Elsevier

Atmospheric Environment

Volume 36, Issues 15–16, May–June 2002, Pages 2553-2562
Atmospheric Environment

Atmospheric chemistry of formaldehyde in the Arctic troposphere at Polar Sunrise, and the influence of the snowpack

https://doi.org/10.1016/S1352-2310(02)00105-XGet rights and content

Abstract

The role of formaldehyde in the atmospheric chemistry of the Arctic marine boundary layer has been studied during both polar day and night at Alert, Nunavut, Canada. Formaldehyde concentrations were determined during two separate field campaigns (PSE 1998 and ALERT2000) from polar night to the light period. The large differences in the predominant chemistry and transport issues in the dark and light periods are examined here. Formaldehyde concentrations during the dark period were found to be dependent on the transport of air masses to the Alert site. Three regimes were identified during the dark period, including background (free-tropospheric) air, transported polluted air from Eurasia, and halogen-processed air transported across the dark Arctic Ocean. In the light period, background formaldehyde levels were compared to a calculation of the steady-state formaldehyde concentrations under background and low-ozone conditions. We found that, for sunlit conditions, the ambient formaldehyde concentrations cannot be reproduced by known gas-phase chemistry. We suggest that snowpack photochemistry contributes to production and emission of formaldehyde in the light period, which could account for the high concentrations observed at Alert.

Introduction

Over the past few years, interest in the photochemistry of the boundary layer in Polar Regions has increased substantially. This stems from continued developments in our understanding of ozone destruction at the time of polar sunrise in the marine boundary layer (Barrie et al., 1988; Impey et al., 1999; Wennberg, 1999; Foster et al., 2001). Among the important issues is the nature of the formaldehyde (HCHO) sources and sinks, since HCHO is an important source of free radicals in the relatively dry Arctic troposphere, and because it can be an important sink for free radicals such as Br atoms that play a role in Arctic boundary-layer ozone depletion (Shepson et al., 1996; Sumner and Shepson, 1999; Michalowski et al., 2000). Sumner and Shepson (1999) found that HCHO is emitted from the snowpack after polar sunrise, and that this source was likely important to the boundary layer. Although the data were somewhat ambiguous, the authors hypothesized that the HCHO source in the snowpack was photochemical in nature. Hutterli et al. (1999) found that HCHO emission from surface snow at Summit Greenland was an important source of HCHO for the Summit boundary layer, with estimated fluxes ranging from ∼1–10×108 molecules/cm2/s. These investigators discussed evidence that HCHO emission resulted from a temperature-dependent desorption from snow that was enriched relative to equilibrium values. During the Polar Sunrise Experiment 1998 (PSE98) and ALERT2000, we conducted measurements of gas phase HCHO concentrations from the dark through the light period, in conjunction with a variety of supporting chemical and meteorological measurements, which provided an opportunity to investigate the sources and sinks of HCHO in this environment in better detail. Additional experiments were conducted during ALERT2000 in which HCHO was measured in the snowpack interstitial air and in the snowpack condensed phase to examine the role of the snowpack in generating and emitting HCHO into the boundary layer. In this paper we discuss the results of these measurements, and their impact on our understanding of formaldehyde in the Arctic marine boundary layer (MBL).

Section snippets

Methods

Gas phase HCHO determinations were conducted from 15 February to 26 April, 1998, and from 17 February to 5 May, 2000, at the Special Studies Laboratory (SSL) at the Canadian Forces Station at Alert, Nunavut, Canada (82.5°N, 62.3°W). The SSL is located 6 km southwest of the base camp, on a plateau that is 145 m above sea level. During both PSE98 and ALERT2000, HCHO gas phase concentrations were determined using a modified version of the fluorometric method described by Fan and Dasgupta (1994).

Results and discussion

The gas phase HCHO concentrations determined for the full experiment period during ALERT2000 are shown in Fig. 1. The gas-phase concentrations ranged from 100–370 ppt during the dark period, and from ∼35–360 ppt after full sunrise. This is consistent with the observations for PSE98 discussed in Sumner and Shepson (1999). The formaldehyde data are segregated according to the corresponding ozone concentrations. We have identified three conditions that are represented: background conditions in which

Conclusions

This study has shown that, in the dark period, ambient HCHO concentrations are influenced by long-range transport. We observed cases of the transport of polluted air to the measurement site and also air that may have been influenced by photochemistry at lower latitudes. We also find that the gas-phase HCHO concentrations observed during the sunlit period cannot be fully accounted for on the basis of known gas phase chemistry. Our measurements in the snowpack and snowpack interstitial air

Acknowledgements

We thank A. Gallant, J. Deary, the Meteorological Service of Canada, and all the personnel of CFS Alert for technical and logistic support. We gratefully acknowledge the National Science Foundation Office of Polar Programs and Atmospheric Chemistry program (OPP-9818257) for financial support of this work.

