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

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 (Utqiaġvik), 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 ∼ 250 km downwind from Barrow (Utqiaġvik). 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 re-freezing 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 ∼ 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 ∼ 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 ∼ 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 (\u3e 0.1 km−1); however, the presence of aerosol particles aloft was not sufficient to produce BrO aloft. Highly depleted ozone (−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

Quantification of urban atmospheric boundary layer greenhouse gas dry mole fraction enhancements in the dormant season: Results from the Indianapolis Flux Experiment (INFLUX)

We assess the detectability of city emissions via a tower-based greenhouse gas (GHG) network, as part of the Indianapolis Flux (INFLUX) experiment. By examining afternoon-averaged results from a network of carbon dioxide (CO2), methane (CH4), and carbon monoxide (CO) mole fraction measurements in Indianapolis, Indiana for 2011–2013, we quantify spatial and temporal patterns in urban atmospheric GHG dry mole fractions. The platform for these measurements is twelve communications towers spread across the metropolitan region, ranging in height from 39 to 136 m above ground level, and instrumented with cavity ring-down spectrometers. Nine of the sites were deployed as of January 2013 and data from these sites are the focus of this paper. A background site, chosen such that it is on the predominantly upwind side of the city, is utilized to quantify enhancements caused by urban emissions. Afternoon averaged mole fractions are studied because this is the time of day during which the height of the boundary layer is most steady in time and the area that influences the tower measurements is likely to be largest. Additionally, atmospheric transport models have better performance in simulating the daytime convective boundary layer compared to the nighttime boundary layer. Averaged from January through April of 2013, the mean urban dormant-season enhancements range from 0.3 ppm CO2 at the site 24 km typically downwind of the edge of the city (Site 09) to 1.4 ppm at the site at the downwind edge of the city (Site 02) to 2.9 ppm at the downtown site (Site 03). When the wind is aligned such that the sites are downwind of the urban area, the enhancements are increased, to 1.6 ppm at Site 09, and 3.3 ppm at Site 02. Differences in sampling height affect the reported urban enhancement by up to 50%, but the overall spatial pattern remains similar. The time interval over which the afternoon data are averaged alters the calculated urban enhancement by an average of 0.4 ppm. The CO2 observations are compared to CO2 mole fractions simulated using a mesoscale atmospheric model and an emissions inventory for Indianapolis. The observed and modeled CO2 enhancements are highly correlated (r2 = 0.94), but the modeled enhancements prior to inversion average 53% of those measured at the towers. Following the inversion, the enhancements follow the observations closely, as expected. The CH4 urban enhancement ranges from 5 ppb at the site 10 km predominantly downwind of the city (Site 13) to 21 ppb at the site near the landfill (Site 10), and for CO ranges from 6 ppb at the site 24 km downwind of the edge of the city (Site 09) to 29 ppb at the downtown site (Site 03). Overall, these observations show that a dense network of urban GHG measurements yield a detectable urban signal, well-suited as input to an urban inversion system given appropriate attention to sampling time, sampling altitude and quantification of background conditions

The Role of Open Lead Interactions in Atmospheric Ozone Variability Between Arctic Coastal and Inland Sites

Boundary layer atmospheric ozone depletion events (ODEs) are commonly observed across polar sea ice regions following polar sunrise. During March-April 2005 in Alaska, the coastal site of Barrow and inland site of Atqasuk experienced ODEs (O3 \u3c 10 nmol mol-1) concurrently for 31% of the observations, consistent with large spatial scale ozone depletion. However, 7% of the time ODEs were exclusively observed inland at Atqasuk. This phenomenon also occurred during one of nine flights during the BRomine, Ozone, and Mercury EXperiment (BROMEX), when atmospheric vertical profiles at both sites showed near-surface ozone depletion only at Atqasuk on 28 March 2012. Concurrent in-flight BrO measurements made using nadir scanning differential optical absorption spectroscopy (DOAS) showed the differences in ozone vertical profiles at these two sites could not be attributed to differences in locally occurring halogen chemistry. During both studies, backward air mass trajectories showed that the Barrow air masses observed had interacted with open sea ice leads, causing increased vertical mixing and recovery of ozone at Barrow and not Atqasuk, where the air masses only interacted with tundra and consolidated sea ice. These observations suggest that, while it is typical for coastal and inland sites to have similar ozone conditions, open leads may cause heterogeneity in the chemical composition of the springtime Arctic boundary layer over coastal and inland areas adjacent to sea ice regions

