The Convective Transport of Active Species in the Tropics (CONTRAST) experiment was conducted from Guam (13.5° N, 144.8° E) during January-February 2014. Using the NSF/NCAR Gulfstream V research aircraft, the experiment investigated the photochemical environment over the tropical western Pacific (TWP) warm pool, a region of massive deep convection and the major pathway for air to enter the stratosphere during Northern Hemisphere (NH) winter. The new observations provide a wealth of information for quantifying the influence of convection on the vertical distributions of active species. The airborne in situ measurements up to 15 km altitude fill a significant gap by characterizing the abundance and altitude variation of a wide suite of trace gases. These measurements, together with observations of dynamical and microphysical parameters, provide significant new data for constraining and evaluating global chemistry climate models. Measurements include precursor and product gas species of reactive halogen compounds that impact ozone in the upper troposphere/lower stratosphere. High accuracy, in-situ measurements of ozone obtained during CONTRAST quantify ozone concentration profiles in the UT, where previous observations from balloon-borne ozonesondes were often near or below the limit of detection. CONTRAST was one of the three coordinated experiments to observe the TWP during January-February 2014. Together, CONTRAST, ATTREX and CAST, using complementary capabilities of the three aircraft platforms as well as ground-based instrumentation, provide a comprehensive quantification of the regional distribution and vertical structure of natural and pollutant trace gases in the TWP during NH winter, from the oceanic boundary to the lower stratosphere.

Very short-lived brominated substances (VSLBr) are an important source of stratospheric bromine, an effective ozone destruction catalyst. However, the accurate estimation of the organic and inorganic partitioning of bromine and the input to the stratosphere remains uncertain. Here, we report near-tropopause measurements of organic brominated substances found over the tropical Pacific during the NASA Airborne Tropical Tropopause Experiment campaigns. We combine aircraft observations and a chemistry−climate model to quantify the total bromine loading injected to the stratosphere. Surprisingly, despite differences in vertical transport between the Eastern and Western Pacific, VSLBr (organic + inorganic) contribute approximately similar amounts of bromine [∼6 (4−9) parts per thousand] to the stratospheric input at the tropical tropopause. These levels of bromine cause substantial ozone depletion in the lower stratosphere, and any increases in future abundances (e.g., as a result of aquaculture) will lead to larger depletions.

Abstract. 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 CON-TRAST 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 Cshape 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 "middleworld" 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 more complex partitioning of gas-phase and aerosol Br y species than previously recognized. Our data provide corroborating evidence that inorganic bromine sources (e.g., SSA-derived gas-phase Br y ) are needed to explain the gas-phase Br y 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 Br y budget in the TTL is currently not closed, because of the lack of concurrent quantitative measurements of gas-phase Br y species (i.e., BrO, HOBr, HBr, etc.) and aerosol bromide. Such simultaneous measurements are needed to (1) quantify SSA-derived Br y in the upper FT, (2) test Br y partitioning, and possibly explain the gas-phase Br y minimum in the aged TTL, (3) constrain heterogeneous reaction rates of bromine, and (4) account for all of the sources of Br y to the lower stratosphere.

A s the primary conduit for CO 2 and heat exchange between the atmosphere and the deep ocean, the Southern Ocean is an important part of the climate system. Approximately 40% of the ocean's inventory of anthropogenic carbon entered through the air-sea interface south of 40°S (Khatiwala et al. 2009), and the region will continue to serve as an important carbon sink into the future (Ito et al. 2015). Despite its importance, the processes controlling air-sea gas exchange in the Southern Ocean are poorly represented by models. This was highlighted in a recent comparison of models from phase 5 of the Coupled Model Intercomparison Project (CMIP5), wherein the simulated seasonal cycles of air-sea CO 2 exchange with the Southern Ocean were widely divergent and in poor agreement with observational estimates (Anav et al. 2013;Jiang et al. 2014), suggesting possible model biases in the timing, spatial A recent Southern Ocean airborne campaign collected continuous, discrete, and remote sensing measurements to investigate biogeochemical and physical processes driving air-sea exchange of CO 2 , O 2 , and reactive biogenic gases.

A chemical ionization mass spectrometer was used to measure BrO and HOBr + Br2 over the Tropical West Pacific Ocean within the altitude range of 1 to 15 km, during the CONvective TRansport of Active Species in the Tropics (CONTRAST) campaign in 2014. Isolated episodes of elevated BrO (up to 6.6 pptv) and/or HOBr + Br2 (up to 7.3 pptv) were observed in the tropical free troposphere (TFT) and were associated with biomass burning. However, most of the time we did not observe significant BrO or HOBr + Br2 in the TFT and the tropical tropopause layer (TTL) above our limits of detection (LOD). The 1 min average LOD for BrO ranged from 0.6 to 1.6 pptv and for HOBr + Br2 ranged from 1.3 to 3.5 pptv. During one flight, BrO observations from the TTL to the extratropical lowermost stratosphere were used to infer a profile of inorganic bromine (Bry). Based on this profile, we estimated the product gas injection of bromine species into the stratosphere to be 2 pptv. Analysis of Bry partitioning further indicates that BrO levels are likely very low in the TFT environment and that future studies should target the measurement of HBr or atomic Br.