Bromine Monoxide Research Articles

Atmospheric formaldehyde at El Teide and Pic du Midi remote high-altitude sites

Formaldehyde (CH2O) is a tracer of the photochemical activity of the atmosphere. Linked to air quality, CH2O is an ozone (O3) precursor and serves as a proxy for natural and anthropogenic reactive organic emissions. As a product of the photooxidation of methane (CH4) and other hydrocarbons (e.g., isoprene), CH2O represents an important source of radicals in the remote free troposphere. This work aims at improving the characterization of this part of the troposphere where data are scarce. In particular, this study assesses the presence of CH2O at two high-altitude remote sites: El Teide (TEI, 3570 m a.s.l., Tenerife, Canary Islands, Spain) and Pic du Midi (PDM, 2877 m a.s.l., French Pyrenees). Through ground-based remote sensing measurements performed during two field campaigns in July (TEI) and September (PDM) 2013, this study presents the vertical distribution of CH2O at both locations. Results at PDM show that CH2O mixing ratios follow a decreasing vertical profile with a mean maximum of 0.5 ± 0.2 nmol mol−1 (i.e., ppbv) at the instruments' altitude. At TEI, observations indicate an uplifted layer of CH2O with a mean maximum of 1.3 ± 0.3 nmol mol−1 at 3.8 km a.s.l. (i.e., 300 m above the instrument's altitude). At both remote sites, the observed CH2O levels are higher than expected for background methane oxidation (a threefold increase in the case of TEI). Air mass back trajectory analysis links CH2O observations with abundant natural (e.g. forests) and/or anthropogenic isoprene emissions from the region nearby PDM, while the high CH2O levels detected at TEI indicate in-plume formation of CH2O resulting from its precursors emitted from west-African and Canadian fires. Finally, as a key trace gas for O3 and HOx chemistries, we estimate the upper limit of bromine monoxide (BrO) in the free troposphere at TEI and PDM to be 0.8 and 1.5 pmol mol−1 (i.e., pptv) respectively.

Arctic Reactive Bromine Events Occur in Two Distinct Sets of Environmental Conditions: A Statistical Analysis of 6 Years of Observations

AbstractTropospheric bromine radicals in the Arctic efficiently remove ambient ozone and oxidize gaseous elemental mercury. Ground‐based bromine monoxide (BrO) observations from the Arctic Ocean and Utqiaġvik (formerly Barrow) are combined with Modern Era Retrospective Analysis for Research and Applications version 2 reanalysis meteorological fields to determine how BrO varies with environmental conditions. The mean seasonal BrO abundance varies from year to year (p < 0.001), while regional variance in mean BrO is not statistically significant (p > 0.11). Principal component analysis derived three important principal components from the environmental data set. The third principal component explains the most variance in BrO and is correlated with low ozone and cold temperatures. This principal component is consistent with high BrO during ozone depletion events at cold temperatures and can work concurrently with each of the other two principal components to generate two distinct environmental types of high BrO events. The first principal component consists of a less‐stable, thick, mixed layer and low atmospheric pressure and is consistent with observations of high BrO in low‐pressure systems (e.g., storms). The second principal component consists of cold and stable conditions and is consistent with high BrO under surface‐based temperature inversions. Our principal component regression model predicted the both the vertical column density of BrO in the lowest 2 km of the troposphere (R = 0.45) and the vertical column density of BrO in the lowest 200 m (R = 0.54). This statistical description of two types of reactive bromine events may help to harmonize space‐based and ground‐based observations.

