Modeling the Uptake of Semivolatile Organic Compounds by Passive Air Samplers: Importance of Mass Transfer Processes within the Porous Sampling Media

• Published in: Environmental science & technology Vol. 46; no. 17; pp. 9563 - 9570
• Main Authors: Zhang, Xianming, Wania, Frank
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 04.09.2012
• Subjects: Adsorption; air; Air Pollutants - isolation & purification; Analysis methods; Applied sciences; Atmospheric boundary layer; Atmospheric pollution; Chemicals; Diffusion; Environmental Monitoring - instrumentation; Exact sciences and technology; foams; Kinetics; mass transfer; Mathematical models; Models, Chemical; Molecules; Pollution; Polystyrenes - chemistry; polyurethanes; Polyurethanes - chemistry; Porosity; Resins, Synthetic - chemistry; samplers; Sensitivity analysis; sorption; temperature; vapors; volatile organic compounds; Volatile Organic Compounds - isolation & purification; wind speed; Passive detection; Sampler; Porous medium; Air pollution; Low volatile compound; Sampling; Mathematical model; Modeling; Mass transfer; Organic compounds
• ISSN: 0013-936X; 1520-5851; 1520-5851
• DOI: 10.1021/es302334r

Air sampling based on diffusion of target molecules from the atmospheric gas phase to passive sampling media (PSMs) is currently modeled using the two-film approach. Originally developed to describe chemical exchange between air and water, it assumes a uniform chemical distribution in the bulk phases on either side of the interfacial films. Although such an assumption may be satisfied when modeling uptake in PSMs in which chemicals have high mobility, its validity is questionable for PSMs such as polyurethane foam disks and XAD-resin packed mesh cylinders. Mass transfer of chemicals through the PSMs may be subject to a large resistance because of the low mass fraction of gas-phase chemicals in the pores, where diffusion occurs. Here we present a model that does not assume that chemicals distribute uniformly in the PSMs. It describes the sequential diffusion of vapors through a stagnant air-side boundary layer and the PSM pores, and the reversible sorption onto the PSM. Sensitivity analyses reveal the potential influence of the latter two processes on passive sampling rates (PSRs) unless the air-side boundary layer is assumed to be extremely thick (i.e., representative of negligible wind speeds). The model also reveals that the temperature dependence of PSRs, differences in PSRs between different compounds, and a two-stage uptake, all observed in field calibrations, can be attributed to those mass transfer processes within the PSM. The kinetics of chemical sorption to the PSM from the gas phase in the macro-pores is a knowledge gap that needs to be addressed before the model can be applied to specific compounds.