Vapor intrusion of toxic volatile organic compounds (VOCs) from subsurface soil vapor, through a building slab/floor, and into the indoor air is an important environmental contaminant transport mechanism. It is widely believed that advective flow, driven by the pressure differential between the subslab and indoor air, is the primary mechanism of subslab soil vapor entry into buildings. This paper explores the hypothesis that molecular diffusion through the slab may potentially play a larger role in vapor intrusion than previously believed and may even be the predominant vapor intrusion mechanism when the subslab vapor source strength is sufficiently high or the pressure differential is relatively low. A novel sampling device, referred to as a Passive Adsorptive Diffusion Sampler (PADS), is presented for the purpose of directly measuring the diffusion of VOCs through a building slab. A vacant warehouse was identified as a case study site where historical sampling had determined that vapor intrusion of trichloroethene (TCE) was adversely impacting the indoor air. Calculations using Fick's First Law of Diffusion are presented which demonstrate that diffusion alone can theoretically account for all the TCE observed in the indoor air at this building based on an effective diffusion coefficient for concrete that was calculated from the Johnson and Ettinger Model. Two groups of nine replicate PADS were deployed at two areas on the slab and used to measure the flux and effective diffusion coefficient at each of the 18 total points, which showed an order of magnitude variability within each area and over two orders of magnitude variability overall. These results indicate that diffusion through concrete is inherently variable when measured at a sub‐meter scale. However, when combined over both areas, the overall average approached that calculated from the Johnson and Ettinger Model. An additional 12 PADS were deployed across the building slab (for a total of 30) to quantify the overall building‐wide diffusive flux. This area‐weighted average diffusive flux was consistent with the predicted diffusive flux as calculated from Fick's First Law and the vapor intrusion mass input required to achieve the observed indoor air TCE concentration. The results of this study show that PADS provides a simple way to measure diffusive flux directly without having to drill through the slab. However, significant variability in the measured flux should be expected and will need to be accounted for by the inclusion of a relatively large number of samples including replicates. When using PADs at a new site, the collection of traditional subslab vapors at a select number of locations is recommended for the verification of a building‐specific effective diffusion coefficient, which may not necessarily be the same as for this building.
