The role of bromine and chlorine chemistry for arctic ozone depletion events in Ny-Ålesund and comparison with model calculations

Martínez, Mònica; Arnold, Tim; Perner, D.

doi:10.1007/s00585-999-0941-4

Cited by 73 publications

(38 citation statements)

References 65 publications

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“…HOBr is often comparable to or larger than BrO during the daytime measurements reported here, assuming that the measured active bromine is only HOBr. The predominance of HOBr over Br 2 is consistent with previous measurements (Impey et al, 1999), and HOBr has been predicted to be more abundant than BrO in ozone depleted air (Martinez et al, 1999). However, the BrO mixing ratios measured here (typically a few pptv in ozone-depleted air) from three different aircraft CIMS instruments were much lower than the tens of pptv that has been observed previously from ground-based instruments.…”

Section: Bromine Chemistrysupporting

confidence: 91%

“…Previous observations of BrO and total bromine in ozone-depleted air show that BrO accounts for a widely varying fraction of total bromine (Martinez et al, 1999;Hausmann and Platt, 1994). But speciated measurements of inorganic bromine other than BrO are sparse Impey et al, 1999;Foster et al, 2001), and the relative contribution of each bromine compound to total bromine is not certain.…”

Section: Bromine Chemistrymentioning

confidence: 98%

“…The relationship between active bromine and photolysis rates is examined to assess the relative contribution of Br 2 and HOBr to active bromine. Br 2 and BrO photolysis rates calculated from actinic flux measurements varied from 0.02/s to 0.06/s, while HOBr photolysis rates were approximately 30 times slower (e.g., Lehrer et al, 2004;Martinez et al, 1999). Models show that rapid Br 2 photolysis should restrict daytime Br 2 to the bottom few cm of the atmosphere (Lehrer et al, 2004).…”

Section: Bromine Distributions and Speciationmentioning

confidence: 98%

“…However, the observed increase in active bromine indicates the presence of bromine chemistry in the sampled ozone-depleted air masses, where both BrO and HOBr are predicted to be enhanced (e.g. Martinez et al, 1999;Evans et al, 2003;Calvert and Lindberg, 2003;Lehrer et al, 2004).…”

Section: Bromine Chemistrymentioning

confidence: 99%

“…Although several bromine-containing compounds are expected to be elevated in air masses where bromine-induced ozone destruction is important, measurement capabilities for low levels of inorganic bromine-containing molecules are limited primarily to BrO (Read et al, 2008;Platt and Honninger, 2003). In particular, HBr, BrO, HOBr, Br 2 , and Br are predicted to be elevated at some point during ozone depletion, and their abundance indicates the temporal evolution of the ozone depletion chemistry (Lehrer et al, 2004;Calvert and Lindberg, 2003;Martinez et al, 1999;Sander and Crutzen, 1996;Evans et al, 2003;Fan and Jacob, 1992). Extending the limited geographical range of bromine observations and number of measured bromine compounds will provide experimental evidence for the effect of reactive halogens upon global lower tropospheric ozone abundance.…”

Section: Introductionmentioning

confidence: 99%

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Bromine measurements in ozone depleted air over the Arctic Ocean

et al. 2010

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Abstract. In situ measurements of ozone, photochemically active bromine compounds, and other trace gases over the Arctic Ocean in April 2008 are used to examine the chemistry and geographical extent of ozone depletion in the arctic marine boundary layer (MBL). Data were obtained from the NOAA WP-3D aircraft during the Aerosol, Radiation, and Cloud Processes affecting Arctic Climate (ARCPAC) study and the NASA DC-8 aircraft during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) study. Fast (1 s) and sensitive (detection limits at the low pptv level) measurements of BrCl and BrO were obtained from three different chemical ionization mass spectrometer (CIMS) instruments, and soluble bromide was measured with a mist chamber. The CIMS instruments also detected Br 2 . Subsequent laboratory studies showed that HOBr rapidly converts to Br 2 on the Teflon instrument inlets. This detected Br 2 is identified as active bromine and represents a lower limit of the sum HOBr + Br 2 . The measured active bromine is shown to likely be HOBr during daytime flights in the arctic. In the MBL over the Arctic Ocean, soluble bromide and active bromine were consistently elevated and ozone was depleted. Ozone depletion and active bromine enhancement were confined to the MBL that was capped by a temperature inversion at 200-500 m altitude. In ozonedepleted air, BrO rarely exceeded 10 pptv and was always substantially lower than soluble bromide that was as high as 40 pptv. BrCl was rarely enhanced above the 2 pptv detection limit, either in the MBL, over Alaska, or in the arctic free troposphere.

