References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-10-7643-2010

Structure-activity relationships to estimate the effective Henry's law constants of organics of atmospheric interest

Raventos-Duran

¹ Camredon

¹ Valorso

¹ Mouchel-Vallon

¹ Aumont

LISA, UMR CNRS/INSU 7583, Université Paris Est Créteil et Université Paris Diderot, Institut Pierre Simon Laplace, 94010 Créteil Cedex, France

17 08 2010

10 16 7643 7654

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The Henry's law constant is a key property needed to address the multiphase behaviour of organics in the atmosphere. Methods that can reliably predict the values for the vast number of organic compounds of atmospheric interest are therefore required. The effective Henry's law constant H* in air-water systems at 298 K was compiled from literature for 488 organic compounds bearing functional groups of atmospheric relevance. This data set was used to assess the reliability of the HENRYWIN bond contribution method and the SPARC approach for the determination of H*. Moreover, this data set was used to develop GROMHE, a new Structure Activity Relationship (SAR) based on a group contribution approach. These methods estimate logH* with a Root Mean Square Error (RMSE) of 0.38, 0.61, and 0.73 log units for GROMHE, SPARC and HENRYWIN respectively. The results show that for all these methods the reliability of the estimates decreases with increasing solubility. The main differences among these methods lie in H* prediction for compounds with H* greater than 103 M atm−1. For these compounds, the predicted values of logH* using GROMHE are more accurate (RMSE = 0.53) than the estimates from SPARC or HENRYWIN.

References 1

Atkinson, R.: Atmospheric chemistry of VOCs and NOx, Atmos. Environ., 34, 2063–2101, 2000.

Aumont, B., Madronich, S., Bey, I., and Tyndall, G. S.: Contribution of secondary VOC to the composition of aqueous atmospheric particles: a modeling approach, J. Atmos. Chem., 35, 59–75, 2000.

Aumont, B., Szopa, S., and Madronich, S.: Modelling the evolution of organic carbon during its gas-phase tropospheric oxidation: development of an explicit model based on a self generating approach, Atmos. Chem. Phys., 5, 2497–2517, doi:10.5194/acp-5-2497-2005, 2005.

Betterton, E. A., and Hoffmann, M. R.: Henry's law constants of some environmentally important aldehydes, Environ. Sci. Technol, 22, 1415–1418, 1988.

Blando, J. D., and Turpin, B. J.: Secondary organic aerosol formation in cloud and fog droplets: a literature evaluation of plausibility, Atmos. Environ., 34, 1623–1632, 2000.

Boethling, R. S., and Mackay, D.: Handbook of Property Estimation Methods for Chemicals: Environmental Health Sciences, CRC Press LLC, Washington, DC, USA, 2000.

Camredon, M., Aumont, B., Lee-Taylor, J., and Madronich, S.: The SOA/VOC/NOx system: an explicit model of secondary organic aerosol formation, Atmos. Chem. Phys., 7, 5599–5610, doi:10.5194/acp-7-5599-2007, 2007.

Chen, J., Griffin, R. J., Grini, A., and Tulet, P.: Modeling secondary organic aerosol formation through cloud processing of organic compounds, Atmos. Chem. Phys., 7, 5343–5355, doi:10.5194/acp-7-5343-2007, 2007.

Dearden, J. C. and Schuurmann, G.: Quantitative structure-property relationships for predicting Henry's law constant from molecular structure, Environ. Toxicol. Chem., 22, 1755–1770, 2003.

Ervens, B., George, C., Williams, J. E., Buxton, G. V., Salmon, G. A., Bydder, M., Wilkinson, F., Dentener, F., Wolke, R., and Herrmann, H.: CAPRAM 2.4 (MODAC mechanism): an extended and condensed tropospheric aqueous phase mechanism and its application, J. Geophys. Res.-Atmos., 108, 4426, doi:4410.1029/2002JD002202, 2003.

Ervens, B., Carlton, A. G., Turpin, B. J., Altieri, K. E., Kreidenweis, S. M., and Feingold, G.: Secondary organic aerosol yields from cloud-processing of isoprene oxidation products, Geophys. Res. Lett., 35, 5, L02816, doi:10.1029/2007JL031828, 2008.

