Analysis of satellite-derived Arctic tropospheric BrO columns in conjunction with aircraft measurements during ARCTAS and ARCPAC

We derive tropospheric column BrO during the ARCTAS and ARCPAC field campaigns in spring 2008 using retrievals of total column BrO from the satellite UV nadir sensors OMI and GOME-2 using a radiative transfer model and stratospheric column BrO from a photochemical simulation. We conduct a comprehensive comparison of satellite-derived tropospheric BrO column to aircraft in-situ observations of BrO and related species. The aircraft profiles reveal that tropospheric BrO, when present during April 2008, was distributed over a broad range of altitudes rather than being confined to the planetary boundary layer (PBL). Perturbations to the total column resulting from tropospheric BrO are the same magnitude as perturbations due to longitudinal variations in the stratospheric component, so proper accounting of the stratospheric signal is essential for accurate determination of satellite-derived tropospheric BrO. We find reasonably good agreement between satellite-derived tropospheric BrO and columns found using aircraft in-situ BrO profiles, particularly when satellite radiances were obtained over bright surfaces (albedo \u3e0.7), for solar zenith angl

Characterization of soluble bromide measurements and a case study of BrO observations during ARCTAS

A focus of the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission was examination of bromine photochemistry in the spring time high latitude troposphere based on aircraft and satellite measurements of bromine oxide (BrO) and related species. The NASA DC-8 aircraft utilized a chemical ionization mass spectrometer (CIMS) to measure BrO and a mist chamber (MC) to measure soluble bromide. We have determined that the MC detection efficiency to molecular bromine (Br2), hypobromous acid (HOBr), bromine oxide (BrO), and hydrogen bromide (HBr) as soluble bromide (Br−) was 0.9±0.1, 1.06+0.30/−0.35, 0.4±0.1, and 0.95±0.1, respectively. These efficiency factors were used to estimate soluble bromide levels along the DC-8 flight track of 17 April 2008 from photochemical calculations constrained to in situ BrO measured by CIMS. During this flight, the highest levels of soluble bromide and BrO were observed and atmospheric conditions were ideal for the space-borne observation of BrO. The good agreement (R2 = 0.76; slope = 0.95; intercept = −3.4 pmol mol−1) between modeled and observed soluble bromide, when BrO was above detection limit (\u3e2 pmol mol−1) under unpolluted conditions (NOmol−1), indicates that the CIMS BrO measurements were consistent with the MC soluble bromide and that a well characterized MC can be used to derive mixing ratios of some reactive bromine compounds. Tropospheric BrO vertical column densities (BrOVCD) derived from CIMS BrO observations compare well with BrOTROPVCD from OMI on 17 April 2008

A new interpretation of total column BrO during Arctic spring

Emission of bromine from sea-salt aerosol, frost flowers, ice leads, and snow results in the nearly complete removal of surface ozone during Arctic spring. Regions of enhanced total column BrO observed by satellites have traditionally been associated with these emissions. However, airborne measurements of BrO and O3 within the convective boundary layer (CBL) during the ARCTAS and ARCPAC field campaigns at times bear little relation to enhanced column BrO. We show that the locations of numerous satellite BrO "hotspots" during Arctic spring are consistent with observations of total column ozone and tropopause height, suggesting a stratospheric origin to these regions of elevated BrO. Tropospheric enhancements of BrO large enough to affect the column abundance are also observed, with important contributions originating from above the CBL. Closure of the budget for total column BrO, albeit with significant uncertainty, is achieved by summing observed tropospheric partial columns with calculated stratospheric partial columns provided that natural, short-lived biogenic bromocarbons supply between 5 and 10 ppt of bromine to the Arctic lowermost stratosphere. Proper understanding of bromine and its effects on atmospheric composition requires accurate treatment of geographic variations in column BrO originating from both the stratosphere and troposphere. Copyright 2010 by the American Geophysical Union

