Uncertainties in isoprene photochemistry and emissions: Implications for the oxidative capacity of past and present atmospheres and for climate forcing agents

Atmospheric Chemistry and Physics

Volumn 15, Issue 14, 2015, Pages 7977-7998

  Achakulwisut, P ^a   Mickley, L J ^b   Murray, L T ^c,d   Tai, A P K ^e   Kaplan, J O ^f   Alexander, B ^g  

^a HARVARD UNIVERSITY   (United States)

^b HARVARD UNIVERSITY   (United States)

^c NASA GODDARD INSTITUTE FOR SPACE STUDIES   (United States)

^d International Research Institute for Climate and Society   (United States)

^e CHINESE UNIVERSITY OF HONG KONG   (Hong Kong)

^f EPFL   (Switzerland)

^g UNIVERSITY OF WASHINGTON   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CLIMATE FORCING; EMISSION; ISOPRENE; LAST GLACIAL MAXIMUM; OZONE; PHOTOCHEMISTRY; RADIATIVE FORCING; TROPOSPHERE; UNCERTAINTY ANALYSIS;

EID: 84937708488     PISSN: 16807316     EISSN: 16807324     Source Type: Journal    
DOI: 10.5194/acp-15-7977-2015     Document Type: Article

References (107)

1. Alexander, B. and Mickley, L. J.: Paleo-perspectives on potential future changes in the oxidative capacity of the atmosphere due to climate change and anthropogenic emissions, Current Pollution Reports, doi:10.1007/s40726-015-0006-0, online first, 2015.
2. Alexander, B., Savarino, J., Barkov, N. I., Delmas, R. J., and Thiemens, M. H.: Climate driven changes in the oxidation pathways of atmospheric sulfur, Geophys. Res. Lett., 29, 30-1-30-4, doi:10.1029/2002GL014879, 2002.
3. Alexander, B., Savarino, J., Kreutz, K. J., and Thiemens, M. H.: Impact of preindustrial biomass-burning emissions on the oxidation pathways of tropospheric sulfur and nitrogen, J. Geophys. Res., 109, D08303, doi:10.1029/2003JD004218, 2004.
4. Bartlein, P. J., Harrison, S. P., Brewer, S., Connor, S., Davis, B. A. S., Gajewski, K., Guiot, J., Harrison-Prentice, T. I., Henderson, A., Peyron, O., Prentice, I. C., Scholze, M., Seppa, H., Shuman, B., Sugita, S., Thompson, R. S., Viau, A. E., Williams, J., and Wu, H.: Pollenbased continental climate reconstructions at 6 and 21 ka: a global synthesis, Clim. Dynam., 37, 775-802, 2011.
5. Beerling, D. J., Nicholas Hewitt, C., Pyle, J. A., and Raven, J. A.: Critical issues in trace gas biogeochemistry and global change, Philos. T. R. Soc. A, 365, 1629-1642, doi:10.1098/rsta.2007.2037, 2007.
6. Bey, I., Jacob, D. J., Yantosca, R. M., Logan, J. A., Field, B. D., Fiore, A. M., and Schultz, M. G.: Global modeling of tropospheric chemistry with assimilated meteorology: Model description and evaluation, J. Geophys. Res., 106, 23073, doi:10.1029/2001JD000807, 2001.
7. Bousquet, P., Hauglustaine, D. A., Peylin, P., Carouge, C., and Ciais, P.: Two decades of OH variability as inferred by an inversion of atmospheric transport and chemistry of methyl chloroform, Atmos. Chem. Phys., 5, 2635-2656, doi:10.5194/acp-5-2635-2005, 2005.
8. Braconnot, P., Harrison, S. P., Kageyama, M., Bartlein, P. J., Masson-Delmotte, V., Abe-Ouchi, A., Otto-Bliesner, B., and Zhao, Y.: Evaluation of climate models using palaeoclimatic data, Nature Climate Change, 2, 417-424, 2012.
9. Brook, E. J., Harder, S., Severinghaus, J., Steig, E. J., and Sucher, C. M.: On the origin and timing of rapid changes in atmospheric methane during the last glacial period, Global Biogeochem. Cy., 14, 559-572, 2000.
10. Carslaw, K. S., Lee, L. A., Reddington, C. L., Pringle, K. J., Rap, A., Forster, P. M., Mann, G. W., Spracklen, D. V, Woodhouse, M. T., Regayre, L. A., and Pierce, J. R.: Large contribution of natural aerosols to uncertainty in indirect forcing, Nature, 503, 67-71, doi:10.1038/nature12674, 2013.