Facchini, M. C., Fuzzi, S., Zappoli, S., Andracchio, A., Gelencser, A., Kiss, G., Krivacsy, Z., Meszaros, E., Hansson, H. C., Alsberg, T., and Zebuhr, Y.: Partitioning of the organic aerosol component between fog droplets and interstitial air, J. Geophys. Res.-Atmos., 104, 26821–26832, 1999.

Finlayson-Pitts, B. J. and Pitts, J. N.: Chemistry of the upper and lower atmosphere, Academic Press, San Diego, USA, 2000.

Gelencser, A., and Varga, Z.: Evaluation of the atmospheric significance of multiphase reactions in atmospheric secondary organic aerosol formation, Atmos. Chem. Phys., 5, 2823–2831, doi:10.5194/acp-5-2823-2005, 2005.

Goldstein, A. H., and Galbally, I. E.: Known and unexplored organic constituents in the earth's atmosphere, Environ. Sci. Technol., 41, 1514–1521, 2007.

Griffin, R. J., Nguyen, K., Dabdub, D., and Seinfeld, J. H.: A coupled hydrophobic-hydrophilic model for predicting secondary organic aerosol formation, J. Atmos. Chem., 44, 171–190, 2003.

Hallquist, M., Wenger, J. C., Baltensperger, U., Rudich, Y., Simpson, D., Claeys, M., Dommen, J., Donahue, N. M., George, C., Goldstein, A. H., Hamilton, J. F., Herrmann, H., Hoffmann, T., Iinuma, Y., Jang, M., Jenkin, M. E., Jimenez, J. L., Kiendler-Scharr, A., Maenhaut, W., McFiggans, G., Mentel, T. F., Monod, A., Prevot, A. S. H., Seinfeld, J. H., Surratt, J. D., Szmigielski, R., and Wildt, J.: The formation, properties and impact of secondary organic aerosol: current and emerging issues, Atmos. Chem. Phys., 9, 5155–5236, doi:10.5194/acp-9-5155-2009, 2009.

Hansch, C., Leo, A. , and Hoekman, D.: Exploring QSAR: Hydrophobic, Electronic, and Steric Constants, American Chemical Society, Washington DC, USA, 1995.

Herrmann, H., Ervens, B., Jacobi, H.-W., Wolke, R., Nowacki, P., and Zellner, R.: CAPRAM2.3: A chemical aqueous phase radical mechanism for tropospheric chemistry, J. Atmos. Chem., 36, 231–284, 2000.

Herrmann, H., Tilgner, A., Barzaghi, P., Majdik, Z., Gligorovski, S., Poulain, L., and Monod, A.: Towards a more detailed description of tropospheric aqueous phase organic chemistry: CAPRAM 3.0, Atmos. Environ., 39, 4351–4363, 2005.

Hilal, S. H., Karickhoff, S. W., and Carreira, L. A.: Prediction of the solubility, activity coefficient and liquid/liquid partition coefficient of organic compounds, Qsar Comb. Sci., 23, 709–720, 2004.

Hilal S. H., Ayyampalayam S. N., and Carreira, L. A.: Air-liquid partition coefficient for a diverse set of organic compounds: Henry's law constant in water and hexadecane, Environ. Sci. Technol., 42(24), 9231–9236, 2008.

Hine, J. and Moorkerjee, P. K.: The intrinsic hydrophilic character of organic compounds, Correlations in terms of structural contributions, J. Org. Chem., 40, 292–298, 1975.

Jacob D., Gottlieb, E. W. and Prather, M. J.: Chemistry of polluted cloudy boundary layer, J. Geophys. Res.-Atmos., 94, 12975–13002, 1989.

Kuhne, R., Ebert, R. U., and Schuurmann, G.: Prediction of the temperature dependency of Henry's law constant from chemical structure, Environ. Sci. Technol., 39(17), 6705–6711, 2005.

Le Henaff, P.: Methodes d'etude et proprietes des hydrates, hemiacetals et hemithioacetals derives des aldehydes et des cetones., P. Bull. Soc. Chim. Fr., 11, 4687–4698, 1968.

