Abstract
Mineral dust aerosol participates in heterogeneous chemistry in the atmosphere. In particular, the hydroxyl groups on the surface of aluminosilicate clay minerals are important for heterogeneous atmospheric processes. These functional groups may be altered by acidic processing during atmospheric transport. In this study, we exposed kaolinite (KGa-1b) and montmorillonite (STx-1b) to aqueous sulfuric acid and then rinsed the soluble reactants and products off in order to explore changes to functional groups on the mineral surface. To quantify the changes due to acid treatment of edge hydroxyl groups, we use 19F magic angle spinning nuclear magnetic resonance spectroscopy and a probe molecule, 3,3,3-trifluoropropyldimethylchlorosilane. We find that the edge hydroxyl groups (OH) increase in both number and density with acid treatment. Chemical reactions in the atmosphere may be impacted by the increase in OH at the mineral edge.
Acknowledgements
We acknowledge the Materials Characterization Lab run by the Materials Research Institute at Penn State for use of the PANanalytical Empyrean XRD. We thank L. Ortiz Rivera for performing BET measurements on the ASAP 2020 automated surface area and porosity system, and V. Bojan and G. Barber for performing the XPS experiments and helpful discussions. We also thank J. V. Badding for use of a centrifuge. A portion of the research was performed using EMSL, a DOE Office of Science User Facility sponsored by the Office of Biological and Environmental Research and located at the Pacific Northwest National Laboratory. M. B. A., S. K. S., and M. A. F. were funded by the Pennsylvania State University and by an NSF CAREER Award (CHE 1351383). K. A. M. and K. T. M. were funded by NSF CHE 1213451.
References
1. O. Boucher, D. Randall, P. Artaxo, C. Bretherton, G. Feingold, P. Forster, V.-M. Kerminen, Y. Kondo, H. Liao, U. Lohmann, P. Rasch, S. K. Satheesh, S. Sherwood, B. Stevens, X. Y. Zhang, in: T. F. Stocker, D. Qin, G.-K. Plattner, M. Tignor, S. K. Allen, J. Boschung, A. Nauels, Y. Xia, V. Bex, P. M. Midgley (Eds.): The Physical Science Basis. Contribution of Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change, Cambridge University Press, New York, NY, USA (2013).Search in Google Scholar
2. F. J. Dentener, G. R. Carmichael, Y. Zhang, J. Lelieveld, P. J. Crutzen, J. Geophys. Res. Atmos. 101 (1996) 22869.10.1029/96JD01818Search in Google Scholar
3. P. Forster, V. Ramaswamy, P. Artaxo, T. Berntsen, R. Betts, D. W. Fahey, J. Haywood, J. Lean, D. C. Lowe, G. Myhre, J. Nganga, R. Prinn, G. Raga, M. Schulz, R. Van Dorland, in: S. Solomon, D. Qin, M. Manning, Z. Chen, M. Marquis, K. B. Averyt, M. Tignor, H. L. Miller (Eds.): Changes in atmospheric constituents and in radiative forcing in climate change 2007: The physical science basis. Contribution of working group I to the fourth assessment report of the intergovernmental panel on climate change, Cambridge University Press, New York, NY, USA (2007).Search in Google Scholar
4. J. M. Prospero, J. E. Bullard, R. Hodgkins, Science 335 (2012) 1078.10.1126/science.1217447Search in Google Scholar PubMed
5. T. Liu, Loess in China, China Ocean Press, Berlin, Germany (1985).Search in Google Scholar