A new interpretation of total column BrO during Arctic spring

Emission of bromine from sea-salt aerosol, frost flowers, ice leads, and snow results in the nearly complete removal of surface ozone during Arctic spring. Regions of enhanced total column BrO observed by satellites have traditionally been associated with these emissions. However, airborne measurements of BrO and O3 within the convective boundary layer (CBL) during the ARCTAS and ARCPAC field campaigns at times bear little relation to enhanced column BrO. We show that the locations of numerous satellite BrO “hotspots” during Arctic spring are consistent with observations of total column ozone and tropopause height, suggesting a stratospheric origin to these regions of elevated BrO. Tropospheric enhancements of BrO large enough to affect the column abundance are also observed, with important contributions originating from above the CBL. Closure of the budget for total column BrO, albeit with significant uncertainty, is achieved by summing observed tropospheric partial columns with calculated stratospheric partial columns provided that natural, short-lived biogenic bromocarbons supply between 5 and 10 ppt of bromine to the Arctic lowermost stratosphere. Proper understanding of bromine and its effects on atmospheric composition requires accurate treatment of geographic variations in column BrO originating from both the stratosphere and troposphere

Characteristics of tropospheric ozone depletion events in the Arctic spring: analysis of the ARCTAS, ARCPAC, and ARCIONS measurements and satellite BrO observations

Arctic ozone depletion events (ODEs) are caused by halogen catalyzed ozone loss. In situ chemistry, advection of ozone-poor air mass, and vertical mixing in the lower troposphere are important factors affecting ODEs. To better characterize the ODEs, we analyze the combined set of surface, ozonesonde, and aircraft in situ measurements of ozone and bromine compounds during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS), the Aerosol, Radiation, and Cloud Processes affecting Arctic Climate (ARCPAC), and the Arctic Intensive Ozonesonde Network Study (ARCIONS) experiments (April 2008). Tropospheric BrO columns retrieved from satellite measurements and back trajectory calculations are also used to investigate the characteristics of observed ODEs. In situ observations from these field experiments are inadequate to validate tropospheric BrO columns derived from satellite measurements. In view of this difficulty, we construct an ensemble of tropospheric column BrO estimates from two satellite (OMI and GOME-2) measurements and with three independent methods of calculating stratospheric BrO columns. Furthermore, we select analysis methods that do not depend on the absolute magnitude of column BrO, such as time-lagged correlation analysis of ozone and tropospheric column BrO, to understand characteristics of ODEs. Time-lagged correlation analysis between in situ (surface and ozonesonde) measurements of ozone and satellite derived tropospheric BrO columns indicates that the ODEs are due to either local halogen-driven ozone loss or short-range (∼1 day) transport from nearby regions with ozone depletion. The effect of in situ ozone loss is also evident in the diurnal variation difference between low (10th and 25th percentiles) and higher percentiles of surface ozone concentrations at Alert, Canada. Aircraft observations indicate low-ozone air mass transported from adjacent high-BrO regions. Correlation analyses of ozone with potential temperature and time-lagged tropospheric BrO column show that the vertical extent of local ozone loss is surprisingly deep (1–2 km) at Resolute and Churchill, Canada. The unstable boundary layer during ODEs at Churchill could potentially provide a source of free-tropospheric BrO through convective transport and explain the significant negative correlation between free-tropospheric ozone and tropospheric BrO column at this site

Gas emission strength and evolution of the molar ratio of BrO/SO2 in the plume of Nyiragongo in comparison to Etna

Airborne and ground-based differential optical absorption spectroscopy observations have been carried out at the volcano Nyiragongo (Democratic Republic of Congo) to measure SO2 and bromine monoxide (BrO) in the plume in March 2004 and June 2007, respectively. Additionally filter pack and multicomponent gas analyzer system (Multi-GAS) measurements were carried out in June 2007. Our measurements provide valuable information on the chemical composition of the volcanic plume emitted from the lava lake of Nyiragongo. The main interest of this study has been to investigate for the first time the bromine emission flux of Nyiragongo (a rift volcano) and the BrO formation in its volcanic plume. Measurement data and results from a numerical model of the evolution of BrO in Nyiragongo volcanic plume are compared with earlier studies of the volcanic plume of Etna (Italy). Even though the bromine flux from Nyiragongo (2.6t/d) is slightly greater than that from Etna (1.9t/d), the BrO/SO2 ratio (maximum 7x10(-5)) is smaller than in the plume of Etna (maximum 2.1x10(-4)). A one-dimensional photochemical model to investigate halogen chemistry in the volcanic plumes of Etna and Nyiragongo was initialized using data from Multi-GAS and filter pack measurements. Model runs showed that the differences in the composition of volcanic volatiles led to a smaller fraction of total bromine being present as BrO in the Nyiragongo plume and to a smaller BrO/SO2 ratio

