Abstract
We report measurements of bromine monoxide (BrO) and use an observationally
constrained chemical box model to infer total gas-phase inorganic bromine
(Bry) over the tropical western Pacific Ocean
(tWPO) during the CONTRAST field campaign
(January–February 2014). The observed BrO and inferred Bry 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
(CBry). 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
1.6×1013 molec cm−2, compared to model predictions of
0.9×1013 molec cm−2 in GEOS-Chem (CBry but no SSA
source), 0.4×1013 molec cm−2 in CAM-Chem (CBry and
SSA), and 2.1×1013 molec cm−2 in GEOS-Chem (CBry and
SSA). Neither global model
fully captures the C-shape of the Bry profile. A local Bry 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 Bry decreases from the convective
TTL to the aged TTL. Analysis of gas-phase Bry against multiple tracers
(CFC-11, H2O ∕ O3 ratio, and potential temperature) reveals a
Bry 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 Bry (estimated from CFC-11 correlations), and is remarkably
insensitive to assumptions about heterogeneous chemistry. Bry increases
to 6.3 ppt (5.6–7.0 ppt; 95 % CI) in the stratospheric "middleworld"
and 6.9 ppt (6.5–7.3 ppt; 95 % CI) in the stratospheric "overworld".
The local Bry minimum in the aged TTL is qualitatively (but not
quantitatively) captured by CAM-Chem, and suggests a more complex
partitioning of gas-phase and aerosol Bry species than previously
recognized. Our data provide corroborating evidence that inorganic bromine
sources (e.g., SSA-derived gas-phase Bry) are needed to explain the
gas-phase Bry budget in the upper free troposphere and TTL. They are
also consistent with observations of significant bromide in Upper
Troposphere–Lower Stratosphere aerosols. The total Bry budget in the
TTL is currently not closed, because of the lack of concurrent quantitative
measurements of gas-phase Bry species (i.e., BrO, HOBr, HBr, etc.) and
aerosol bromide. Such simultaneous measurements are needed to (1) quantify
SSA-derived Bry in the upper FT,
(2) test Bry partitioning, and possibly explain the gas-phase Bry
minimum in the aged TTL, (3) constrain heterogeneous reaction rates of
bromine, and (4) account for all of the sources of Bry to the lower
stratosphere.
Citation
ID:
211098
Ref Key:
koenig2017atmosphericbro