11. CLIMAP Project Members: The Surface of the Ice-Age Earth, Science, 191, 1131-1137, 1976.
12. de Reus, M., Fischer, H., Sander, R., Gros, V., Kormann, R., Salisbury, G., Van Dingenen, R., Williams, J., Zöllner, M., and Lelieveld, J.: Observations and model calculations of trace gas scavenging in a dense Saharan dust plume during MINATROC, Atmos. Chem. Phys., 5, 1787-1803, doi:10.5194/acp-5-1787-2005, 2005.
13. Faïn, X., Chappellaz, J., Rhodes, R. H., Stowasser, C., Blunier, T., McConnell, J. R., Brook, E. J., Preunkert, S., Legrand, M., Debois, T., and Romanini, D.: High resolution measurements of carbon monoxide along a late Holocene Greenland ice core: evidence for in situ production, Clim. Past., 10, 987-1000, doi:10.5194/cp-10-987-2014, 2014.
14. Fiore, A. M., Dentener, F. J., Wild, O., Cuvelier, C., Schultz, M. G., Hess, P., and Zuber, A.: Multimodel estimates of intercontinental source-receptor relationships for ozone pollution, J. Geophys. Res., 114, D04301, doi:10.1029/2008JD010816, 2009.
15. Fiore, A. M., Naik, V., Spracklen, D. V, Steiner, A., Unger, N., Prather, M., and Zeng, G.: Global air quality and climate, Chem. Soc. Rev., 41, 6663-6683, doi:10.1039/c2cs35095e, 2012.
16. Gildor, H., Ashkenazy, Y., Tziperman, E., and Lev, I.: The role of sea ice in the temperatureprecipitation feedback of glacial cycles, Clim. Dynam., 43, 1001-1010, doi:10.1007/s00382-013-1990-7, 2014.
17. Guenther, A., Karl, T., Harley, P., Wiedinmyer, C., Palmer, P. I., and Geron, C.: Estimates of global terrestrial isoprene emissions using MEGAN (Model of Emissions of Gases and Aerosols from Nature), Atmos. Chem. Phys., 6, 3181-3210, doi:10.5194/acp-6-3181-2006, 2006.
18. Guenther, A. B., Jiang, X., Heald, C. L., Sakulyanontvittaya, T., Duhl, T., Emmons, L. K., and Wang, X.: The Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2.1): an extended and updated framework for modeling biogenic emissions, Geosci. Model. Dev., 5, 1471-1492, doi:10.5194/gmd-5-1471-2012, 2012.
19. Guilderson, T. P., Fairbanks, R. G., and Rubenstone, J. L.: Tropical Temperature Variations Since 20,000 Years Ago: Modulating Interhemispheric Climate Change, Science, 253, 663-665, doi:10.1126/science.263.5147.663, 1994.
20. 2ice core record anomalies, J. Geophys. Res., 112, D10123, doi:10.1029/2006JD007886, 2007.
21. Haan, D. and Raynaud, D.: Ice core record of CO variations during the last two millennia: atmospheric implications and chemical interactions within the Greenland ice, Tellus B, 50, 253-262, 1998.
22. 4 emissions during the Holocene and glacial-interglacial transitions constrained by ice core data, Global Biogeochem. Cy., 21, GB1011, doi:10.1029/2005GB002680, 2007.
23. Heald, C. L. and Spracklen, D. V.: Land use change impacts on air quality and climate, Chem. Rev., 115, 4476-4496, doi:10.1021/cr500446g, 2015.
24. Heald, C. L., Ridley, D. A., Kroll, J. H., Barrett, S. R. H., Cady-Pereira, K. E., Alvarado, M. J., and Holmes, C. H.: Contrasting the direct radiative effect and direct radiative forcing of aerosols, Atmos. Chem. Phys., 14, 5513-5527, doi:10.5194/acp-14-5513-2014, 2014.
25. Henze, D. K. and Seinfeld, J. H.: Global secondary organic aerosol from isoprene oxidation, Geophys. Res. Lett., 33, L09812, doi:10.1029/2006GL025976,2006.