A surface-stabilized ozonide triggers bromide oxidation at the aqueous solution-vapour interface

Oxidation of bromide in aqueous environments initiates the formation of molecular halogen compounds, which is important for the global tropospheric ozone budget. In the aqueous bulk, oxidation of bromide by ozone involves a [Br•OOO−] complex as intermediate. Here we report liquid jet X-ray photoelectron spectroscopy measurements that provide direct experimental evidence for the ozonide and establish its propensity for the solution-vapor interface. Theoretical calculations support these findings, showing that water stabilizes the ozonide and lowers the energy of the transition state at neutral pH. Kinetic experiments confirm the dominance of the heterogeneous oxidation route established by this precursor at low, atmospherically relevant ozone concentrations. Taken together, our results provide a strong case of different reaction kinetics and mechanisms of reactions occurring at the aqueous phase-vapor interface compared with the bulk aqueous phase

Observations of bromine monoxide transport in the Arctic sustained on aerosol particles

The return of sunlight in the polar spring leads to the production of reactive halogen species from the surface snowpack, significantly altering the chemical composition of the Arctic near-surface atmosphere and the fate of long-range transported pollutants, including mercury. Recent work has shown the initial production of reactive bromine at the Arctic surface snowpack; however, we have limited knowledge of the vertical extent of this chemistry, as well as the lifetime and possible transport of reactive bromine aloft. Here, we present bromine monoxide (BrO) and aerosol particle measurements obtained during the March 2012 BRomine Ozone Mercury EXperiment (BROMEX) near Utqiaġvik (Barrow), AK. The airborne differential optical absorption spectroscopy (DOAS) measurements provided an unprecedented level of spatial resolution, over 2 orders of magnitude greater than satellite observations and with vertical resolution unable to be achieved by satellite methods, for BrO in the Arctic. This novel method provided quantitative identification of a BrO plume, between 500 m and 1 km aloft, moving at the speed of the air mass. Concurrent aerosol particle measurements suggest that this lofted reactive bromine plume was transported and maintained at elevated levels through heterogeneous reactions on colocated supermicron aerosol particles, independent of surface snowpack bromine chemistry. This chemical transport mechanism explains the large spatial extents often observed for reactive bromine chemistry, which impacts atmospheric composition and pollutant fate across the Arctic region, beyond areas of initial snowpack halogen production. The possibility of BrO enhancements disconnected from the surface potentially contributes to sustaining BrO in the free troposphere and must also be considered in the interpretation of satellite BrO column observations, particularly in the context of the rapidly changing Arctic sea ice and snowpack

Field and Satellite Observations of the Formation and Distribution of Arctic Atmospheric Bromine Above a Rejuvenated Sea Ice Cover

Recent drastic reduction of the older perennial sea ice in the Arctic Ocean has resulted in a vast expansion of younger and saltier seasonal sea ice. This increase in the salinity of the overall ice cover could impact tropospheric chemical processes. Springtime perennial ice extent in 2008 and 2009 broke the half-century record minimum in 2007 by about one million km2. In both years seasonal ice was dominant across the Beaufort Sea extending to the Amundsen Gulf, where significant field and satellite observations of sea ice, temperature, and atmospheric chemicals have been made. Measurements at the site of the Canadian Coast Guard Ship Amundsen ice breaker in the Amundsen Gulf showed events of increased bromine monoxide (BrO), coupled with decreases of ozone (O3) and gaseous elemental mercury (GEM), during cold periods in March 2008. The timing of the main event of BrO, O3, and GEM changes was found to be consistent with BrO observed by satellites over an extensive area around the site. Furthermore, satellite sensors detected a doubling of atmospheric BrO in a vortex associated with a spiral rising air pattern. In spring 2009, excessive and widespread bromine explosions occurred in the same region while the regional air temperature was low and the extent of perennial ice was significantly reduced compared to the case in 2008. Using satellite observations together with a Rising-Air-Parcel model, we discover a topographic control on BrO distribution such that the Alaskan North Slope and the Canadian Shield region were exposed to elevated BrO, whereas the surrounding mountains isolated the Alaskan interior from bromine intrusion

The Indianapolis Flux Experiment (INFLUX): A test-bed for developing urban greenhouse gas emission measurements