Thermodynamics and kinetics of 1-fluoro-2-methoxypropane vs Bromine monoxide radical (BrO): A computational view

CFCs containing volatile compounds are detrimental to atmospheric environment and to all living organisms. These compounds are frequently reported to be chemically stable/inert. Also their photodissociation reaction results to reasonable amount of Chlorine atoms formation in the stratospheric part of atmosphere. This eventually bring out depletion of Ozone (lives and properties protecting compound) in the stratosphere. In order to cope this environmental havoc, there is need to find substitutable compounds for CFCs and possibly predict their atmospheric effects. Ethers when fluorinated can serve as CFCs substitute. Therefore, in this work, an Insilco investigation was conducted on the thermochemistry, mechanism and kinetics of the Hydrogen abstraction reactions of partially fluorinated isopropyl methyl ether (1-fluoro-2-methoxypropane i.e. (CH2FCH(OCH3)CH3)) with Bromine monoxide radical (BrO.) using the Density Functional Theory (DFT) based M06-2X/6-311++G** strategy. To computationally refine/improve the energy data, the single-point calculations (DFT/M06-2X/6-311++G(2df,2p) were immediately executed on the reacting species involved. The Monte Carlo search on the investigating CH2FCH(OCH3)CH3 showed nine conformers with the lowest global minimum configuration being studied. The results of this investigation showed that the atmospheric oxidation reaction of CH2FCH(OCH3)CH3 with the BrO radical proceeded in four (4) plausible reaction routes. The computed total theoretical rate of 7.95*〖10〗^(-11) M-1 sec-1, the first of its kind with BrO radical was recorded. The atmospheric lifetime/global warming potential of 1.35*10-2 days/72.8 were also reported. The potential energy surface (PES) for each reaction route with the BrO radical was constructed at absolute temperature of 298.15 K.

Variation of the BrO/SO2 Molar Ratio in the Plume of Tungurahua Volcano Between 2007 and 2017 and Its Relationship to Volcanic Activity

We present the results of ten years (2007 to 2017) of observation of the bromine monoxide (BrO) to sulphur dioxide (SO2) molar ratio in the volcanic plume of Tungurahua volcano and study the relation to volcanic activity. Following the nearly continuous eruptive activity from 1999 to 2008, Tungurahua showed alternating phases of eruptive activity separated by periods of quiescence between late 2008 and March 2016, after which degassing intensity decreased below the detection limit of the UV scanning DOAS instruments. Recent long-term observations have suggested a link between changes in the BrO/SO2 molar ratio and the volcanic activity. Nevertheless, understanding of the mechanisms determining this link is still limited due to the lack of studies on volcanic bromine release from the melt into the atmosphere. This study aims to broaden the global observational database through analysis of BrO/SO2 molar ratios collected from 13 eruptive phases at Tungurahua volcano during 10 years of continuous observations. For this purpose, we combine three different methods to retrieve the BrO/SO2 molar ratio to analyse variations over different time-scales. We identify a cyclic pattern in BrO/SO2 molar ratios for 11 of the 13 eruptive phases. The phases are initialised by low BrO/SO2 molar ratios between 2 and 6x10-5 coinciding with vulcanian-type activity followed by a strong increase to ratios ranging between 4 and 17x10-5 when eruptive dynamism shifts to strombolian. For 5 phases, we additionally observe a progressive decrease to the initial values of 2 to 5x10-5 towards the end of the phase. This clear pattern indicates a connection between the BrO/SO2 molar ratio and eruptive dynamics. Based on our new data, we propose a conceptual model of the volcanic processes taking place at Tungurahua during the eruptive phases. Our data furthermore indicates that maximal BrO/SO2 ratio observed during each phases could be related to the input of volatile-rich magma into the active part of the volcanic system of Tungurahua. This study shows that long-term BrO/SO2 ratios can be used as a proxy for the volatile status as well as temporal evolution of the volcanic system.

First high-resolution BrO column retrievals from TROPOMI

Abstract. For more than 2 decades, satellite observations from instruments such as GOME, SCIAMACHY, GOME-2, and OMI have been used for the monitoring of bromine monoxide (BrO) distributions on global and regional scales. In October 2017, the TROPOspheric Monitoring Instrument (TROPOMI) was launched on board the Copernicus Sentinel-5 Precursor platform with the goal of continuous daily global trace gas observations with unprecedented spatial resolution. In this study, sensitivity tests were performed to find an optimal wavelength range for TROPOMI BrO retrievals under various measurement conditions. From these sensitivity tests, a wavelength range for TROPOMI BrO retrievals was determined and global data for April 2018 as well as for several case studies were retrieved. Comparison with GOME-2 and OMI BrO retrievals shows good consistency and low scatter of the columns. The examples of individual TROPOMI overpasses show that due to the better signal-to-noise ratio and finer spatial resolution of 3.5×7 km2, TROPOMI BrO retrievals provide good data quality with low fitting errors and unique information on small-scale variabilities in various BrO source regions such as Arctic sea ice, salt marshes, and volcanoes.

