In fact, we found that the ratio between the ozone production and the alkyl nitrates production (observed) approximate the unity; on the contrary the calculated ratio is 7. In order to explain this discrepancy, we made sensitivity tests changing the alkyl nitrates branching ratio for some VOCs and we investigated the impact of the unmeasured VOCs during the flight, founding that the calculated ratio decreases from 7 to 2 and that, in this condition, the major contribution to the σANs production is given by Alkanes. Observations and analysis reported here suggest that in the London plume the high NO emissions and the chemistry of some VOCs (mainly Alkanes) produce high concentrations of σANs competing against the local ozone production.
Original languageEnglish
Pages (from-to)479-488
Number of pages10
JournalAtmospheric Environment
Publication statusPublished - 1 Sep 2014

Cite this