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Section: Bromine Chemistrysupporting

confidence: 91%

Section: Bromine Chemistrymentioning

confidence: 98%

Section: Bromine Distributions and Speciationmentioning

confidence: 98%

Section: Bromine Chemistrymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Bromine measurements in ozone depleted air over the Arctic Ocean

et al. 2010

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Observations of gas phase hydrochloric acid in the polluted marine boundary layer

et al. 2014

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Ship-based measurements of gas phase hydrochloric acid (HCl), particulate chloride (pCl À ), and reactive nitrogen oxides (NO y ) were made in the polluted marine boundary layer along the California coastline during spring 2010. These observations are used to assess both the rate of Cl atom production from HCl and the role of direct HCl emissions and subsequent partitioning as a source for pCl À . Observations of HCl made in coastal Southern California are broadly correlated with NO z (NO z ≡ NO y -NO x ), peaking at 11 A.M. The observed median HCl mixing ratio in Southern California is 1.3 ppb (interquartile range: 0.53-2.7 ppb), as compared to 0.19 ppb (interquartile range: 0.10-0.38 ppb) measured along the Sacramento River between San Francisco and Sacramento. Concurrent measurements of aerosol ion chemistry indicate that aerosol particles sampled in Northern California are heavily depleted in Cl À , corresponding to a mean pCl À deficit of 0.05 ± 0.03 (1σ) ppb for sub-10 μm aerosol particles. In comparison, aerosols measured in Southern California indicate that over 25% of particles showed an addition of Cl À to the particle population. Observations presented here suggest that primary sources of HCl, or gas phase chlorine precursors to HCl, are likely underestimated in the California Air Resource Board emissions inventory. These results highlight the need for future field observations designed to better constrain direct reactive halogen emissions.

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Molecular Halogens Above the Arctic Snowpack: Emissions, Diurnal Variations, and Recycling Mechanisms

Wang

Pratt

2017

JGR Atmospheres

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Elevated levels of reactive bromine and chlorine species in the springtime Arctic boundary layer contribute to ozone depletion and mercury oxidation, as well as reactions with volatile organic compounds. Recent laboratory and field studies have revealed that snowpack photochemistry leads to Br2 and Cl2 production, the mechanisms of which remain poorly understood. In this work, we use a photochemical box model, with a simplified snow module, to examine the halogen chemistry occurring during the March 2012 Bromine, Ozone, and Mercury Experiment (BROMEX) near Utqiaġvik (Barrow), Alaska. Elevated daytime Br2 levels (e.g., 6–30 parts per trillion (ppt) at around local noon) reported in previous studies and in this work may be explained by Br + BrNO2/BrONO2 reactions under conditions of depleted O3 (<~10 ppb) and background NO2 (10–100 ppt). Even at low background NOx levels at Utqiaġvik, ClONO2 is predicted to be important in the production of Cl2 via multiphase reaction with Cl−. In the late afternoon, photolysis alone cannot explain the rapid decrease of Cl2 observed in the Arctic boundary layer. Heterogeneous reactions of Cl2 on aerosol particles and surface snowpack are suggested to play a key role in atmospheric Cl2 removal and possible BrCl production. Given the importance of the snowpack in the multiphase chemistry of the Arctic boundary layer, future measurements should focus on vertically resolved measurements of NOx and reactive halogens, as well as simultaneous particulate and snow halide measurements, to further evaluate and isolate the halogen production and vertical propagation mechanisms through one‐dimensional modeling.

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The role of bromine and chlorine chemistry for arctic ozone depletion events in Ny-Ålesund and comparison with model calculations

Cited by 73 publications

References 65 publications

Bromine measurements in ozone depleted air over the Arctic Ocean

Bromine measurements in ozone depleted air over the Arctic Ocean

Observations of gas phase hydrochloric acid in the polluted marine boundary layer

Molecular Halogens Above the Arctic Snowpack: Emissions, Diurnal Variations, and Recycling Mechanisms

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