BrO and inferred Bry profiles over the western Pacific

. We report measurements of bromine monoxide (BrO) and use an observationally constrained chemical box model to infer total gas-phase inorganic bromine (Br y ) over the tropical western Pacific Ocean (tWPO) during the CONTRAST field campaign (January–February 2014). The observed BrO and inferred Br y profiles peak in the marine boundary layer (MBL), suggesting the need for a bromine source from sea-salt aerosol (SSA), in addition to organic bromine (CBr y ). Both profiles are found to be C-shaped with local maxima in the upper free troposphere (FT). The median tropospheric BrO vertical column density (VCD) was measured as 1 . 6 × 10 13 molec cm − 2 , compared to model predictions of 0 . 9 × 10 13 molec cm − 2 in GEOS-Chem (CBr y but no SSA source), 0 . 4 × 10 13 molec cm − 2 in CAM-Chem (CBr y and SSA), and 2 . 1 × 10 13 molec cm − 2 in GEOS-Chem (CBr y and SSA). Neither global model fully captures the C-shape of the Br y profile. A local Br y maximum of 3.6 ppt (2.9–4.4 ppt; 95 % confidence interval, CI) is inferred between 9.5 and 13.5 km in air masses influenced by recent convective outflow. Unlike BrO, which increases from the convective tropical tropopause layer (TTL) to the aged TTL, gas-phase Br y decreases from the convective TTL to the aged TTL. Analysis of gas-phase Br y against multiple tracers (CFC-11, H 2 O / O 3 ratio, and potential temperature) reveals a Br y minimum of 2.7 ppt (2.3–3.1 ppt; 95 % CI) in the aged TTL, which agrees closely with a stratospheric injection of 2 . 6 ± 0 . 6 ppt of inorganic Br y (estimated from CFC-11 correlations), and is remarkably insensitive to assumptions about heterogeneous chemistry. Br y increases to 6.3 ppt (5.6–7.0 ppt; 95 % CI) in the stratospheric “mid-dleworld” and 6.9 ppt (6.5–7.3 ppt; 95 % CI) in the stratospheric “overworld”. The local Br y minimum in the aged TTL is qualitatively (but not quantitatively) captured by CAM-Chem, and suggests a

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