Kinetics of the HO_2 + BrO reaction over the temperature range 233–348 K

The reaction BrO + HO_2 → products is the rate-limiting step in a key catalytic ozone destruction cycle in the lower stratosphere. In this study a discharge-flow reactor coupled with molecular beam mass spectrometry has been used to study the BrO + HO_2 reaction over the temperature range 233-348 K. Rate constants were measured under pseudo-first-order conditions in separate experiments with first HO_2 and then BrO in excess in an effort to identify possible complications in the reaction conditions. At 298 K, the rate constant was determined to be (1.73 ± 0.61) x 10^(-11) cm^3 molecule^(-1) s^(-1) with HO_2 in excess and (2.05 ± 0.64) x 10^(-11) cm^3 molecule^(-1) s^(-1) with BrO in excess. The combined results of the temperature-dependent experiments gave the following fit to the Arrhenius expression : k = (3.13 ± 0.33)]10^(-12) exp(536 ± 206/T) where the quoted uncertainties represent two standard deviations. The reaction mechanism is discussed in light of recent ab initio results on the thermochemistry of isomers of possible reaction intermediates

Symbol Error Rate Performance of Box-relaxation Decoders in Massive MIMO

The maximum-likelihood (ML) decoder for symbol detection in large multiple-input multiple-output wireless communication systems is typically computationally prohibitive. In this paper, we study a popular and practical alternative, namely the Box-relaxation optimization (BRO) decoder, which is a natural convex relaxation of the ML. For iid real Gaussian channels with additive Gaussian noise, we obtain exact asymptotic expressions for the symbol error rate (SER) of the BRO. The formulas are particularly simple, they yield useful insights, and they allow accurate comparisons to the matched-filter bound (MFB) and to the zero-forcing decoder. For BPSK signals the SER performance of the BRO is within 3dB of the MFB for square systems, and it approaches the MFB as the number of receive antennas grows large compared to the number of transmit antennas. Our analysis further characterizes the empirical density function of the solution of the BRO, and shows that error events for any fixed number of symbols are asymptotically independent. The fundamental tool behind the analysis is the convex Gaussian min-max theorem

In situ observations of BrO over Antarctica: ER-2 aircraft results from 54 S to 72 S latitude

Bromine monoxide was observed in situ at approximately 18 km altitude during nine flights of the NASA ER-2 aircraft from Punta Arenas, Chile (54 altitude) to 72 S latitude over the Palmer Peninsula, Antarctica. The first flight for the BrO detection system was on 28 August. Here, the results from the flights over Antarctica and from the ferry flights from Punta Arenas to Moffett Field, CA (37 N latitude are reported. A key question concerning BrO, then, is how it is distributed with respect to the chemical containment vessel defined by elevated ClO mixing ratios. This question is answered with greatest statistical significance if the data are averaged into five regions: outside the vessel, aircraft heading south; inside the vessel on the same potential temperature surface; in the dive region; inside the vessel on a given potential temperature surface, aircraft heading north; and outside the vessel on the same surface. The result is that the BrO distribution inside the chemical containment vessel was different from that found outside. Inside, the BrO mixing ratio was (5.0 plus or minus 1.1) pptv between the 400 K and 460 K potential temperature surfaces, decreasing only slightly with potential temperature, and was less than 3.6 pptv below the 4 00 K surface. The abundance of BrO inside the chemical containment vessel showed no discernible temporal trend during the course of the nine flights. Outside the vessel, the BrO mixing ratio was (4.7 plus or minus 1.3) pptv near the 450 K surface, but decreased to (2.8 plus or minus 1.0) pptv near the 420 K surface