26. Hewitt, C. N., Lee, J. D., MacKenzie, A. R., Barkley, M. P., Carslaw, N., Carver, G. D., Chappell, N. A., Coe, H., Collier, C., Commane, R., Davies, F., Davison, B., DiCarlo, P., Di Marco, C. F., Dorsey, J. R., Edwards, P. M., Evans, M. J., Fowler, D., Furneaux, K. L., Gallagher, M., Guenther, A., Heard, D. E., Helfter, C., Hopkins, J., Ingham, T., Irwin, M., Jones, C., Karunaharan, A., Langford, B., Lewis, A. C., Lim, S. F., MacDonald, S. M., Mahajan, A. S., Malpass, S., McFiggans, G., Mills, G., Misztal, P., Moller, S., Monks, P. S., Nemitz, E., Nicolas-Perea, V., Oetjen, H., Oram, D. E., Palmer, P. I., Phillips, G. J., Pike, R., Plane, J. M. C., Pugh, T., Pyle, J. A., Reeves, C. E., Robinson, N. H., Stewart, D., Stone, D., Whalley, L. K., and Yin, X.: Overview: oxidant and particle photochemical processes above a south-east Asian tropical rainforest (the OP3 project): introduction, rationale, location characteristics and tools, Atmos. Chem. Phys., 10, 169-199, doi:10.5194/acp-10-169-2010, 2010.
27. Hofzumahaus, A., Rohrer, F., Lu, K., Bohn, B., Brauers, T., Chang, C.-C., and Zhang, Y.: Amplified trace gas removal in the troposphere, Science, 324, 1702-1704, doi:10.1126/science.1164566, 2009.
28. Holden, P. B., Edwards, N. R., Wolff, E.W., Lang, N. J., Singarayer, J. S., Valdes, P. J., and Stocker, T. F.: Interhemispheric coupling, the West Antarctic Ice Sheet and warm Antarctic interglacials, Clim. Past, 6, 431-443, doi:10.5194/cp-6-431-2010, 2010.
29. Holmes, C. D., Prather, M. J., Søvde, O. A., and Myhre, G.: Future methane, hydroxyl, and their uncertainties: key climate and emission parameters for future predictions, Atmos. Chem. Phys., 13, 285-302, doi:10.5194/acp-13-285-2013, 2013.
30. Horowitz, L. W., Liang, J., Gardner, G. M., and Jacob, D. J.: Export of reactive nitrogen from North America during summertime: Sensitivity to hydrocarbon chemistry, J. Geophys. Res., 103, 13451-13476, 1998.
31. Hutterli, M. A., Bales, R. C., Mcconnell, J. R., and Stewart, R. W.: HCHO in Antarctic snow: Preservation in ice cores and air-snow exchange, Geophys. Res. Lett., 29, 1235, doi:10.1029/2001GL014256, 2002.
32. Isaksen, I. S. and Dalsøren, S. B.: Atmospheric science. Getting a better estimate of an atmospheric radical, Science, 331, 38-39, doi:10.1126/science.1199773, 2011.
33. Kaplan, J. O.: Wetlands at the Last Glacial Maximum: Distribution and methane emissions, Geophys. Res. Lett., 29, 1079, doi:10.1029/2001GL013366, 2002.
34. Kaplan, J. O., Folberth, G., and Hauglustaine, D. A.: Role of methane and biogenic volatile organic compound sources in late glacial and Holocene fluctuations of atmospheric methane concentrations, Global Biogeochem. Cy., 20, GB2016, doi:10.1029/2005GB002590, 2006.
35. Khalil, M. A. K. and Rasmussen, R. A.: Atmospheric methane: Trends over the last 10 000 years, Atmos. Environ., 21, 2445-2452, 1987.
36. Kirschke, S., Bousquet, P., Ciais, P., Saunois, M., Canadell, J. G., Dlugokencky, E. J., Bergamaschi, P., Bergmann, D., Blake, D. R., Bruhwiler, L., Cameron-Smith, P., Castaldi, S., Chevallier, F., Feng, L., Fraser, A., Heimann, M., Hodson, E. L., Houweling, S., Josse, B., Fraser, P. J., Krummel, P. B., Lamarque, J.-F., Langenfelds, R. L., Le Quere, C., Naik, V., O'Doherty, S., Palmer, P. I., Pison, I., Plummer, D., Poulter, B., Prinn, R. G., Rigby, M., Ringeval, B., Santini, M., Schmidt, M., Shindell, D. T., Simpson, I. J., Spahni, R., Steele, L. P., Strode, S. A., Sudo, K., Szopa, S., van der Werf, G. R., Voulgarakis, A., van Weele, M., Weiss, R. F., Williams, J. E., and Zeng, G.: Three decades of global methane sources and sinks, Nat. Geosci, 6, 813-823, doi:10.1038/ngeo1955, 2013.