References (36)

  • Beine, H., Honrath, R., Dominé, F., Simpson, W.R., Fuentes, J., 2002. NOx during background and ozone depletion periods...
  • H. Boudries et al.

    Cl and Br atom concentrations during a surface boundary layer ozone depletion event in the Canadian High Arctic

    Geophysical Research Letters

    (2000)
  • Boudries, H., Bottenheim, J.W., Guimbaud, C., Grannas, A., Shepson, P.B., Houdier, S., Perrier, S., Dominé, F., 2002....
  • T.L. Couch et al.

    An Investigation of the interaction of carbonyl compounds with the snowpack

    Geophysical Research Letters

    (2000)
  • C. deServes

    Gas-phase formaldehyde and peroxide measurements in the arctic atmosphere

    Journal of Geophysical Research

    (1994)
  • Q. Fan et al.

    Continuous automated determination of atmospheric formaldehyde at the parts per trillion level

    Analytical Chemistry

    (1994)
  • K. Foster et al.

    The Role of Br2 and BrCl in surface Ozone destruction at Polar Sunrise

    Science

    (2001)
  • G.W. Harris et al.

    Measurements of formaldehyde in the troposphere by tunable diode laser absorption spectroscopy

    Journal of Atmospheric Chemistry

    (1989)
  • Cited by (82)

    • The interaction between bacterial abundance and selected pollutants concentration levels in an arctic catchment (southwest Spitsbergen, Svalbard)

      2018, Science of the Total Environment
      Citation Excerpt :

      They should not be considered less harmful than polycyclic aromatic hydrocarbons or polychlorinated biphenyls. Besides anthropogenic sources, formaldehyde can be also emitted from the snowpack after polar sunrise (Sumner et al., 2002). The low annual average temperatures of the polar regions slow down the microbiological degradation of organic compounds to a minimum.

    • High-resolution FTIR analysis of the anharmonic resonance between the v<inf>2</inf> = 1 and v<inf>3</inf> = 1 states of formaldehyde-<sup>13</sup>C (H<inf>2</inf><sup>13</sup>CO)

      2017, Journal of Molecular Spectroscopy
      Citation Excerpt :

      The importance of formaldehyde (H212CO) in atmospheric chemistry has been widely reported [1–11].

    • Spectrophotometric evaluation of the photocatalytic degradation of formaldehyde by Fe<inf>2</inf>O<inf>3</inf>-TiO<inf>2</inf> nano hybrid

      2014, Journal of Industrial and Engineering Chemistry
      Citation Excerpt :

      Considering the noticeable consumption of formaldehyde in different aspects of chemical industry, e.g. urea–formaldehyde resins, wood products, soil fertilizers, and also as a stabilizers and also, retentive and antiseptic reagent and according to the toxicity of formaldehyde, it is known as a carcinogenic agent, which is one of the main components of troposphere layer [1–3].

    • Development of an extended chemical mechanism for global- through-urban applications

      2012, Atmospheric Pollution Research
      Citation Excerpt :

      Marine ARCTIC scenario. Typical initial mixing ratios (see Table 6) of NOx (NO + NO2), NOz (NOx oxidation products), O3, H2O2, and volatile organic compounds (VOCs) such as alkenes, formaldehyde and acetaldehyde are specified under the Arctic scenario based on Arctic field study measurements (e.g., Li, 1994; Bottenheim et al., 2002a, 2002b; Sumner et al., 2002; Boudries et al., 2002). The simulations are performed both with and without heterogeneous chemistry on Arctic aerosols.

    • Sensitive determination of glyoxal, methylglyoxal and hydroxyacetaldehyde in environmental water samples by using dansylacetamidooxyamine derivatization and liquid chromatography/fluorescence

      2011, Analytica Chimica Acta
      Citation Excerpt :

      Like many other substances, carbonyls can also be incorporated in snow [9]. As already shown for FA [10,11], acetaldehyde (CH3CHO, AA) [12–14] or acetone (CH3COCH3, AC) [13,15], the behavior of carbonyls in snow is rather complex, involving physical exchanges with the atmosphere or photochemical production within the snowpack from organic precursors. Carbonyls can also absorb photons and generate radicals which can in turn react with other substances, including organic compounds [16].

    View all citing articles on Scopus
    View full text