US EPA

4173657 

Journal Article 

Horizontal and vertical structure of reactive bromine events probed by bromine monoxide MAX-DOAS 

Simpson, WR; Peterson, PK; Friess, Udo; Sihler, H; Lampel, J; Platt, U; Moore, C; Pratt, K; Shepson, P; Halfacre, J; Nghiem, S 

2017 

Yes 

Atmospheric Chemistry and Physics
ISSN: 1680-7316
EISSN: 1680-7324 

COPERNICUS GESELLSCHAFT MBH 

GOTTINGEN 

17 

15 

9291-9309 

10.5194/acp-17-9291-2017 

WOS:000407201800002 

Heterogeneous photochemistry converts bromide (Br) to reactive bromine species (Br atoms and bromine monoxide, BrO) that dominate Arctic springtime chemistry. This phenomenon has many impacts such as boundary-layer ozone depletion, mercury oxidation and deposition, and modification of the fate of hydrocarbon species. To study environmental controls on reactive bromine events, the BRomine, Ozone, and Mercury EXperiment (BROMEX) was carried out from early March to mid-April 2012 near Barrow (Utqiagvik), Alaska. We measured horizontal and vertical gradients in BrO with multiple-axis differential optical absorption spectroscopy (MAX-DOAS) instrumentation at three sites, two mobile and one fixed. During the campaign, a large crack in the sea ice (an open lead) formed pushing one instrument package similar to 250 km downwind from Barrow (Utqiagvik). Convection associated with the open lead converted the BrO vertical structure from a surface-based event to a lofted event downwind of the lead influence. The column abundance of BrO downwind of the refreezing lead was comparable to upwind amounts, indicating direct reactions on frost flowers or open seawater was not a major reactive bromine source. When these three sites were separated by similar to 30 km length scales of unbroken sea ice, the BrO amount and vertical distributions were highly correlated for most of the time, indicating the horizontal length scales of BrO events were typically larger than similar to 30 km in the absence of sea ice features. Although BrO amount and vertical distribution were similar between sites most of the time, rapid changes in BrO with edges significantly smaller than this similar to 30 km length scale episodically transported between the sites, indicating BrO events were large but with sharp edge contrasts. BrO was often found in shallow layers that recycled reactive bromine via heterogeneous reactions on snowpack. Episodically, these surface-based events propagated aloft when aerosol extinction was higher (> 0.1 km(-1)) however, the presence of aerosol particles aloft was not sufficient to produce BrO aloft. Highly depleted ozone (< 1 nmol mol(-1) ) repartitioned reactive bromine away from BrO and drove BrO events aloft in cases. This work demonstrates the interplay between atmospheric mixing and heterogeneous chemistry that affects the vertical structure and horizontal extent of reactive bromine events.