37. Krol, M. and Lelieveld, J.: Can the variability in tropospheric OH be deduced from measurements of 1,1,1-trichloroethane (methyl chloroform)?, J. Geophys. Res., 108, 4125, doi:10.1029/2002JD002423, 2003.
38. Lamarque, J.-F., Shindell, D. T., Josse, B., Young, P. J., Cionni, I., Eyring, V., Bergmann, D., Cameron-Smith, P., Collins, W. J., Doherty R., Dalsoren, S., Faluvegi, G., Folberth, G., Ghan, S. J., Horowitz, L. W., Lee, Y. H., MacKenzie, I. A., Nagashima, T., Naik, V., Plummer, D., Righi, M., Rumbold, S. T., Schulz, M., Skeie, R. B., Stevenson, D. S., Strode, S., Sudo, K., Szopa, S., Voulgarakis, A., and Zeng, G.: The Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP): overview and description of models, simulations and climate diagnostics, Geosci. Model Dev., 6, 179-206, doi:10.5194/gmd-6-179-2013, 2013.
39. Lathière, J., Hauglustaine, D. A., De Noblet-Ducoudré, N., Krinner, G., and Folberth, G. A.: Past and future changes in biogenic volatile organic compound emissions simulated with a global dynamic vegetation model, Geophys. Res. Lett., 32, L20818, doi:10.1029/2005GL024164, 2005.
40. 2 concentration, climate, and land use, Global Biogeochem. Cy., 24, GB1004, doi:10.1029/2009GB003548, 2010.
41. Lee, C. C.W., Savarino, J., and Thiemsen, M. H.: Mass independent oxygen isotopic composition of atmospheric sulfate: Origin and implications for the present and past atmospheres of Earth and Mars, Geophys. Res. Lett., 28, 1783-1786, 2001.
42. Lee, H.-M., Henze, D. K., Alexander, B., and Murray, L. T.: Investigating the sensitivity of surface-level nitrate seasonality in Antarctica to primary sources using a global model, Atmos. Environ., 89, 757-767, doi:10.1016/j.atmosenv.2014.03.003, 2014.
43. LeGrande, A. N., Schmidt, G. A., Shindell, D. T., Field, C. V., Miller, R. L., Koch, D. M., and Hoffmann, G.: Consistent simulations of multiple proxy responses to an abrupt climate change event, P. Natl. Acad. Sci. USA, 103, 837-842, 2006.
44. Lelieveld, J., Butler, T. M., Crowley, J. N., Dillon, T. J., Fischer, H., Ganzeveld, L., and Williams, J.: Atmospheric oxidation capacity sustained by a tropical forest, Nature, 452, 737-740, doi:10.1038/nature06870, 2008.
45. Levine, J. G., Wolff, E. W., Jones, A. E., Hutterli, M. A., Wild, O., Carver, G. D., and Pyle, J. A.: In search of an ice core signal to differentiate between source-driven and sink-driven changes in atmospheric methane, J. Geophys. Res., 116, D05305, doi:10.1029/2010JD014878, 2011a.
46. Levine, J. G., Wolff, E. W., Jones, A. E., Sime, L. C., Valdes, P. J., Archibald, A. T., Carver, G. D., Warwick, N. J., and Pyle, J. A.: Reconciling the Changes in Atmospheric Methane Sources and Sinks between the Last Glacial Maximum and the Pre-Industrial Era, J. Geophys. Res., 38, L23804, doi:10.1029/2011gl049545, 2011b.
47. Liu, S. C., Trainer, M., Fehsenfeld, F. C., Parrish, D. D., Williams, E. J., Fahey, D. W., and Murphy, P. C.: Ozone production in the rural troposphere and the implications for regional and global ozone distributions, J. Geophys. Res., 92, 4191-4207, 1987.
48. Liu, Y. J., Herdlinger-Blatt, I., McKinney, K. A., and Martin, S. T.: Production of methyl vinyl ketone and methacrolein via the hydroperoxyl pathway of isoprene oxidation, Atmos. Chem. Phys., 13, 5715-5730, doi:10.5194/acp-13-5715-2013, 2013.
49. Mahowald, N. M., Yoshioka, M., Collins, W. D., Conley, A. J., Fillmore, D.W., and Coleman, D. B.: Climate response and radiative forcing from mineral aerosols during the last glacial maximum, pre-industrial, current and doubled-carbon dioxide climates, Geophys. Res. Lett., 33, L20705, doi:10.1029/2006GL026126, 2006.