The objective of the Indianapolis Flux Experiment (INFLUX) is to develop, evaluate and improve methods for measuring greenhouse gas (GHG) emissions from cities. INFLUX’s scientific objectives are to quantify CO2 and CH4 emission rates at 1 km2 resolution with a 10% or better accuracy and precision, to determine whole-city emissions with similar skill, and to achieve high (weekly or finer) temporal resolution at both spatial resolutions. The experiment employs atmospheric GHG measurements from both towers and aircraft, atmospheric transport observations and models, and activity-based inventory products to quantify urban GHG emissions. Multiple, independent methods for estimating urban emissions are a central facet of our experimental design. INFLUX was initiated in 2010 and measurements and analyses are ongoing. To date we have quantified urban atmospheric GHG enhancements using aircraft and towers with measurements collected over multiple years, and have estimated whole-city CO2 and CH4 emissions using aircraft and tower GHG measurements, and inventory methods. Significant differences exist across methods; these differences have not yet been resolved; research to reduce uncertainties and reconcile these differences is underway. Sectorally- and spatially-resolved flux estimates, and detection of changes of fluxes over time, are also active research topics. Major challenges include developing methods for distinguishing anthropogenic from biogenic CO2 fluxes, improving our ability to interpret atmospheric GHG measurements close to urban GHG sources and across a broader range of atmospheric stability conditions, and quantifying uncertainties in inventory data products. INFLUX data and tools are intended to serve as an open resource and test bed for future investigations. Well-documented, public archival of data and methods is under development in support of this objective

Assessing the optimized precision of the aircraft mass balance method for measurement of urban greenhouse gas emission rates through averaging

To effectively address climate change, aggressive mitigation policies need to be implemented to reduce greenhouse gas emissions. Anthropogenic carbon emissions are mostly generated from urban environments, where human activities are spatially concentrated. Improvements in uncertainty determinations and precision of measurement techniques are critical to permit accurate and precise tracking of emissions changes relative to the reduction targets. As part of the INFLUX project, we quantified carbon dioxide (CO2), carbon monoxide (CO) and methane (CH4) emission rates for the city of Indianapolis by averaging results from nine aircraft-based mass balance experiments performed in November-December 2014. Our goal was to assess the achievable precision of the aircraft-based mass balance method through averaging, assuming constant CO2, CH4 and CO emissions during a three-week field campaign in late fall. The averaging method leads to an emission rate of 14,600 mol/s for CO2, assumed to be largely fossil-derived for this period of the year, and 108 mol/s for CO. The relative standard error of the mean is 17% and 16%, for CO2 and CO, respectively, at the 95% confidence level (CL), i.e. a more than 2-fold improvement from the previous estimate of ~40% for single-flight measurements for Indianapolis. For CH4, the averaged emission rate is 67 mol/s, while the standard error of the mean at 95% CL is large, i.e. ±60%. Given the results for CO2 and CO for the same flight data, we conclude that this much larger scatter in the observed CH4 emission rate is most likely due to variability of CH4 emissions, suggesting that the assumption of constant daily emissions is not correct for CH4 sources. This work shows that repeated measurements using aircraft-based mass balance methods can yield sufficient precision of the mean to inform emissions reduction efforts by detecting changes over time in urban emissions

Importance of biogenic volatile organic compounds to acyl peroxy nitrates (APN) production in the southeastern US during SOAS 2013

Gas-phase atmospheric concentrations of peroxyacetyl nitrate (PAN), peroxypropionyl nitrate (PPN), and peroxymethacryloyl nitrate (MPAN) were measured on the ground using a gas chromatograph electron capture detector (GC-ECD) during the Southern Oxidants and Aerosols Study (SOAS) 2013 campaign (1 June to 15 July 2013) in Centreville, Alabama, in order to study biosphere&ndash;atmosphere interactions. Average levels of PAN, PPN, and MPAN were 169, 5, and 9&thinsp;pptv, respectively, and the sum accounts for an average of 16&thinsp;% of NOy during the daytime (10:00 to 16:00 local time). Higher concentrations were seen on average in air that came to the site from the urban NOx sources to the north. PAN levels were the lowest observed in ground measurements over the past two decades in the southeastern US. A multiple regression analysis indicates that biogenic volatile organic compounds (VOCs) account for 66&thinsp;% of PAN formation during this study. Comparison of this value with a 0-D model simulation of peroxyacetyl radical production indicates that at least 50&thinsp;% of PAN formation is due to isoprene oxidation. MPAN has a statistical correlation with isoprene hydroxynitrates (IN). Organic aerosol mass increases with gas-phase MPAN and IN concentrations, but the mass of organic nitrates in particles is largely unrelated to MPAN.</p