1D_RnDPM: A freely available 222Rn production, diffusion, and partition model to evaluate confounding factors in the radon-deficit technique.

The radon-deficit technique is a powerful tool to detect and delineate sub-surface accumulations of organic contaminants. Field measurements of 222Rn in soil air, however, are affected by several confounding factors that can lead to the misinterpretation of results. Among the most influential are: vertical and lateral changes of lithology, fluctuating contaminant saturations with depth, varying water saturation ratios along the soil profile and atmospheric (and, therefore, soil) thermal oscillations. To evaluate and minimize the effect of these confounding factors on the interpretation of the results of the Rn deficit technique, a Matlab® based multi-layer model of 222Rn production-partition-diffusion in unsaturated porous media (1D_RnDPM: One-Dimensional 222Rn Diffusion and Partition Model) has been developed and is freely available as Supplementary Material in this work. A laboratory protocol has also been proposed to obtain site-specific input parameters for the model, i.e., 222Rn equilibrium concentration (as determined by the accumulation chamber method), soil bulk density and soil solid-phase density. The model predictions have been contrasted with field information obtained from successive sampling campaigns in which 222Rn in soil air was measured at a site where the vadose zone, consisting of an anthropogenic backfill underlain by a silt layer, is affected by a complex mixture of benzene, phenol, (poly) chlorobenzenes, (poly) chlorophenols and hexachlorocyclohexane isomers, among other compounds. The model has successfully predicted the vertical profile of 222Rn concentrations in soil air, including the effect of the oscillations of the water table and of ground-level temperature. The results also underline that 222Rn measurements in subsoil air are representative only of local conditions around the sampling point, an expected result given that 222Rn maximum effective diffusion length is very limited. As a consequence, the influence of a highly fluctuating water table at the site goes undetected at the sampling depths used in the field campaigns. MAIN FINDINGS: The combination of a numerical model and a laboratory protocol allows to predict the activity of 222Rn along the soil profile and to assess the influence of site-specific confounding factors.

Field performance of the radon-deficit technique to detect and delineate a complex DNAPL accumulation in a multi-layer soil profile.

The performance of the radon (222Rn)-deficit technique has been evaluated at a site in which a complex DNAPL mixture (mostly hexachlorocyclohexanes and chlorobenzenes) has contaminated all four layers (from top to bottom: anthropic backfill, silt, gravel and marl) of the soil profile. Soil gas samples were collected at two depths (0.8 m and 1.7 m) in seven field campaigns and a total of 186 222Rn measurements were performed with a pulse ionization detector. A statistical assessment of the influence of field parameters on the results revealed that sampling depth and atmospheric pressure did not significantly affect the measurements, while the location of the sampling point and ground-level atmospheric temperature did. In order to remove the bias introduced by varying field temperatures and hence to be able to jointly interpret 222Rn measurements from different campaigns, 222Rn concentrations were rescaled by dividing each individual datum by the mean 222Rn concentration of its corresponding field campaign. Rescaled 222Rn maps showed a high spatial correlation between 222Rn minima and maximum contaminant concentrations in the top two layers of the soil profile, successfully delineating the surface trace of DNAPL accumulation in the anthropic backfill and silt layers. However, no correlation could be established between 222Rn concentrations in superficial soil gas and contaminant concentration in the deeper two layers of the soil profile. These results indicate that the 222Rn-deficit technique is unable to describe the vertical variation of contamination processes with depth but can be an effective tool for the preliminary characterization of sites in which the distance between the inlet point of the sampling probe and the contaminant accumulation falls within the effective diffusion length of 222Rn in the affected soil profile.

Applicability and limitations of the radon-deficit technique for the preliminary assessment of sites contaminated with complex mixtures of organic chemicals: A blind field-test.

A blind field test with 136 independent measurements of radon (222Rn) in soil air retrieved from a depth of 0.8 m in a decommissioned lindane (γ-hexachlorocyclohexane) production plant was undertaken to evaluate the performance of the 222Rn-deficit technique as a screening methodology for the location and delineation of subsurface accumulations of complex mixtures of organic contaminants. Maps of 222Rn iso-concentrations were drawn and interpreted before direct analytical information regarding concentrations of hexachlorocyclohexanes, chlorobenzenes and BTEX compounds in soil, groundwater and soil air were disclosed to the authors. The location and extension of pollution hot spots inferred from the 222Rn campaigns agrees remarkably well with the analytical data obtained from the intrusive sampling campaigns and with the location of contaminant source zones (chemical reactor and waste-storage area) and geological sinks of those contaminants (paleochannel). Two main limitations to the applicability of the 222Rn-deficit technique were identified and assessed: The statistically significant variation of 222Rn concentrations with diurnal changes of ground-level air temperature and the maximum depth of investigation in the absence of significant advective and co-advective transport of radon. If the influence of those two factors is accounted for and/or minimized (by averaging replicated measurements during the workday and in different days), the 222Rn-deficit technique has the potential to be an efficient technique which delivers information in quasi-real time, with a much higher spatial density than that of intrusive techniques, at a much faster rate and at a significantly lower cost. MAIN FINDINGS: The 222Rn-deficit technique is an effective tool for real-time site characterization only limited by diffusion length of radon and diurnal temperature variations.