50. x) in the Arctic troposphere in spring, Atmos. Chem. Phys., 10, 5823-5838, doi:10.5194/acp-10-5823-2010, 2010.
51. Mao, J., Ren, X., Zhang, L., Van Duin, D. M., Cohen, R. C., Park, J.-H., Goldstein, A. H., Paulot, F., Beaver, M. R., Crounse, J. D., Wennberg, P. O., DiGangi, J. P., Henry, S. B., Keutsch, F. N., Park, C., Schade, G. W., Wolfe, G. M., Thornton, J. A., and Brune, W. H.: Insights into hydroxyl measurements and atmospheric oxidation in a California forest, Atmos. Chem. Phys., 12, 8009-8020, doi:10.5194/acp-12-8009-2012, 2012.
52. Mao, J., Fan, S., Jacob, D. J., and Travis, K. R.: Radical loss in the atmosphere from Cu-Fe redox coupling in aerosols, Atmos. Chem. Phys., 13, 509-519, doi:10.5194/acp-13-509-2013, 2013a.
53. Mao, J., Paulot, F., Jacob, D. J., Cohen, R. C., Crounse, J. D., Wennberg, P. O., and Horowitz, L. W.: Ozone and organic nitrates over the eastern United States: Sensitivity to isoprene chemistry, J. Geophys. Res.-Atmos., 118, 11256-11268, doi:10.1002/jgrd.50817, 2013b.
54. McLinden, C. A., Olsen, S. C., Hannegan, B., Wild, O., and Prather, M. J.: Stratospheric ozone in 3-D models: A simple chemistry and the cross-tropopause flux, J. Geophys. Res., 14653-14665, 2000.
55. Michalski, G.: First measurements and modeling of 117O in atmospheric nitrate, Geophys. Res. Lett., 30, 1870, doi:10.1029/2003GL017015, 2003.
56. Montzka, S. A., Spivakovsky, C. M., Butler, J. H., Elkins, J. W., Lock, L. T., and Mondeel, D. J.: New observational constraints, for atmospheric hydroxyl on global and hemispheric scales, Science, 288, 500-503, 2000.
57. Murray, L. T., Mickley, L. J., Kaplan, J. O., Sofen, E. D., Pfeiffer, M., and Alexander, B.: Factors controlling variability in the oxidative capacity of the troposphere since the Last Glacial Maximum, Atmos. Chem. Phys., 14, 3589-3622, doi:10.5194/acp-14-3589-2014, 2014.
58. Murray, L. T., Fiore, A. M., Shindell, D. T., Naik, V., Horowitz, L. W., and Evans, M. J.: Uncertainties in global atmospheric hydroxyl projections tied to fate of reactive nitrogen and carbon, in preparation, 2015.
59. Naik, V., Voulgarakis, A., Fiore, A. M., Horowitz, L. W., Lamarque, J.-F., Lin, M., Prather, M. J., Young, P. J., Bergmann, D., Cameron-Smith, P. J., Cionni, I., Collins, W. J., Dalsøren, S. B., Doherty, R., Eyring, V., Faluvegi, G., Folberth, G. A., Josse, B., Lee, Y. H., MacKenzie, I. A., Nagashima, T., van Noije, T. P. C., Plummer, D. A., Righi, M., Rumbold, S. T., Skeie, R., Shindell, D. T., Stevenson, D. S., Strode, S., Sudo, K., Szopa, S., and Zeng, G.: Preindustrial to present-day changes in tropospheric hydroxyl radical and methane lifetime from the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP), Atmos. Chem. Phys., 13, 5277-5298, doi:10.5194/acp-13-5277-2013, 2013.
60. Novelli, P. C., Masarie, K. A., and Lang, P. M.: Distributions and recent changes of carbon monoxide in the lower troposphere, J. Geophys. Res., 103, 19015-19033, doi:10.1029/98JD01366, 1998.
61. Oyarzun, R., Lillo, J., Sánchez-Hernández, J. C., and Higueras, P.: Pre-industrial Metal Anomalies in Ice Cores: A Simplified Reassessment of Windborne Soil Dust Contribution and Volcanic Activity during the Last Glaciation, Int. Geol. Rev., 47, 1120-1130, doi:0.2747/0020-6814.47.11.1120, 2005.
62. Pacifico, F., Folberth, G. A., Jones, C. D., Harrison, S. P., and Collins, W. J.: Sensitivity of biogenic isoprene emissions to past, present, and future environmental conditions and implications for atmospheric chemistry, J. Geophys. Res., 117, D22303, doi:10.1029/2012JD018276, 2012.