Effect of sea salt aerosol on tropospheric bromine chemistry

Abstract. Bromine radicals influence global tropospheric chemistry by depleting ozone and by oxidizing elemental mercury and reduced sulfur species. Observations typically indicate a 50 % depletion of sea salt aerosol (SSA) bromide relative to seawater composition, implying that SSA debromination could be the dominant global source of tropospheric bromine. However, it has been difficult to reconcile this large source with the relatively low bromine monoxide (BrO) mixing ratios observed in the marine boundary layer (MBL). Here we present a new mechanistic description of SSA debromination in the GEOS-Chem global atmospheric chemistry model with a detailed representation of halogen (Cl, Br, and I) chemistry. We show that observed levels of SSA debromination can be reproduced in a manner consistent with observed BrO mixing ratios. Bromine radical sinks from the HOBr + S(IV) heterogeneous reactions and from ocean emission of acetaldehyde are critical in moderating tropospheric BrO levels. The resulting HBr is rapidly taken up by SSA and also deposited. Observations of SSA debromination at southern midlatitudes in summer suggest that model uptake of HBr by SSA may be too fast. The model provides a successful simulation of free-tropospheric BrO in the tropics and midlatitudes in summer, where the bromine radical sink from the HOBr + S(IV) reactions is compensated for by more efficient HOBr-driven recycling in clouds compared to previous GEOS-Chem versions. Simulated BrO in the MBL is generally much higher in winter than in summer due to a combination of greater SSA emission and slower conversion of bromine radicals to HBr. An outstanding issue in the model is the overestimate of free-tropospheric BrO in extratropical winter–spring, possibly reflecting an overestimate of the HOBr∕HBr ratio under these conditions where the dominant HOBr source is hydrolysis of BrNO3.

OMI total bromine monoxide (OMBRO) data product: algorithm, retrieval and measurement comparisons

Abstract. This paper presents the retrieval algorithm for the operational Ozone Monitoring Instrument (OMI) total bromine monoxide (BrO) data product (OMBRO) developed at the Smithsonian Astrophysical Observatory (SAO) and shows comparisons with correlative measurements and retrieval results. The algorithm is based on direct nonlinear least squares fitting of radiances from the spectral range 319.0–347.5 nm. Radiances are modeled from the solar irradiance, attenuated by contributions from BrO and interfering gases, and including rotational Raman scattering, additive and multiplicative closure polynomials, correction for Nyquist undersampling and the average fitting residual spectrum. The retrieval uses albedo- and wavelength-dependent air mass factors (AMFs), which have been pre-computed using a single mostly stratospheric BrO profile. The BrO cross sections are multiplied by the wavelength-dependent AMFs before fitting so that the vertical column densities (VCDs) are retrieved directly. The fitting uncertainties of BrO VCDs typically vary between 4 and 7×1012 molecules cm−2 (∼10 %–20 % of the measured BrO VCDs). Additional fitting uncertainties can be caused by the interferences from O2-O2 and H2CO and their correlation with BrO. AMF uncertainties are estimated to be around 10 % when the single stratospheric-only BrO profile is used. However, under conditions of high tropospheric concentrations, AMF errors due to this assumption of profile can be as high as 50 %. The retrievals agree well with GOME-2 observations at simultaneous nadir overpasses and with ground-based zenith-sky measurements at Harestua, Norway, with mean biases less than -0.22±1.13×1013 and 0.12±0.76×1013 molecules cm−2, respectively. Global distribution and seasonal variation of OMI BrO are generally consistent with previous satellite observations. Finally, we confirm the capacity of OMBRO retrievals to observe enhancements of BrO over the US Great Salt Lake despite the current retrieval setup considering a stratospheric profile in the AMF calculations. OMBRO retrievals also show significant BrO enhancements from the eruption of the Eyjafjallajökull volcano, although the BrO retrievals are affected under high SO2 loading conditions by the sub-optimum choice of SO2 cross sections.

