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Atmospheric Fate of Volatile Methyl Siloxanes

  • Michael S. McLachlanEmail author
Chapter
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Part of the The Handbook of Environmental Chemistry book series (HEC, volume 89)

Abstract

Volatile methyl siloxanes (VMS) are emitted primarily to air, and the bulk of VMS present in the environment resides in the atmosphere. Therefore, the atmospheric fate of VMS is a core component of the environmental chemistry of these chemicals. In this chapter the phase partitioning of VMS in the atmosphere is first examined, and then the different mechanisms by which they can be removed from the atmosphere are evaluated, both physical removal via deposition and chemical removal via reactions. We find that VMS are almost entirely present in gaseous form and that reaction with OH radicals is the dominant process for their removal. Consequently, for most purposes, the atmospheric fate of VMS can be simplified to three processes: the emission function, advection, and removal via reaction with OH radicals. However, each of these processes is complex, so we explore how mathematical models have been used to capture this complexity, quantify the expected atmospheric fate, and describe the variability of VMS concentrations in time and space.

Keywords

D4 D5 Deposition Modeling Phototransformation 

References

  1. 1.
    Brooke DN, Crookes MJ, Gray D, Robertson S (2009) Environmental risk assessment report: octamethylcyclotetrasiloxane. UK Environment Agency, BristolGoogle Scholar
  2. 2.
    Brooke DN, Crookes MJ, Gray D, Robertson S (2009) Environmental risk assessment report: decaamethylcyclopentasiloxane. UK Environment Agency, BristolGoogle Scholar
  3. 3.
    Brooke DN, Crookes MJ, Gray D, Robertson S (2009) Environmental risk assessment report: dodecamethylcyclohexasiloxane. UK Environment Agency, BristolGoogle Scholar
  4. 4.
    Environment Canada, Health Canada (2008) Screening assessment for the challenge: octamethylcyclotetrasiloxane (D4). CAS RN 556-67-2, Environment CanadaGoogle Scholar
  5. 5.
    Environment Canada, Health Canada (2008) Screening assessment for the challenge: decamethylcyclopentasiloxane (D5). CAS RN 541-02-6, Environment CanadaGoogle Scholar
  6. 6.
    Environment Canada, Health Canada (2008) Screening assessment for the challenge: dodecamethylcyclohexasiloxane (D6). CAS RN 540-97-6, Environment CanadaGoogle Scholar
  7. 7.
    Hughes L, Mackay D, Powell DE, Kim I (2012) An updated state of the science EQC model for evaluating chemical fate in the environment: application to D5 (decamethylcyclopentasiloxane). Chemosphere 87:118–124Google Scholar
  8. 8.
    Xu S, Wania F (2013) Chemical fate, latitudinal distribution and long-range transport of cyclic volatile methylsiloxanes in the global environment: a modeling assessment. Chemosphere 93:835–843Google Scholar
  9. 9.
    Mackay D, Paterson S, Schroeder WH (1986) Model describing the rates of transfer processes of organic chemicals between atmosphere and water. Environ Sci Technol 20:810–816Google Scholar
  10. 10.
    Arp HPH, Schwarzenbach RP, Goss K-U (2008) Ambient gas/particle partitioning. 1. Sorption mechanisms of apolar, polar, and ionisable organic compounds. Environ Sci Technol 42:5541–5547Google Scholar
  11. 11.
    Bidleman TF, Harner T (2000) Sorption to aerosols. In: Mackay D, Boethling RS (eds) Property estimation methods for chemicals – environmental and health sciences. CRC Press, Boca Raton, pp 233–260Google Scholar
  12. 12.
    Arp HPH, Schwarzenbach RP, Goss K-U (2008) Ambient gas/particle partitioning. 2. The influence of particle source and temperature on sorption to dry terrestrial aerosols. Environ Sci Technol 42:5951–5957Google Scholar
  13. 13.
    Xu S, Kropscott B (2013) Octanol/air partition coefficients of volatile methylsiloxanes and their temperature dependence. J Chem Eng Data 58:136–142Google Scholar
  14. 14.
    Xu S (2013) Correction to “Octanol/air partition coefficients of volatile methylsiloxanes and their temperature dependence”. J Chem Eng Data 58:2136Google Scholar
  15. 15.
    Mackay D (2001) Multimedia environmental models: the fugacity approach. CRC Press, Boca RatonGoogle Scholar