63. Park, R., Jacob, D. J., Field, B., Yantosca, R., and Chin, M.: Natural and transboundary pollution influences on sulfate-nitrateammonium aerosols in the United States: Implications for policy, J. Geophys. Res., 109, D15204, doi:10.1029/2003JD004473, 2004.
64. Parrella, J. P., Jacob, D. J., Liang, Q., Zhang, Y., Mickley, L. J., Miller, B., Evans, M. J., Yang, X., Pyle, J. A., Theys, N., and Van Roozendael, M.: Tropospheric bromine chemistry: implications for present and pre-industrial ozone and mercury, Atmos. Chem. Phys., 12, 6723-6740, doi:10.5194/acp-12-6723-2012, 2012.
65. Paulot, F., Crounse, J. D., Kjaergaard, H. G., Kroll, J. H., Seinfeld, J. H., and Wennberg, P. O.: Isoprene photooxidation: new insights into the production of acids and organic nitrates, Atmos. Chem. Phys., 9, 1479-1501, doi:10.5194/acp-9-1479-2009, 2009a.
66. Paulot, F., Crounse, J. D., Kjaergaard, H. G., Kürten, A., Clair, J. M. S., Seinfeld, J. H., andWennberg, P. O.: Unexpected Epoxide Formation in the Gas-Phase Photooxidation of Isoprene, Science, 325, 730-733, 2009b.
67. Paulot, F., Henze, D. K., and Wennberg, P. O.: Impact of the isoprene photochemical cascade on tropical ozone, Atmos. Chem. Phys., 12, 1307-1325, doi:10.5194/acp-12-1307-2012, 2012.
68. Paulot, F., Jacob, D. J., and Henze, D. K.: Sources and Processes Contributing to Nitrogen Deposition: An Adjoint Model Analysis Applied to Biodiversity Hotspots Worldwide, Environ. Sci. Technol., 47, 3226-3233, 2013.
69. Pavelin, E. G., Johnson, C. E., Rughooputh, S., and Toumi, R.: Evaluation of pre-industrial surface ozone measurements made using Schönbein's method, Atmos. Environ., 33, 919-929, 1999.
70. Peñuelas, J. and Staudt, M.: BVOCs and global change, Trends Plant Sci., 15, 133-144, doi:10.1016/j.tplants.2009.12.005, 2010.
71. Pfeiffer, M., Spessa, A., and Kaplan, J. O.: A model for global biomass burning in preindustrial time: LPJ-LMfire (v1.0), Geosci. Model Dev., 6, 643-685, doi:10.5194/gmd-6-643-2013, 2013.
72. Pike, R. C. and Young, P. J.: How plants can influence tropospheric chemistry?: the role of isoprene emissions from the biosphere, Weather, 64, 332-336, 2009.
73. 2 concentrations, Glob. Change Biol., 17, 1595-1610, doi:10.1111/j.1365-2486.2010.02306.x, 2011.
74. Power, M. J., Marlon, J., Ortiz, N., Bartlein, P. J., Harrison, S. P., Mayle, F. E., and Zhang, J. H.: Changes in fire regimes since the Last Glacial Maximum: an assessment based on a global synthesis and analysis of charcoal data, Clim. Dynam., 30, 887-907, doi:10.1007/s00382-007-0334-x, 2007.
75. Power, M. J., Marlon, J. R., Bartlein, P. J., and Harrison, S. P.: Fire history and the Global Charcoal Database: A new tool for hypothesis testing and data exploration, Palaeogeogr. Palaeocl., 291, 52-59, doi:10.1016/j.palaeo.2009.09.014, 2010.
76. Prather, M. J., Holmes, C. D., and Hsu, J.: Reactive greenhouse gas scenarios: Systematic exploration of uncertainties and the role of atmospheric chemistry, Geophys. Res. Lett., 39, L09803, doi:10.1029/2012GL051440, 2012.
77. Prinn, R. G., Huang, J., Weiss, R. F., Cunnold, D. M., Fraser, P. J., Simmonds, P. G., McCulloch, A., Harth, C., Salameh, P., O'Doherty, S., Wang, R. H. J., Porter, L., and Miller, B. R.: Evidence for substantial variations of atmospheric hydroxyl radicals over the past two decades, Science, 292, 1882-1888, 2001.
78. Prinn, R. G., Huang, J., Weiss, R. F., Cunnold, D. M., Fraser, P. J., Simmonds, P. G., and Krummel, P. B.: Evidence for variability of atmospheric hydroxyl radicals over the past quarter century, Geophys. Res. Lett., 32, L07809, doi:10.1029/2004GL022228, 2005.
