Surface Water Structure and Hygroscopic Properties of Light Absorbing Secondary Organic Polymers of Atmospheric Relevance

[Image: see text] Hygroscopic properties and chemical reactivity of secondary organic aerosols (SOA) influence their overall contribution to the indirect effect on the climate. In this study, we investigate the hygroscopic properties of organic and organometallic polymeric particles, namely polycatechol, polyguaiacol, Fe-polyfumarte, and Fe-polymuconate. These particles efficiently form in iron-catalyzed reactions with aromatic and aliphatic dicarboxylic acid compounds detected in field-collected SOA. The structure of surface water was studied using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), and the uptake of gas water was quantified using quartz crystal microbalance (QCM) as a function of relative humidity. Spectroscopic data show that water bonding with organic functional groups acting as hydrogen bond acceptors causes shifts in their vibrational modes. Analysis of the hydroxyl group stretching region revealed weak and strong hydrogen bonding networks that suggest cluster formation reflecting water–water and water–organics interactions, respectively. A modified Type II multilayer Brunauer–Emmett–Teller adsorption model described the adsorption isotherm on the nonporous materials, polycatechol, polyguaiacol, and Fe-polymuconate. However, water adsorption on porous Fe-polyfumarate was best described using a Type V adsorption model, namely the Langmuir–Sips model that accounts for condensation in pores. The data revealed that organometallic polymers are more hygroscopic than organic polymers. The implications of these investigations are discussed in the context of the chemical reactivity of these particles relative to known SOA.