A study of photochemical and physical processes affecting carbonyl compounds in the Arctic atmospheric boundary layer

Grannas, A. M.; Shepson, P. B.; Guimbaud, Christophe; Sumner, Ann Louise; Albert, M. R.; Simpson, W. R.; Dominé, Florent; Boudries, H.; Bottenheim, J. W.; Beine, H. J.; Honrath, R. E.; Zhou, Xianliang

doi:10.1016/s1352-2310(02)00134-6

Cited by 99 publications

(109 citation statements)

References 36 publications

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“…Thus, while some significant gas-phase production of HCHO and CH 3 CHO can occur if [Cl] is high , it is far more likely that in the Arctic, surface concentrations of these compounds are primarily derived from snowpack emissions (Grannas et al, 2007;Barret et al, 2011). The production of HCHO and CH 3 CHO from the snowpack has been documented in previous studies (Sumner and Shepson, 1999;Grannas et al, 2002) and strong vertical fluxes of both compounds were observed during OASIS (Barret et al, 2011;Gao et al, 2012).…”

Section: The Impact Of Chlorine Chemistry On Oxidative Capacitymentioning

confidence: 79%

Interactions of bromine, chlorine, and iodine photochemistry during ozone depletions in Barrow, Alaska

et al. 2015

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Abstract. The springtime depletion of tropospheric ozone in the Arctic is known to be caused by active halogen photochemistry resulting from halogen atom precursors emitted from snow, ice, or aerosol surfaces. The role of bromine in driving ozone depletion events (ODEs) has been generally accepted, but much less is known about the role of chlorine radicals in ozone depletion chemistry. While the potential impact of iodine in the High Arctic is more uncertain, there have been indications of active iodine chemistry through observed enhancements in filterable iodide, probable detection of tropospheric IO, and recently, observation of snowpack photochemical production of I 2 . Despite decades of research, significant uncertainty remains regarding the chemical mechanisms associated with the bromine-catalyzed depletion of ozone, as well as the complex interactions that occur in the polar boundary layer due to halogen chemistry. To investigate this, we developed a zero-dimensional photochemical model, constrained with measurements from the 2009 OA-SIS field campaign in Barrow, Alaska. We simulated a 7-day period during late March that included a full ozone depletion event lasting 3 days and subsequent ozone recovery to study the interactions of halogen radicals under these different conditions. In addition, the effects of iodine added to our Base Model were investigated. While bromine atoms were primarily responsible for ODEs, chlorine and iodine were found to enhance the depletion rates and iodine was found to be more efficient per atom at depleting ozone than Br. The interaction between chlorine and bromine is complex, as the presence of chlorine can increase the recycling and production of Br atoms, while also increasing reactive bromine sinks under certain conditions. Chlorine chemistry was also found to have significant impacts on both HO 2 and RO 2 , with organic compounds serving as the primary reaction partner for Cl atoms. The results of this work highlight the need for future studies on the production mechanisms of Br 2 and Cl 2 , as well as on the potential impact of iodine in the High Arctic.

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Section: The Impact Of Chlorine Chemistry On Oxidative Capacitymentioning

confidence: 79%

Interactions of bromine, chlorine, and iodine photochemistry during ozone depletions in Barrow, Alaska

et al. 2015

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“…A total of 9 of 17 weeks with detectable carbonyl groups occurred in spring when snowpack chemistry can be a significant source of gas-phase carbonyls (Grannas et al, 2002).…”

Section: Discussionmentioning

confidence: 99%

“…A total of 9 of the 17 weeks were during spring when gas-phase carbonyls (formaldehyde, acetaldehyde and acetone) can exhibit a diurnal cycle related to snowpack chemistry during periods of ozone depletion (Grannas et al, 2002). During these 9 weeks, the acid groups and alcohol groups were much lower fractions of the OM (2 and 11 %, respectively), and 6 of the weeks were during periods of depleted ozone (Fig.…”

Section: Chemical Component Correlationsmentioning

confidence: 99%

“…Fu et al (2013) quantified 5 % of the sampled OC, and found the largest organic compound class was primary saccharides from marine emissions followed by secondary organic groups likely formed from the oxidation of isoprene and terpenoids. The snow pack is another potential source of organic precursors (e.g., Grannas et al, 2002;Kos et al, 2014). Reported here are the first multi-year measurements of organic aerosol composition in combination with particle size distributions above 80 • N. A total of 126 weeklyaveraged observations of submicron-particle chemistry and particle microphysics made at the Dr. Neil Trivett Global Atmospheric Watch Observatory at Alert, Nunavut (82.5 • N, 62.5 • W; elevation 210 m a.m.s.l.…”