AN INSILCO STUDY OF 1,1-DIFLUORO-2-METHOXYPROPANE REACTION MECHANISM WITH THE BROMINE MONOXIDE (BrO) RADICAL

An Insilco study was carried out on the thermochemistry, mechanism and kinetics of the Hydrogen abstraction reaction of 1,1-difluoro-2-methoxypropane (CH 3 CH(OCH 3 )CHF 2 ) with the Bromine monoxide radical (BrO) using the Density Functional Theory (DFT) based M06-2X/ 6-311++G ** method. The energy values were immediately improved via optimization at DFT/M06-2X/6-311++G(2df,2p) level ( single-point calculations) of the reacting species involved. The Monte Carlo search on the investigating hydrofluoroether (HFE) showed nine conformers with the lowest global minimum conformer being predicted and considered for this work. The results of this study showed that the atmospheric oxidation reaction of CH 3 CH(OCH 3 )CHF 2 with the BrO radical proceeded in four (4) plausible reaction routes. The total experimental rate of 4.34*10 -06 cm -3 molecule -1 sec -1 for HFE + BrO reaction was estimated with atmospheric lifetime (ALT)/global warming potential (GWP) of 1.80 years and 165.30 respectively. The 3D potential energy surfaces (PES) for the reaction was however constructed at absolute temperature of 298.15 K.

Snowpack measurements suggest role for multi-year sea ice regions in Arctic atmospheric bromine and chlorine chemistry

As sources of reactive halogens, snowpacks in sea ice regions control the oxidative capacity of the Arctic atmosphere. However, measurements of snowpack halide concentrations remain sparse, particularly in the high Arctic, limiting our understanding of and ability to parameterize snowpack participation in tropospheric halogen chemistry. To address this gap, we measured concentrations of chloride, bromide, and sodium in snow samples collected during polar spring above remote multi-year sea ice (MYI) and first-year sea ice (FYI) north of Greenland and Alaska, as well as in the central Arctic, and compared these measurements to a larger dataset collected in the Alaskan coastal Arctic by Krnavek et al. (2012). Regardless of sea ice region, these surface snow samples generally featured lower salinities, compared to coastal snow. Surface snow in FYI regions was typically enriched in bromide and chloride compared to seawater, indicating snowpack deposition of bromine and chlorine-containing trace gases and an ability of the snowpack to participate further in bromine and chlorine activation processes. In contrast, surface snow in MYI regions was more often depleted in bromide, indicating it served as a source of bromine-containing trace gases to the atmosphere prior to sampling. Measurements at various snow depths indicate that the deposition of sea salt aerosols and halogen-containing trace gases to the snowpack surface played a larger role in determining surface snow halide concentrations compared to upward brine migration from sea ice. Calculated enrichment factors for bromide and chloride, relative to sodium, in the MYI snow samples suggests that MYI regions, in addition to FYI regions, have the potential to play an active role in Arctic boundary layer bromine and chlorine chemistry. The ability of MYI regions to participate in springtime atmospheric halogen chemistry should be considered in regional modeling of halogen activation and interpretation of satellite-based tropospheric bromine monoxide column measurements.