79. Quiquet, A., Archibald, A. T., Friend, A. D., Chappellaz, J., Levine, J. G., Stone, E. J., Telford, P. J., and Pyle, J. A.: The relative importance of methane sources and sinks over the Last Interglacial period and into the last glaciation, Quaternary Sci. Rev., 112, 1-16, doi:10.1016/j.quascirev.2015.01.004, 2015.
80. Rind, D., Chandler, M., Lonergan, P., and Lerner, J.: Climate change and the middle atmosphere: 5. Paleostratosphere in cold and warm climates, J. Geophys. Res., 106, 20195, doi:10.1029/2000JD900548, 2001.
81. Rind, D., Lerner, J., McLinden, C., and Perlwitz, J.: Stratospheric ozone during the Last Glacial Maximum, Geophys. Res. Lett., 36, L09712, doi:10.1029/2009GL037617, 2009.
82. Rohrer, F., Lu, K., Hofzumahaus, A., Bohn, B., Brauers, T., Chang, C.-C., and Wahner, A.: Maximum efficiency in the hydroxylradical-based self-cleansing of the troposphere, Nat. Geosci., 7, 559-563, doi:10.1038/ngeo2199, 2014.
83. Savarino, J., Lee, C. C. W., and Thiemens, M. H.: Laboratory oxygen isotopic study of sulfur (IV) oxidation: Origin of the mass-independent oxygen isotopic anomaly in atmospheric sulfates and sulfate mineral deposits on Earth, J. Geophys. Res., 105, 29079-29088, doi:10.1029/2000JD900456, 2000.
84. Scott, C. E., Rap, A., Spracklen, D. V., Forster, P. M., Carslaw, K. S., Mann, G. W., Pringle, K. J., Kivekäs, N., Kulmala, M., Lihavainen, H., and Tunved, P.: The direct and indirect radiative effects of biogenic secondary organic aerosol, Atmos. Chem. Phys., 14, 447-470, doi:10.5194/acp-14-447-2014, 2014.
85. Sitch, S., Cox, P. M., Collins, W. J., and Huntingford, C.: Indirect radiative forcing of climate change through ozone effects on the land-carbon sink, Nature, 448, 791-794, doi:10.1038/nature06059, 2007.
86. 2-), Atmos. Chem. Phys., 11, 3565-3578, doi:10.5194/acp-11-3565-2011, 2011.
87. Sofen, E. D., Alexander, B., Steig, E. J., Thiemens, M. H., Kunasek, S. A., Amos, H. M., Schauer, A. J., Hastings, M. G., Bautista, J., Jackson, T. L., Vogel, L. E., McConnell, J. R., Pasteris, D. R., and Saltzman, E. S.: WAIS Divide ice core suggests sustained changes in the atmospheric formation pathways of sulfate and nitrate since the 19th century in the extratropical Southern Hemisphere, Atmos. Chem. Phys., 14, 5749-5769, doi:10.5194/acp-14-5749-2014, 2014.
88. Spolaor, A., Vallelonga, P., Cozzi, G., Gabrieli, J., Varin, C., Kehrwald, N., Zennaro, P., Boutron, C., and Barbante, C.: Iron speciation in aerosol dust influences iron bioavailability over glacial-interglacial timescales, Geophys. Res. Lett., 40, 1-6, doi:10.1002/grl.50296, 2013.
89. Stevenson, D. S., Young, P. J., Naik, V., Lamarque, J.-F., Shindell, D. T., Voulgarakis, A., Skeie, R. B., Dalsoren, S. B., Myhre, G., Berntsen, T. K., Folberth, G. A., Rumbold, S. T., Collins, W. J., MacKenzie, I. A., Doherty, R. M., Zeng, G., van Noije, T. P. C., Strunk, A., Bergmann, D., Cameron-Smith, P., Plummer, D. A., Strode, S. A., Horowitz, L., Lee, Y. H., Szopa, S., Sudo, K., Nagashima, T., Josse, B., Cionni, I., Righi, M., Eyring, V., Conley, A., Bowman, K. W., Wild, O., and Archibald, A.: Tropospheric ozone changes, radiative forcing and attribution to emissions in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP), Atmos. Chem. Phys., 13, 3063-3085, doi:10.5194/acp-13-3063-2013, 2013.