6. C. S. McNaughton, A. D. Clarke, V. Kapustin, Y. Shinozuka, S. G. Howell, B. E. Anderson, E. Winstead, J. Dibb, E. Scheuer, R. C. Cohen, P. Wooldridge, A. Perring, L. G. Huey, S. Kim, J. L. Jimenez, E. J. Dunlea, P. F. DeCarlo, P. O. Wennberg, J. D. Crounse, A. J. Weinheimer, F. Flocke, Atmos. Chem. Phys. 9 (2009) 8283.10.5194/acp-9-8283-2009Search in Google Scholar
7. R. E. Grim, Clay Mineralogy, 2nd Ed., McGraw-Hill (1968).Search in Google Scholar
8. G. N. White, J. B. Dixon, in: J. B. Dixon, D. G. Schulze (Eds.): Soil Mineralogy with Environmental Applications, Soil Science Society of America Book Series 7; Soil Science Society of America, Inc. (2002), p. 389.Search in Google Scholar
9. J. D. Schuttlefield, D. Cox, V. H. Grassian, J. Geophys. Res. 112 (2007) D21303.10.1029/2007JD008973Search in Google Scholar
10. C. D. Hatch, J. S. Wiese, C. C. Crane, K. J. Harris, H. G. Kloss, J. Baltrusaitis, Langmuir 28 (2012) 1790.10.1021/la2042873Search in Google Scholar PubMed
11. D. W. Rutherford, C. T. Chiou, D. D. Eberl, Clay. Clay Miner. 45 (1997) 534.10.1346/CCMN.1997.0450405Search in Google Scholar
12. D. A. Reid-Soukup, A. L. Ulery, in: J. B. Dixon, D. G. Schulze (Eds.): Soil mineralogy with environmental applications, Soil Science Society of America Book Series 7; Soil Science Society of America, Inc. (2002), p. 467.Search in Google Scholar
13. C. R. Usher, H. Al-Hosney, S. Carlos-Cuellar, V. H. Grassian, J. Geophys. Res. Atmos. 107 (2002) 4713.10.1029/2002JD002051Search in Google Scholar
14. M. Ullerstam, M. S. Johnson, R. Vogt, E. Ljungström, Atmos. Chem. Phys. 3 (2003) 2043.10.5194/acp-3-2043-2003Search in Google Scholar
15. A. R. Ravishankara, Science 276 (1997) 1058.10.1126/science.276.5315.1058Search in Google Scholar
16. G. Rubasinghege, V. H. Grassian, Chem. Commun. 49 (2013) 3071.10.1039/c3cc38872gSearch in Google Scholar
17. Z. Zhang, J. Shang, T. Zhu, H. Li, D. Zhao, Y. Liu, C. Ye, J. Environ. Sci. 24 (2012) 1753.10.1016/S1001-0742(11)61014-0Search in Google Scholar
18. C. Brandt, R. Van Eldik, Chem. Rev. 95 (1995) 119.10.1021/cr00033a006Search in Google Scholar
19. L. Deguillaume, M. Leriche, K. Desboeufs, G. Mailhot, C. George, N. Chaumerliac, Chem. Rev. 105 (2005) 3388.10.1021/cr040649cSearch in Google Scholar PubMed
20. B. Ervens, Chem. Rev. 115 (2015) 4157.10.1021/cr5005887Search in Google Scholar PubMed
21. C. J. Weschler, M. L. Mandich, T. E. Graedel, J. Geophys. Res. 91 (1986) 5189.10.1029/JD091iD04p05189Search in Google Scholar
22. X. Zhao, L. Kong, Z. Sun, X. Ding, T. Cheng, X. Yang, J. Chen, J. Phys. Chem. A 119 (2015) 4001.10.1021/acs.jpca.5b01359Search in Google Scholar PubMed
23. P. Li, K. A. Perreau, E. Covington, C. H. Song, G. R. Carmichael, V. H. Grassian, J. Geophys. Res. 106 (2001) 5517.10.1029/2000JD900573Search in Google Scholar
24. C. H. Lochmüller, M. T. Kersey, Langmuir 4 (1988) 572.10.1021/la00081a013Search in Google Scholar
25. P. Van Der Voort, I. Gillis-D’Hamers, E. F. Vansant, J. Chem. Soc. Faraday Trans. 86 (1990) 3751.10.1039/ft9908603751Search in Google Scholar
26. T. Kawai, K. Tsutsumi, Colloid Polym. Sci. 276 (1998) 992.10.1007/s003960050338Search in Google Scholar
27. T. Kawai, K. Tsutsumi, J. Colloid Interface Sci. 212 (1999) 310.10.1006/jcis.1999.6093Search in Google Scholar PubMed
28. R. L. Sanders, N. M. Washton, K. T. Mueller, J. Phys. Chem. C 114 (2010) 5491.10.1021/jp906132kSearch in Google Scholar
29. X. S. Zhao, G. Q. Lu, J. Phys. Chem. B 102 (1998) 1556.10.1021/jp972788mSearch in Google Scholar