Advances in Bromine Speciation in Volcanic Plumes

Volcanoes are a significant halogen source to the atmosphere. After water, carbon dioxide and sulfur compounds, halogens are often the most abundant gases in volcanic plumes. In the past, less attention was given to the heavy halogens bromine and iodine. However, the discovery of bromine monoxide (BrO) in volcanic plumes led to new interest especially in volcanic bromine chemistry and its impact on atmospheric processes. The BrO detection came along with advances in volcanic remote sensing techniques, in particular, robust DOAS applications and the possibility of continuous measurements by automated instruments located at safe distances from the volcano. As one of the consequences, the volcanic community developed an increased interest to use BrO/SO2 ratios as a potential tracer of volcanic activity. BrO is a secondary volcanic gas, but the only bromine species in volcanic plumes, which has been measured by remote sensing techniques today. For a better understanding on bromine chemistry in volcanic plumes and to gain information on the original amount of emitted bromine by only measuring BrO, additional techniques were developed (alkaline traps, diffusion denuders) and adapted for drone-based sampling to determine further gaseous bromine species (i.e. Br2, HBr, HOBr, interhalogens) at various plume ages. Additionally models of plume-atmospheric chemistry were developed to help the interpretation of field-measurements. Model studies simulating plume conditions indicated that a complex atmospheric chemistry mechanism transforms emitted HBr into BrO and other reactive bromine species such as BrOH, Br2, BrCl, BrONO2 or BrNO2. To reproduce the very rapid formation of BrO observed in volcanic plumes, the volcanic emission input to the (low-temperature) plume chemistry models also needs to consider the high-temperature near-vent plume conditions, as represented by thermodynamic models. The formation of BrO and other reactive bromine species depend not only on the amount of bromine emitted but also on plume mixing processes, relative humidity, and aerosol particle acidity. However, uncertainties remain in the validation of the plume chemistry models by a lack of field-measurements. This review provides an overview on volcanic bromine data achieved from established and cutting edge measurement techniques as well as their treatment and interpretation in recent model experiments.

Polar Nighttime Chemistry Produces Intense Reactive Bromine Events

AbstractBy examining the origin of airmasses that arrive at Utqiaġvik (formerly Barrow), Alaska, soon after polar sunrise (late January/early February), we identified periods when air arriving at Utqiaġvik had previously resided primarily at higher latitudes in near total darkness. Upon illumination, these airmasses produced high concentrations of reactive bromine, which was detected by differential optical absorption spectroscopy as bromine monoxide (BrO). These observations are consistent with nighttime production of a photolabile reactive bromine precursor (e.g., Br2 or BrCl). A large polar night source of photolabile reactive bromine precursors would contribute seed reactive bromine to daytime reactive bromine events and could export reactive halogens to lower latitudes and the free troposphere.

Observations and source investigations of the boundary layer bromine monoxide (BrO) in the Ny-Ålesund Arctic

Abstract. During polar spring, the presence of reactive bromine in the polar boundary layer is considered to be the main cause of ozone depletion and mercury deposition. However, many uncertainties still remain regarding understanding the mechanisms of the chemical process and source of the bromine. As Arctic sea ice has recently been dramatically reduced, it is critical to investigate the mechanisms using more accurate measurements with higher temporal and spatial resolution. In this study, a typical process of enhanced bromine and depleted ozone in the Ny-Ålesund boundary layer in late April 2015 was observed by applying ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) technique. The results showed that there were bromine monoxide (BrO) slant columns as high as 5.6 × 1014 molec cm−2 above the Kings Bay area on 26 April. Meanwhile, the boundary layer ozone and gaseous elemental mercury (GEM) were synchronously reduced by 85 and 90 %, respectively. Based on the meteorology, sea ice distribution and air mass history, the sea ice in the Kings Bay area, which emerged for only a very short period of time when the enhanced BrO was observed, was considered to be the major source of this bromine enhancement event. The oxidized GEM may be directly deposited onto snow/ice and thereby influence the polar ecosystem.

BrO and inferred Br<sub><i>y</i></sub> profiles over the western Pacific: relevance of inorganic bromine sources and a Br<sub><i>y</i></sub> minimum in the aged tropical tropopause layer

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.

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

Abstract. 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 (> 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.

