title: A modelling assessment of the atmospheric fate of volatile methyl siloxanes and their reaction products.
abstract: Volatile methyl siloxanes break down in the atmosphere by reacting with OH radicals to form OH-substituted silanols. As the silanols become increasingly OH substituted they are increasingly likely to be removed from the atmosphere by wet and dry deposition. A simple equilibrium partitioning model was constructed to explore the relative rates of removal by different mechanisms (reaction vs. deposition) for siloxanes and their resultant silanols. A mass balance is calculated for the parent siloxane molecule and for each silanol, characterised by the number of OH substitutions. The model includes the effect of incomplete equilibrium between the vapour, adsorbed and dissolved phases of silanols in the atmosphere using a non-equilibrium factor (epsilon) expressing relative departure from equilibrium. Model results show: (1) maximum vapour-phase concentrations for non-substituted siloxanes and single-OH-substituted silanols; (2) maximum dissolved-phase and adsorbed-phase concentrations for two-OH-substituted silanols; (3) >99% of the original material will be removed in wet deposition and <1% in dry deposition as silanols. For increasing OH-substitutions, the decreasing concentration of precursor molecules (as a consequence of combined removal processes) means that concentrations are negligible, in all phases, beyond three or four substitutions. Predictions were relatively insensitive to assumed departures from phase equilibrium. Predictions of silanol hydrolysis in liquid water droplets suggest that the mix of diol chain lengths in precipitation may not be in thermodynamic equilibrium and will depend on atmospheric residence time and pH.
authors.affiliation: Unilever Colworth Laboratory, Safety and Environmental Assurance Centre, Sharnbrook, Bedfordshire, MK44 1LQ, UK. mick.whelan@unilever.com
authors.forename: M J
authors.initials: MJ
authors.lastname: Whelan
authors.forename: E
authors.initials: E
authors.lastname: Estrada
authors.forename: R
authors.initials: R
authors.lastname: van Egmond
mesh_terms: D001272:Atmosphere / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D017665:Hydroxyl Radical / Q000737:chemistry; D008956:Models, Chemical; D011891:Rain; D012833:Siloxanes / Q000737:chemistry*; D013696:Temperature; D013997:Time Factors; D014835:Volatilization; D014867:Water / Q000737:chemistry
chemical_list: D012833:Siloxanes; D014867:Water; D017665:Hydroxyl Radical