30. N. M. Washton, S. L. Brantley, K. T. Mueller, Geochim. Cosmochim. Acta 72 (2008) 5949.10.1016/j.gca.2008.09.018Search in Google Scholar
31. S. J. Chipera, D. L. Bish, Clays Clay Miner. 49 (2001) 398.10.1346/CCMN.2001.0490507Search in Google Scholar
32. K. D. Froyd, D. M. Murphy, T. J. Sanford, D. S. Thomson, J. C. Wilson, L. Pfister, L. Lait, Atmos. Chem. Phys. 9 (2009) 4363.10.5194/acp-9-4363-2009Search in Google Scholar
33. J. Liao, K. D. Froyd, D. M. Murphy, F. N. Keutsch, G. Yu, P. O. Wennberg, J. M. St. Clair, J. D. Crounse, A. Wisthaler, T. Mikoviny, T. B. Ryerson, I. B. Pollack, J. Peischl, J. L. Jimenez, P. C. Jost, D. A. Day, B. E. Anderson, L. D. Ziemba, D. R. Blake, S. Meinardi, G. Diskin, J. Geophys. Res. Atmos. 120 (2015) 2990.10.1002/2014JD022378Search in Google Scholar PubMed
34. S. K. Sihvonen, G. P. Schill, N. A. Lyktey, D. P. Veghte, M. A. Tolbert, M. A. Freedman, J. Phys. Chem. A 118 (2014) 8787.10.1021/jp504846gSearch in Google Scholar PubMed
35. A. Labouriau, Y. W. Kim, S. Chipera, D. L. Bish, W. L. Earl, Clays Clay Miner. 43 (1995) 697.10.1346/CCMN.1995.0430606Search in Google Scholar
36. Y. Xiao, A. C. Lasaga, Geochim. Cosmochim. Acta 58 (1994) 5379.10.1016/0016-7037(94)90237-2Search in Google Scholar
37. J. Cama, V. Metz, J. Ganor, Geochim. Cosmochim. Acta 66 (2002) 3913.10.1016/S0016-7037(02)00966-3Search in Google Scholar
38. F. J. Huertas, L. Chou, R. Wollast, Geochim. Cosmochim. Acta 63 (1999) 3261.10.1016/S0016-7037(99)00249-5Search in Google Scholar
39. F. J. Huertas, L. Chou, R. Wollast, Geochim. Cosmochim. Acta 62 (1998) 417.10.1016/S0016-7037(97)00366-9Search in Google Scholar
40. M. Rozalen, F. J. Huertas, P. V. Brady, Geochim. Cosmochim. Acta 73 (2009) 3752.10.1016/j.gca.2009.03.026Search in Google Scholar
41. M. Zysset, P. W. Schindler, Geochim. Cosmochim. Acta 60 (1996) 921.10.1016/0016-7037(95)00451-3Search in Google Scholar
42. V. Metz, K. Amram, J. Ganor, Geochim. Cosmochim. Acta 69 (2005) 1755.10.1016/j.gca.2004.09.027Search in Google Scholar
43. R. L. Sanders, N. M. Washton, K. T. Mueller, Geochim. Cosmochim. Acta 92 (2012) 100.10.1016/j.gca.2012.05.038Search in Google Scholar
44. Y. Bereznitski, M. Jaroniec, P. Maurice, J. Colloid. Interface Sci. 205 (1998) 528.10.1006/jcis.1998.5633Search in Google Scholar PubMed
45. R. J. Pruett, H. L. Webb, Clays Clay Miner. 41 (1993) 514.10.1346/CCMN.1993.0410411Search in Google Scholar
46. in: H. Van Olphen, J. J. Fripiat (Eds.): Data Handbook for CLAY materials and Other Nonmetallic Minerals, Pergamon Press, Oxford, UK (1979).Search in Google Scholar
47. S. L. Brantley, N. P. Mellott, Am. Mineral. 85 (2000) 1767.10.2138/am-2000-11-1220Search in Google Scholar
48. A. F. White, A. E. Blum, M. S. Schulz, T. D. Bullen, J. W. Harden, M. L. Peterson, Geochim. Cosmochim. Acta 60 (1996) 2533.10.1016/0016-7037(96)00106-8Search in Google Scholar
49. S. A. Shaw, M. J. Hendry, Appl. Geochem. 24 (2009) 333.10.1016/j.apgeochem.2008.10.011Search in Google Scholar
50. A. Davis, D. B. Kent, in: Michael, F.; J. Hochella, A. F. White (Eds.): Mineral-water Interface Geochemistry, Mineralogical Society of America (1990) 177.10.1515/9781501509131-009Search in Google Scholar
51. P. Van Der Voort, S. Vercauteren, K. Peeters, E. F. Vansant, J. Colloid Interface Sci. 157 (1993) 518.10.1006/jcis.1993.1219Search in Google Scholar
©2018 Walter de Gruyter GmbH, Berlin/Boston