  16. 16.
    Xu S, Kozerski G, Mackay D (2014) Critical review and interpretation of environmental data for volatile methylsiloxanes: partition properties. Environ Sci Technol 48:11748–11759Google Scholar
  17. 17.
    Xu S, Kropscott B (2014) Evaluation of the three-phase equilibrium method for measuring temperature dependence of internally consistent partition coefficients (KOW, KOA, and KAW) for volatile methylsiloxanes and trimethylsilanol. Environ Toxicol Chem 33:2702–2710Google Scholar
  18. 18.
    Kim J, Xu S (2016) Sorption and desorption kinetics and isotherms of volatile methylsiloxanes with atmospheric aerosols. Chemosphere 144:555–563Google Scholar
  19. 19.
    Goss K-U, Buschmann J, Schwarzenbach RP (2003) Determination of the surface sorption properties of talc, different salts, and clay minerals at various relative humidities using adsorption data of a diverse set of organic vapors. Environ Toxicol Chem 22:2667–2672Google Scholar
  20. 20.
    Navea JG, Xu S, Stanier CO, Young MA, Grassian VH (2009) Heterogeneous uptake of octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) onto mineral dust aerosol under variable RH conditions. Atmos Environ 43:4060–4069Google Scholar
  21. 21.
    MacLeod M, Scheringer M, Götz C, Hungerbühler K, Davidson CI, Holsen TM (2011) Deposition form the atmosphere to water and soils with aerosol particles and precipitation. In: Thibodeaux LJ, Mackay D (eds) Handbook of chemical mass transport in the environment. CRC Press, Boca Raton, pp 103–136Google Scholar
  22. 22.
    Mackay D, Gobas F, Solomon K, Macleod M, McLachlan M, Powell DE, Xu S (2015) Comment on “Unexpected occurrence of volatile dimethylsiloxanes in Antarctic soils, vegetation, phytoplankton, and krill”. Environ Sci Technol 49:7507–7509Google Scholar
  23. 23.
    Ahrens L, Harner T, Shoeib M (2014) Temporal variations of cyclic and linear volatile methylsiloxanes in the atmosphere using passive samplers and high-volume air samplers. Environ Sci Technol 48:9374–9381Google Scholar
  24. 24.
    McLachlan MS (2011) Mass transfer between the atmosphere and plant canopy systems. In: Thibodeaux LJ, Mackay D (eds) Handbook of chemical mass transport in the environment. CRC Press, Boca Raton, pp 103–136Google Scholar
  25. 25.
    Gaj K, Pakuluk A (2015) Volatile methyl siloxanes as potential hazardous air pollutants. Pol J Environ Stud 24:937–943Google Scholar
  26. 26.
    Atkinson R (1991) Kinetics of the gas-phase reactions of a series of organosilicon compounds with OH and NO3 radicals and O3 at 297 ± 2 K. Environ Sci Technol 25:863–866Google Scholar
  27. 27.
    Whelan MJ, Estrada E, van Egmond R (2004) A modelling assessment of the atmospheric fate of volatile methyl siloxanes and their reaction products. Chemosphere 57:1427–1437Google Scholar
  28. 28.
    Janechek NJ, Hansen KM, Stanier CO (2017) Comprehensive atmospheric modeling of reactive cyclic siloxanes and their oxidation products. Atmos Chem Phys 17:8357–8370Google Scholar
  29. 29.
    Wu Y, Johnston MV (2016) Molecular characterization of secondary aerosol from oxidation of cylic methylsiloxanes. J Am Soc Mass Spectrom 27:402–409Google Scholar
  30. 30.
    Wu Y, Johnston MV (2017) Aerosol formation from OH oxidation of the volatile cyclic methyl siloxane (cVMS) decamethylcyclopentasiloxane. Environ Sci Technol 51:4445–4451Google Scholar
  31. 31.
    Sommerlade R, Parlar H, Wrobel D, Kochs P (1993) Product analysis and kinetics of the gas-phase reactions of selected organosilicon compounds with OH radicals using a smog chamber-mass spectrometer system. Environ Sci Technol 27:2435–2440Google Scholar
  32. 32.
    Markgraf SI, Wells JR (1997) The hydroxyl radical reaction rate constants and atmospheric reaction products of three siloxanes. In J Chem Kinet 29:445–451Google Scholar
  33. 33.
    Safron A, Strandell M, Kierkegaard A, MacLeod M (2015) Activation energies for gas-phase reactions of three cyclic volatile methyl siloxanes with the hydroxyl radical. In J Chem Kinet 47:420–428Google Scholar
  34. 34.
    MacLeod M, Kierkegaard A, Genualdi S, Harner T, Scheringer M (2013) Junge relationships in measurement data for cyclic siloxanes in air. Chemosphere 93:830–834Google Scholar
