skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: The Essential Role for Laboratory Studies in Atmospheric Chemistry

Abstract

Laboratory studies of atmospheric chemistry characterize the nature of atmospherically relevant processes down to the molecular level, providing fundamental information used to assess how human activities drive environmental phenomena such as climate change, urban air pollution, ecosystem health, indoor air quality, and stratospheric ozone depletion. Laboratory studies have a central role in addressing the incomplete fundamental knowledge of atmospheric chemistry. This paper highlights the evolving science needs for this community and emphasizes how our knowledge is far from complete, hindering our ability to predict the future state of our atmosphere and to respond to emerging global environmental change issues. Finally, laboratory studies provide rich opportunities to expand our understanding of the atmosphere via collaborative research with the modeling and field measurement communities, and with neighboring disciplines.

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [1];  [4]; ORCiD logo [5];  [6];  [7]; ORCiD logo [8];  [9];  [10];  [11]; ORCiD logo [12];  [13];  [14];  [15];  [16];  [17];  [18]; ORCiD logo [8] more »;  [19];  [20];  [21];  [22];  [13];  [23];  [24];  [25];  [26];  [19];  [27];  [28];  [29];  [4] « less
  1. National Oceanic and Atmospheric Administration (NOAA), Boulder, CO (United States)
  2. Univ. of Toronto, ON (Canada)
  3. Univ. of Wuppertal (Germany)
  4. Univ. of Colorado, Boulder, CO (United States)
  5. Paul Scherrer Inst. (PSI), Villigen (Switzerland)
  6. Univ. of British Columbia, Vancouver, BC (Canada)
  7. Univ. of California, Davis, CA (United States)
  8. Univ. of California, Irvine, CA (United States)
  9. Univ. of York (United Kingdom)
  10. Max Planck Inst. of Chemistry, Mainz (Germany)
  11. Technion-Israel Inst. of Tech., Haifa (Israel)
  12. Univ. of Lyon (France)
  13. Univ. of Leeds (United Kingdom)
  14. Leibniz Inst. for Tropospheric Research (ITR), Leipzig (Germany)
  15. Harvard Univ., Cambridge, MA (United States)
  16. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  17. Columbia Univ., New York, NY (United States)
  18. Georgia Inst. of Technology, Atlanta, GA (United States)
  19. National Center for Atmospheric Research, Boulder, CO (United States)
  20. Univ. of Manchester (United Kingdom)
  21. Inst. Pierre-Simon Laplace, Creteil (France)
  22. Weizmann Inst. of Science, Rehovot (Israel)
  23. Univ. of North Carolina, Chapel Hill, NC (United States)
  24. National Inst. for Environmental Studies, Tsukuba (Japan)
  25. Univ. of Washington, Seattle, WA (United States)
  26. Peking Univ., Beijing (China)
  27. Forschungszentrum Julich (Germany)
  28. Rutgers Univ., Piscataway, NJ (United States)
  29. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1393134
DOE Contract Number:
AC02-05CH11231
Resource Type:
Journal Article
Resource Relation:
Journal Name: Environmental Science and Technology; Journal Volume: 51; Journal Issue: 5
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES

Citation Formats

Burkholder, James B., Abbatt, Jonathan P. D., Barnes, Ian, Roberts, James M., Melamed, Megan L., Ammann, Markus, Bertram, Allan K., Cappa, Christopher D., Carlton, Annmarie G., Carpenter, Lucy J., Crowley, John N., Dubowski, Yael, George, Christian, Heard, Dwayne E., Herrmann, Hartmut, Keutsch, Frank N., Kroll, Jesse H., McNeill, V. Faye, Ng, Nga Lee, Nizkorodov, Sergey A., Orlando, John J., Percival, Carl J., Picquet-Varrault, Bénédicte, Rudich, Yinon, Seakins, Paul W., Surratt, Jason D., Tanimoto, Hiroshi, Thornton, Joel A., Tong, Zhu, Tyndall, Geoffrey S., Wahner, Andreas, Weschler, Charles J., Wilson, Kevin R., and Ziemann, Paul J. The Essential Role for Laboratory Studies in Atmospheric Chemistry. United States: N. p., 2017. Web. doi:10.1021/acs.est.6b04947.
Burkholder, James B., Abbatt, Jonathan P. D., Barnes, Ian, Roberts, James M., Melamed, Megan L., Ammann, Markus, Bertram, Allan K., Cappa, Christopher D., Carlton, Annmarie G., Carpenter, Lucy J., Crowley, John N., Dubowski, Yael, George, Christian, Heard, Dwayne E., Herrmann, Hartmut, Keutsch, Frank N., Kroll, Jesse H., McNeill, V. Faye, Ng, Nga Lee, Nizkorodov, Sergey A., Orlando, John J., Percival, Carl J., Picquet-Varrault, Bénédicte, Rudich, Yinon, Seakins, Paul W., Surratt, Jason D., Tanimoto, Hiroshi, Thornton, Joel A., Tong, Zhu, Tyndall, Geoffrey S., Wahner, Andreas, Weschler, Charles J., Wilson, Kevin R., & Ziemann, Paul J. The Essential Role for Laboratory Studies in Atmospheric Chemistry. United States. doi:10.1021/acs.est.6b04947.
Burkholder, James B., Abbatt, Jonathan P. D., Barnes, Ian, Roberts, James M., Melamed, Megan L., Ammann, Markus, Bertram, Allan K., Cappa, Christopher D., Carlton, Annmarie G., Carpenter, Lucy J., Crowley, John N., Dubowski, Yael, George, Christian, Heard, Dwayne E., Herrmann, Hartmut, Keutsch, Frank N., Kroll, Jesse H., McNeill, V. Faye, Ng, Nga Lee, Nizkorodov, Sergey A., Orlando, John J., Percival, Carl J., Picquet-Varrault, Bénédicte, Rudich, Yinon, Seakins, Paul W., Surratt, Jason D., Tanimoto, Hiroshi, Thornton, Joel A., Tong, Zhu, Tyndall, Geoffrey S., Wahner, Andreas, Weschler, Charles J., Wilson, Kevin R., and Ziemann, Paul J. Tue . "The Essential Role for Laboratory Studies in Atmospheric Chemistry". United States. doi:10.1021/acs.est.6b04947.
@article{osti_1393134,
title = {The Essential Role for Laboratory Studies in Atmospheric Chemistry},
author = {Burkholder, James B. and Abbatt, Jonathan P. D. and Barnes, Ian and Roberts, James M. and Melamed, Megan L. and Ammann, Markus and Bertram, Allan K. and Cappa, Christopher D. and Carlton, Annmarie G. and Carpenter, Lucy J. and Crowley, John N. and Dubowski, Yael and George, Christian and Heard, Dwayne E. and Herrmann, Hartmut and Keutsch, Frank N. and Kroll, Jesse H. and McNeill, V. Faye and Ng, Nga Lee and Nizkorodov, Sergey A. and Orlando, John J. and Percival, Carl J. and Picquet-Varrault, Bénédicte and Rudich, Yinon and Seakins, Paul W. and Surratt, Jason D. and Tanimoto, Hiroshi and Thornton, Joel A. and Tong, Zhu and Tyndall, Geoffrey S. and Wahner, Andreas and Weschler, Charles J. and Wilson, Kevin R. and Ziemann, Paul J.},
abstractNote = {Laboratory studies of atmospheric chemistry characterize the nature of atmospherically relevant processes down to the molecular level, providing fundamental information used to assess how human activities drive environmental phenomena such as climate change, urban air pollution, ecosystem health, indoor air quality, and stratospheric ozone depletion. Laboratory studies have a central role in addressing the incomplete fundamental knowledge of atmospheric chemistry. This paper highlights the evolving science needs for this community and emphasizes how our knowledge is far from complete, hindering our ability to predict the future state of our atmosphere and to respond to emerging global environmental change issues. Finally, laboratory studies provide rich opportunities to expand our understanding of the atmosphere via collaborative research with the modeling and field measurement communities, and with neighboring disciplines.},
doi = {10.1021/acs.est.6b04947},
journal = {Environmental Science and Technology},
number = 5,
volume = 51,
place = {United States},
year = {Tue Feb 07 00:00:00 EST 2017},
month = {Tue Feb 07 00:00:00 EST 2017}
}
  • A pulse radiolysis technique was used to measure the UV absorption spectra of (CH{sub 3}O){sub 2}CHOCH{sub 2}({center_dot}) [A] and (CH{sub 3}O){sub 2}CHOCH{sub 2}O{sub 2}({center_dot}) [B] radicals derived from trimethoxymethane over the range 220--320 nm. The self-reaction rate constants for these radicals were k{sub 5} = (3.5 {+-} 0.5) {times} 10{sup {minus}11} and k{sub 6 obs} = (1.3 {+-} 0.2) {times} 10{sup {minus}11} cm{sup 3}/molecule s. Rate constants for reactions of B radicals with NO and NO{sub 2} were k{sub 7} = (9.0 {+-} 1.2) {times} 10{sup {minus}12} and k{sub 8} = (1.0 {+-} 0.2) {times} 10{sup {minus}11} cm{sup 3}/molecule s,more » respectively. Rate constants for the reaction of OH radicals and F atoms with trimethoxymethane and the reaction of A radicals with O{sub 2} were k{sub 1} = (6.0 {+-} 0.5) {times} 10{sup {minus}12}, k{sub 3} = (3.0 {+-} 0.7) {times} 10{sup {minus}10}, and k{sub 2} = (9.2 {+-} 1.5) {times} 10{sup {minus}12} cm{sup 3}/molecule s, respectively. Relative rate techniques were used to measure k(Cl + trimethoxymethane) = (1.5 {+-} 0.2) {times} 10{sup {minus}10} cm{sup 3}/molecule s. OH-radical-initiated oxidation of trimethoxymethane in air gives dimethyl carbonate in a molar yield of 81 {+-} 10%. These results are discussed with respect to the atmospheric chemistry of automotive fuel additives.« less