90. Stute, M., Forster, M., Frischkorn, H., Serejo, A., Clark, J. F., Schlosser, P., Broecker, W. S., and Bonani, G.: Cooling of Tropical Brazil (5°C) During the Last Glacial Maximum, Science, 269, 379-383, doi:10.1126/science.269.5222.379, 1995.
91. 2 concentration leads to increased whole-plant isoprene emission in hybrid aspen (Populus tremula x Populus tremuloides), New Phytol., 198, 788-800, doi:10.1111/nph.12200, 2013.
92. 2 inhibition on biogenic isoprene emission: Implications for air quality under 2000 to 2050 changes in climate, vegetation, and land use, Geophys. Res. Lett., 40, 3479-3483, doi:10.1002/grl.50650, 2013.
93. 2 loss in aqueous atmospheric aerosols: Regional and global impacts on tropospheric oxidants, J. Geophys. Res., 113, D05303, doi:10.1029/2007JD009236, 2008.
94. 2 concentrations, PloS One, 7, e32387, doi:10.1371/journal.pone.0032387, 2012.
95. Unger, N.: Isoprene emission variability through the twentieth century, J. Geophys. Res.-Atmos., 118, 13606-13613, doi:10.1002/2013JD020978, 2013.
96. Unger, N.: Human land-use-driven reduction of forest volatiles cools global climate, Nature Climate Change, 4, 1-4, doi:10.1038/nclimate2347, 2014a.
97. Unger, N.: On the role of plant volatiles in anthropogenic global climate change, Geophys. Res. Lett., 41, 8563-8569, doi:10.1002/2014GL061616, 2014b.
98. Unger, N. and Yue, X.: Strong chemistry-climate feedbacks in the Pliocene, Geophys. Res. Lett., 41, 527-533, doi:10.1002/2013GL058773, 2014.
99. Valdes, P. J., Beering, D. J., and Johnson, C. E.: The ice age methane budget, Geophys. Res. Lett., 32, L02704, doi:10.1029/2004GL021004, 2005.
100. van der Werf, G. R., Peters, W., van Leeuwen, T. T., and Giglio, L.: What could have caused pre-industrial biomass burning emissions to exceed current rates?, Clim. Past., 9, 289-306, doi:10.5194/cp-9-289-2013, 2013.
101. Voulgarakis, A., Naik, V., Lamarque, J.-F., Shindell, D. T., Young, P. J., Prather, M. J., Wild, O., Field, R. D., Bergmann, D., Cameron-Smith, P., Cionni, I., Collins, W. J., Dalsøren, S. B., Doherty, R. M., Eyring, V., Faluvegi, G., Folberth, G. A., Horowitz, L. W., Josse, B., MacKenzie, I. A., Nagashima, T., Plummer, D. A., Righi, M., Rumbold, S. T., Stevenson, D. S., Strode, S. A., Sudo, K., Szopa, S., and Zeng, G.: Analysis of present day and future OH and methane lifetime in the ACCMIP simulations, Atmos. Chem. Phys., 13, 2563-2587, doi:10.5194/acp-13-2563-2013, 2013.
102. Waelbroeck, C., Paul, A., Kucera, M., Rosell-Melé, A., Weinelt, M., Schneider, R., and Turon, J.-L.: Constraints on the magnitude and patterns of ocean cooling at the Last Glacial Maximum, Nat. Geosci., 2, 127-132, doi:10.1038/ngeo411, 2009.
103. Wang, Y. and Jacob, D. J.: Anthropogenic forcing on tropospheric ozone and OH since preindustrial times, J. Geophys. Res., 103, 31123-31135, doi:10.1029/1998JD100004, 1998.
104. Wang, Z., Chappellaz, J., Park, K., and Mak, J. E.: Large variations in Southern Hemisphere biomass burning during the last 650 years, Science, 330, 1663-1666, doi:10.1126/science.1197257, 2010.
105. Webb, R. S., Rind, D. H., Lehman, S. J., Healy, R. J., and Sigman, D.: Influence of ocean heat transport on the climate of the Last Glacial Maximum, Nature, 385, 695-699, 1997.
106. Weber, S. L., Drury, A. J., Toonen, W. H. J., and van Weele, M.: Wetland methane emissions during the Last Glacial Maximum estimated from PMIP2 simulations: Climate, vegetation, and geographic controls, J. Geophys. Res., 115, D06111, doi:10.1029/2009JD012110, 2010.
107. 2 concentration, Glob. Change. Biol., 15, 1189-1200, doi:10.1111/j.1365-2486.2008.01803.x, 2009.