  35. 35.
    Xiao R, Zammit I, Wei Z, Hu W-P, MacLeod M, Spinney R (2015) Kinetics and mechanism of the oxidation of cyclic methylsiloxanes by hydroxyl radical in the gas phase: an experimental and theoretical study. Environ Sci Technol 49:13322–13330Google Scholar
  36. 36.
    Kim J, Xu S (2017) Quantitative structure-reactivity relationships of hydroxyl radical rate constants for linear and cyclic volatile methylsiloxanes. Environ Toxicol Chem 36:3240–3245Google Scholar
  37. 37.
    Bernard F, Papanastasiou DK, Papadimitriou VC, Burkholder JB (2018) Temperature dependent rate coefficients for the gas-phase reaction of the OH radical with linear (L2, L3) and cyclic (D3, D4) permethylsiloxanes. J Phys Chem 122:4252–4264Google Scholar
  38. 38.
    Xu S (1998) Hydrolysis of poly(dimethylsiloxanes) on clay minerals as influenced by exchangeable cations and moisture. Environ Sci Technol 32:3162–3168Google Scholar
  39. 39.
    Xu S (1999) Fate of cyclic methylsiloxanes in soils. 1. The degradation pattern. Environ Sci Technol 33:603–608Google Scholar
  40. 40.
    Navea JG, Xu S, Stanier CO, Young MA, Grassian VH (2009) Effect of ozone and relative humidity on the heterogeneous uptake of octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane on model mineral dust aerosol components. J Phys Chem A 113:7030–7038Google Scholar
  41. 41.
    Navea JG, Young MA, Xu S, Grassian VH, Stanier CO (2011) The atmospheric lifetimes and concentrations of cyclic methylsiloxanes octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5) and the influence of heterogeneous uptake. Atmos Environ 45:3181–3191Google Scholar
  42. 42.
    McLachlan MS, Kierkegaard A, Hansen KM, van Egmond R, Christensen JH, Skjøth CA (2010) Concentrations and fate of decamethylcyclopentasiloxane (D5) in the atmosphere. Environ Sci Technol 44:5365–5370Google Scholar
  43. 43.
    Krogseth IS, Kierkegaard A, McLachlan MS, Breivik K, Hansen KM, Schlabach M (2013) Occurrence and seasonality of cyclic volatile methyl siloxanes in Arctic air. Environ Sci Technol 47:502–509Google Scholar
  44. 44.
    Genualdi S, Harner T, Cheng Y, MacLeod M, Hansen KM, van Egmond R, Shoeib M, Lee SC (2011) Global distribution of linear and cyclic volatile methyl siloxanes in air. Environ Sci Technol 45Ö:3349–3354Google Scholar
  45. 45.
    Buser AM, Kierkegaard A, Bogdal C, MacLeod M, Scheringer M, Hungerbühler K (2013) Concentrations in ambient air and emissions of cyclic volatile methylsiloxanes in Zurich, Switzerland. Environ Sci Technol 47:7045–7051Google Scholar
  46. 46.
    Companioni-Damas EY, Santos FJ, Galceran MT (2014) Linear and cyclic methylsiloxanes in air by concurrent solvent recondensation – large volume injection – gas chromatography – mass spectrometry. Talanta 118:245–252Google Scholar
  47. 47.
    Gallego E, Perales JF, Roca FJ, Guardino X, Gadea E (2017) Volatile methyl siloxanes (VMS) concentrations in outdoor air of several Catalan urban areas. Atmos Environ 155:108–118Google Scholar
  48. 48.
    Krogseth IS, Zhang X, Lei YD, Wania F, Breivik K (2013) Calibration and application of a passive air sampler (XADE-PAS) for volatile methyl siloxanes. Environ Sci Technol 47:4463–4470Google Scholar
  49. 49.
    Yucuis RA, Stanier CO, Hornbucke KC (2013) Cyclic siloxanes in air, including identification of high levels in Chicago and distinct diurnal variation. Chemosphere 92:905–910Google Scholar
  50. 50.
    Coggon MM, McDonald BC, Vlasenko A, Veres PR, Bernard F, Koss AR, Yuan B, Gilman JB, Peischl J, Aikin KC, DuRant J, Warneke C, Li S-M, de Gouw JA (2018) Diurnal variability and emission pattern of decamethylcyclopentasiloxane (D5) from the application of personal care products in two North American cities. Environ Sci Technol 52:5610–5618Google Scholar
  51. 51.
    Kierkegaard A, McLachlan MS (2013) Determination of linear and cyclic volatile methylsiloxanes in air at a regional background site in Sweden. Atmos Environ 80:322–329Google Scholar

Copyright information

© Springer Nature Switzerland AG 2018

Authors and Affiliations

  1. 1.Department of Environmental Science and Analytical ChemistryStockholm UniversityStockholmSweden

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