Section: Introductionmentioning

confidence: 99%

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Organic functional groups in the submicron aerosol at 82.5° N, 62.5° W from 2012 to 2014

et al. 2018

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Abstract. The first multi-year contributions from organic functional groups to the Arctic submicron aerosol are documented using 126 weekly-integrated samples collected from April 2012 to October 2014 at the Alert Observatory (82.45 • N, 62.51 • W). Results from the particle transport model FLEXPART, linear regressions among the organic and inorganic components and positive matrix factorization (PMF) enable associations of organic aerosol components with source types and regions. Lower organic mass (OM) concentrations but higher ratios of OM to non-sea-salt sulfate mass concentrations (nss-SO = 4 ) accompany smaller particles during the summer (JJA). Conversely, higher OM but lower OM / nss-SO = 4 accompany larger particles during winter-spring. OM ranges from 7 to 460 ng m −3 , and the study average is 129 ng m −3 . The monthly maximum in OM occurs during May, 1 month after the peak in nss-SO = 4 and 2 months after that of elemental carbon (EC). Winter (DJF), spring (MAM), summer and fall (SON) values of OM / nss-SO = 4 are 26, 28, 107 and 39 %, respectively, and overall about 40 % of the weekly variability in the OM is associated with nss-SO = 4 . Respective study-averaged concentrations of alkane, alcohol, acid, amine and carbonyl groups are 57, 24, 23, 15 and 11 ng m −3 , representing 42, 22, 18, 14 and 5 % of the OM, respectively. Carbonyl groups, detected mostly during spring, may have a connection with snow chemistry. The seasonally highest O / C occurs during winter (0.85) and the lowest O / C is during spring (0.51); increases in O / C are largely due to increases in alcohol groups. During winter, more than 50 % of the alcohol groups are associated with primary marine emissions, consistent with Shaw et al. (2010) and Frossard et al. (2011). A secondary marine connection, rather than a primary source, is suggested for the highest and most persistent O / C observed during the coolest and cleanest summer (2013), when alcohol and acid groups made up 63 % of the OM. A secondary marine source may be a general feature of the summer OM, but higher contributions from alkane groups to OM during the warmer summers of 2012 (53 %) and 2014 (50 %) were likely due to increased contributions from combustion sources. Evidence for significant contributions from biomass burning (BB) was present in 4 % of the weeks. During the dark months (NDJF), 29, 28 and 14 % of the nss-SO = 4 , EC and OM were associated with transport times over the gas flaring region of northern Russia and other parts of Eurasia. During spring, those percentages dropped to 11 % for each of nss-SO = 4 and EC values, respectively, and there is no association of OM.

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“…It has been suggested that recorded levels of OH are a product of photochemical transformations at the snow-air interface. Molecules and radicals such as HCHO, [22] NO x , [23] HONO, [24] hydrogen peroxide, [25] higher aldehydes, [26] and HO 2 radicals, [27] produced by other photochemical processes taking place in the snowpack, are considered as sources of OH formation Measured levels of these compounds were used in calculations by a steady-state photochemical box model. [27,28] For data obtained in 2000 at the South Pole, model predictions of OH were accurate only in a certain range of NO levels.…”

Section: Unknown Sources Of Oh Formationmentioning

confidence: 99%

Possible contribution of triboelectricity to snow - air interactions

Tkachenko¹,

Kozachkov²

2012

Environ. Chem.

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Environmental context. Polar near-surface snow can act as a chemical reactor that alters the composition and chemistry of snow and the overlying air. Although the mechanisms and driving forces of these reactions have long been debated, triboelectrification (production of electrostatic charges by friction) of snow by wind has not yet been considered as a factor. It is proposed that in polar regions, triboelectrification could significantly influence the composition and chemistry of snow.Abstract. Reactions that proceed in polar snow cover may significantly affect the chemistry of the overlying atmosphere, but mechanisms and driving forces of these reactions are still under discussion. The proposed hypothesis attempts to explain some experimental data that cannot be fully understood (e.g. the effect of wind on OH radicals, ozone and persistent organic pollutants levels) by taking into account the influence of electrical phenomena on the snow surface. We assumed that a combination of such factors as low humidity, high wind speed and low temperatures makes the influence of triboelectrification of snow significant for polar areas, where purity and the depth of snow cover prevent fast charge dissipation. The major points of the hypothesis are: (1) when the electric field reaches a value sufficient for the onset of corona discharge, various free radical processes are initiated resulting in changes in the concentrations of ozone, OH radical, nitrate, etc., and the decomposition of pollutant molecules; (2) the high electric field can stimulate transport of ions (such as bromide and nitrate) from the condensed phase to the gas phase; and (3) the ageing of charged snow can increase its electrical potential.

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A study of photochemical and physical processes affecting carbonyl compounds in the Arctic atmospheric boundary layer

Cited by 99 publications

References 36 publications

Interactions of bromine, chlorine, and iodine photochemistry during ozone depletions in Barrow, Alaska

Interactions of bromine, chlorine, and iodine photochemistry during ozone depletions in Barrow, Alaska

Organic functional groups in the submicron aerosol at 82.5° N, 62.5° W from 2012 to 2014

Possible contribution of triboelectricity to snow - air interactions

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A study of photochemical and physical processes affecting carbonyl compounds in the Arctic atmospheric boundary layer

Cited by 99 publications

References 36 publications

Interactions of bromine, chlorine, and iodine photochemistry during ozone depletions in Barrow, Alaska

Interactions of bromine, chlorine, and iodine photochemistry during ozone depletions in Barrow, Alaska

Organic functional groups in the submicron aerosol at 82.5° N, 62.5° W from 2012 to 2014

Possible contribution of triboelectricity to snow - air interactions

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Product

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Organic functional groups in the submicron aerosol at 82.5° N, 62.5° W from 2012 to 2014