Legrand, M., Preunkert, S., Wagenbach, D., Cachier, H., and Puxbaum, H.: A historical record of formate and acetate from a high-elevation alpine glacier: Implications for their natural versus anthropogenic budgets at the European scale, J. Geophys. Res.-Atmos., 108(15), 4788, doi:10.1029/2003JD003594, 2003.

Legrand, M., Preunkert, S., Galy-Lacaux, C., Liousse, C., and Wagenbach, D.: Atmospheric year-round records of dicarboxylic acids and sulfate at three French sites located between 630 and 4360 m elevation, J. Geophys. Res., 110, D13302, doi:10.1029/2004JD005515, 2005.

Lelieveld, J., and Crutzen, P. J.: Influences of cloud photochemical processes on tropospheric ozone, Nature, 343, 227–233, 1990.

Levine I.N.: Physical Chemistry, fifth edition, McGraw-Hill Higher Education, New York, USA, 2002.

Lim, H. J., Carlton, A. G., and Turpin, B. J.: Isoprene forms secondary organic aerosol through cloud processing: Model simulations, Environ. Sci. Technol., 39(12), 4441–4446, 2005.

Lin, S. T., and Sandler, S. I.: Henry's law constant of organic compounds in water from a group contribution model with multipole corrections, Chem. Eng. Sci., 57, 2727–2733, 2002.

Mackay, D., and Shiu, W. Y.: A critical-review of Henrys law constants for chemicals of environmental interest, J. Phys. Chem. Ref. Data., 10, 1175–1199, 1981.

Meylan, W. M. and Howard, P. H.: Bond contribution method for estimating Henry's law constants, Environ. Toxicol. Chem, 10, 1283–1293, 1991.

Meylan, W. M. and Howard, P. H.: Src's epi suite, v3.20, Syracuse Research Corporation: Syracuse. NY, 2000.

Perrin, D. D., Dempsey, B., and Serjeant, E. P.: pKa prediction for organic acids and bases, Chapman and Hall, London, UK and New York, USA, 1981.

Pun, B. K., Griffin, R. J., Seigneur, C., and Seinfeld, J. H.: Secondary organic aerosol-2. Thermodynamic model for gas/particule partitioning of molecular constituents, J. Geophys. Res., 107(D17), 4333, doi:10.1029/2001JD000542, 2002.

Russell, C. J., Dixon, S. L., and Jurs, P. C.: Computer-assisted study of the relationship between molecular-structure and Henry Law constant, Anal. Chem., 64, 1350–1355, 1992.

Sander, R.: Compilation of Henry's law constants for inorganic and organic species of potential importance in environmental chemistry (Version 3): www.henrys-law.org, 1999.

Saunders, S. M., Jenkin, M. E., Derwent, R. G., and Pilling, M. J.: Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part A): tropospheric degradation of non-aromatic volatile organic compounds, Atmos. Chem. Phys., 3, 161–180, doi:10.5194/acp-3-161-2003, 2003.

Saxena, P., and Hildemann, L. M.: Water-soluble organics in atmospheric particles : a critical review of the literature and application of thermodynamics to identify candidate compounds, J. Atmos. Chem., 24, 57–109, 1996.

Seinfeld, J. H. and Pandis, S. N.: Atmospheric chemistry and physics, Wiley, New York, USA, 1997.

Suzuki, T., Ohtaguchi, K., and Koide, K.: Application of principal components-analysis to calculate Henry constant from molecular-structure, Comput. Chem., 16, 41–52, 1992.

Walcek, C. J., Yuan, H. H., and Stockwell, W. R.: The influence of aqueous-phase chemical reactions on ozone formation in polluted and nonpolluted clouds, Atmos. Environ., 31, 1221–1237, 1997.

Yu, L. E., Shulman, M. L., Kopperud, R., and Hildemann, L. M.: Characterization of organic compounds collected during southeastern aerosol and visibility study: Water-soluble organic species, Environ. Sci. Technol., 39(3), 707–715, 2005.