Snowmelt onset hinders bromine monoxide heterogeneous recycling in the Arctic

AbstractReactive bromine radicals (bromine atoms, Br, and bromine monoxide, BrO) deplete ozone and alter tropospheric oxidation chemistry during the Arctic springtime (February–June). As spring transitions to summer (May–June) and snow begins to melt, reactive bromine events cease and BrO becomes low in summer. In this study, we explore the relationship between the end of the reactive bromine season and snowmelt timing. BrO was measured by Multi‐AXis Differential Optical Absorption Spectrometer at Utqiaġvik (Barrow), AK, from 2012 to 2016 and on drifting buoys deployed in Arctic sea ice from 2011 to 2016, a total of 13 site and year combinations. The BrO seasonal end date (SED) was objectively determined and was compared to surface‐air‐temperature‐derived melt onset date (MOD). The SED was highly correlated with the MOD (N = 13, R2 = 0.983, RMS = 1.9 days), and BrO is only observed at subfreezing temperatures. In subsets of these sites and years where ancillary data were available, we observed that snowpack depth reduced and rain precipitation occurred within a few days of the SED. These data are consistent with snowpack melting hindering BrO recycling, which is necessary to maintain enhanced BrO concentrations. With a projected warmer Arctic, a shift to earlier snowmelt seasons could alter the timing and role of halogen chemical reactions in the Arctic with impacts on ozone depletion and mercury deposition.

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

Abstract. 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.

Space-based observation of volcanic iodine monoxide

Abstract. Volcanic eruptions inject substantial amounts of halogens into the atmosphere. Chlorine and bromine oxides have frequently been observed in volcanic plumes from different instrumental platforms such as from ground, aircraft and satellites. The present study is the first observational evidence that iodine oxides are also emitted into the atmosphere during volcanic eruptions. Large column amounts of iodine monoxide, IO, are observed in satellite measurements following the major eruption of the Kasatochi volcano, Alaska, in 2008. The IO signal is detected in measurements made both by SCIAMACHY (Scanning Imaging Absorption Spectrometer for Atmospheric CHartographY) on ENVISAT (Environmental Satellite) and GOME-2 (Global Ozone Monitoring Experiment-2) on MetOp-A (Meteorological Operational Satellite A). Following the eruption on 7 August 2008, strongly elevated levels of IO slant columns of more than 4 × 1013 molec cm−2 are retrieved along the volcanic plume trajectories for several days. The retrieved IO columns from the different instruments are consistent, and the spatial distribution of the IO plume is similar to that of bromine monoxide, BrO. Details in the spatial distribution, however, differ between IO, BrO and sulfur dioxide, SO2. The column amounts of IO are approximately 1 order of magnitude smaller than those of BrO. Using the GOME-2A observations, the total mass of IO in the volcanic plume injected into the atmosphere from the eruption of Kasatochi on 7 August 2008, is determined to be on the order of 10 Mg.

Enhanced ozone loss by active inorganic bromine chemistry in the tropical troposphere

Bromine chemistry, particularly in the tropics, has been suggested to play an important role in tropospheric ozone loss although a lack of measurements of active bromine species impedes a quantitative understanding of its impacts. Recent modelling and measurements of bromine monoxide (BrO) by Wang et al. (2015) have shown current models under predict BrO concentrations over the Pacific Ocean and allude to a missing source of BrO. Here, we present the first simultaneous aircraft measurements of atmospheric bromine monoxide, BrO (a radical that along with atomic Br catalytically destroys ozone) and the inorganic Br precursor compounds HOBr, BrCl and Br2 over the Western Pacific Ocean from 0.5 to 7 km. The presence of 0.17–1.64 pptv BrO and 3.6–8 pptv total inorganic Br from these four species throughout the troposphere causes 10–20% of total ozone loss, and confirms the importance of bromine chemistry in the tropical troposphere; contributing to a 6 ppb decrease in ozone levels due to halogen chemistry. Observations are compared with a global chemical transport model and find that the observed high levels of BrO, BrCl and HOBr can be reconciled by active multiphase oxidation of halide (Br− and Cl−) by HOBr and ozone in cloud droplets and aerosols. Measurements indicate that 99% of the instantaneous free Br in the troposphere up to 8 km originates from inorganic halogen photolysis rather than from photolysis of organobromine species.