  • Atmospheric aerosols play important roles in climate and atmospheric chemistry: They scatter sunlight, provide condensation nuclei for cloud droplets, and participate in heterogeneous chemical reactions. Two important aerosol species, sulfate and organic particles, have large natural biogenic sources that depend in a highly complex fashion on environmental and ecological parameters and therefore are prone to influence by global change. Reactions in and on sea-salt aerosol particles may have a strong influence on oxidation processes in the marine boundary layer through the production of halogen radicals, and reactions on mineral aerosols may significantly affect the cycles of nitrogen, sulfur, and atmosphericmore » oxidants. 85 refs., 3 figs.« less
  • Titan’s thermospheric photochemistry is primarily driven by solar radiation. Similarly to other planetary atmospheres, such as Mars’, Titan’s atmospheric structure is also directly affected by variations in the solar extreme-UV/UV output in response to the 11-year-long solar cycle. Here, we investigate the influence of nitrogen on the vertical production, loss, and abundance profiles of hydrocarbons as a function of the solar cycle. Our results show that changes in the atmospheric nitrogen atomic density (primarily in its ground state N({sup 4}S)) as a result of photon flux variations have important implications for the production of several minor hydrocarbons. The solar minimummore » enhancement of CH{sub 3}, C{sub 2}H{sub 6}, and C{sub 3}H{sub 8}, despite the lower CH{sub 4} photodissociation rates compared with solar maximum conditions, is explained by the role of N({sup 4}S). N({sup 4}S) indirectly controls the altitude of termolecular versus bimolecular chemical regimes through its relationship with CH{sub 3}. When in higher abundance during solar maximum at lower altitudes, N({sup 4}S) increases the importance of bimolecular CH{sub 3} + N({sup 4}S) reactions producing HCN and H{sub 2}CN. The subsequent remarkable CH{sub 3} loss and decrease in the CH{sub 3} abundance at lower altitudes during solar maximum affects the overall hydrocarbon chemistry.« less
  • [1] Individual calcium carbonate particles reacted with gas- phase nitric acid at 293 K have been followed using Scanning Electron Microscopy (SEM) and Energy Dispersive X-Ray (EDX) analysis as a function of time and relative humidity (RH). The rate of calcium carbonate to calcium nitrate conversion is significantly enhanced in the presence of water vapor. The SEM images clearly show that solid CaCO3 particles are converted to spherical droplets as the reaction proceeds. The process occurs through a two-step mechanism involving the conversion of calcium carbonate into calcium nitrate followed by the deliquescence of the calcium nitrate product. The changemore » in phase of the particles and the significant reactivity of nitric acid and CaCO3 at low RH are a direct result of the deliquescence of the product at low RH. This is the first laboratory study to show the phase transformation of solid particles into liquid droplets through heterogeneous chemistry.« less
  • The authors report on a laboratory study of the atmospheric corrosion of zinc in air containing different concentrations of carbon dioxide (CO{sub 2}) (< 1,350, 1,000, and 40,000 ppm CO{sub 2}). The samples were exposed to synthetic atmospheres with careful control of CO{sub 2} concentration, sulfur dioxide (SO{sub 2}) concentration, relative humidity, and flow conditions. The relative humidity was 95%. Mass gain and metal loss results are reported. The corrosion products were analyzed quantitatively and qualitatively by a combination of grazing-angle x-ray diffraction, scanning electron microscopy, gravimetry, and quantitative analysis for carbonate. The corrosion rate of zinc increased with increasingmore » CO{sub 2} concentration. In the presence of carbon dioxide Zn{sub 4}CO{sub 3}(OH){sub 6} {center_dot} H{sub 2}O formed. Hydrozincite, Zn{sub 5}(CO{sub 3}){sub 2}(OH){sub 6} was only identified after exposure to high CO{sub 2} concentration. Zinc hydroxycarbonate was converted into hydroxysulfate exposed to air containing 225 ppb SO{sub 2}. Zn{sub 4}SO{sub 4}(OH){sub 6} {center_dot} 4H{sub 2}O was produced in all exposures including SO{sub 2}. The zinc hydroxycarbonate surface film formed in the presence of CO{sub 2} was not protective in humid SO{sub 2} polluted air.« less