Remote sensing of volcanic CO<sub>2</sub>, HF, HCl, SO<sub>2</sub>, and BrO in the downwind plume of Mt. Etna

Abstract. Remote sensing of the gaseous composition of non-eruptive, passively degassing volcanic plumes can be a tool to gain insight into volcano interior processes. Here, we report on a field study in September 2015 that demonstrates the feasibility of remotely measuring the volcanic enhancements of carbon dioxide (CO2), hydrogen fluoride (HF), hydrogen chloride (HCl), sulfur dioxide (SO2), and bromine monoxide (BrO) in the downwind plume of Mt. Etna using portable and rugged spectroscopic instrumentation. To this end, we operated the Fourier transform spectrometer EM27/SUN for the shortwave-infrared (SWIR) spectral range together with a co-mounted UV spectrometer on a mobile platform in direct-sun view at 5 to 10 km distance from the summit craters. The 3 days reported here cover several plume traverses and a sunrise measurement. For all days, intra-plume HF, HCl, SO2, and BrO vertical column densities (VCDs) were reliably measured exceeding 5 × 1016, 2 × 1017, 5 × 1017, and 1 × 1014 molec cm−2, with an estimated precision of 2.2 × 1015, 1.3 × 1016, 3.6 × 1016, and 1.3 × 1013 molec cm−2, respectively. Given that CO2, unlike the other measured gases, has a large and well-mixed atmospheric background, derivation of volcanic CO2 VCD enhancements (ΔCO2) required compensating for changes in altitude of the observing platform and for background concentration variability. The first challenge was met by simultaneously measuring the overhead oxygen (O2) columns and assuming covariation of O2 and CO2 with altitude. The atmospheric CO2 background was found by identifying background soundings via the co-emitted volcanic gases. The inferred ΔCO2 occasionally exceeded 2 × 1019 molec cm−2 with an estimated precision of 3.7 × 1018 molec cm−2 given typical atmospheric background VCDs of 7 to 8 × 1021 molec cm−2. While the correlations of ΔCO2 with the other measured volcanic gases confirm the detection of volcanic CO2 enhancements, correlations were found of variable significance (R2 ranging between 0.88 and 0.00). The intra-plume VCD ratios ΔCO2 ∕ SO2, SO2 ∕ HF, SO2 ∕ HCl, and SO2 ∕ BrO were in the range 7.1 to 35.4, 5.02 to 21.2, 1.54 to 3.43, and 2.9 × 103 to 12.5 × 103, respectively, showing pronounced day-to-day and intra-day variability.

Kinetics of the BrO + HO2 reaction over the temperature range T = 246-314 K.

The kinetics of the reaction between gas phase BrO and HO2 radicals, BrO + HO2 → HOBr + O2 (1), have been studied over the atmospherically relevant temperature range T = 246-314 K and at ambient pressure, p = 760 ± 20 Torr, using laser flash photolysis coupled with ultraviolet absorption spectroscopy. The reaction was initiated by the generation of bromine monoxide radicals following laser photolytic generation of Br atoms from Br2/Cl2 containing mixtures and their reaction with ozone. Subsequently, the addition of methanol vapour to the reaction mixture, in the presence of excess oxygen, afforded the efficient simultaneous post-photolysis formation of HO2 radicals using well-defined chemistry. The decay of BrO radicals, in the presence and absence of HO2, was interrogated to determine the rate coefficients for the BrO + BrO and the BrO + HO2 reactions. A detailed sensitivity analysis was performed to ensure that the BrO + HO2 reaction was unequivocally monitored. The rate coefficient for reaction (1) is described by the Arrhenius expression: where statistical errors are 1σ. The negative temperature dependence of this reaction is in general accord with those reported by previous studies of this reaction. However, the present work reports greater absolute values for k1 than those of several previous studies. An assessment of previous laboratory studies of k1 is presented. This work confirms that reaction (1) plays a significant role in HOBr formation throughout the atmosphere following both anthropogenic, biogenic and volcanic emissions of brominated species. Reaction (1) therefore contributes to an efficient ozone depleting process in the atmosphere, and further confirms the significance of interactions between two different families of reactive atmospheric trace species.