Radon deficit technique applied to the study of the ageing of a spilled LNAPL in a shallow aquifer.

A recent diesel spill (dated January 2019 ± 1 month) in a refilling station is investigated by the Radon deficit technique. The primary focus was on quantifying the LNAPL pore saturation as a function of duration of ageing, and on proposing a predictive model for on-site natural attenuation. A biennial monitoring of the local fluctuating shallow aquifer has involved the saturated zone nine times, and the vadose zone only once. Rn background generally measured in external and upstream wells is elaborated further due to the site characteristics, using drilling logs and phreatic oscillations. Notably, this study marks the first application of the Rn deficit method to produce a detailed Rn background mapping throughout the soil depth. Simultaneously, tests are performed on LNAPL surnatant samples to study diesel ageing. In particular, they are focused on temporal variations of LNAPL viscosity (from an initial 3.90 cP to 8.99 cP, measured at 25 °C, after 34 months), and Rn partition coefficient between the pollutant and water (from 47.7 to 80.2, measured at 25 °C, after 14 months). Rn diffusion is also measured in different fluids (0.092 cm2 s-1, 1.14 × 10-5 cm2 s-1, and 2.53 × 10-6 cm2 s-1 at 25 °C for air, water and LNAPL, respectively) directly. All parameters and equations utilized during this study are introduced, discussing their influence on Radon deficit technique from a theoretical point of view. Experimental findings are used to mitigate the effect of LNAPL ageing and of phreatic oscillations on determination of LNAPL saturation index (S.I.LNAPL). Finally, S.I.LNAPL dataset is discussed and elaborated to show the pollutant attenuation across subsurface over time, induced by natural processes primarily. The proposed predictive model for on-site natural attenuation suggests a half-removal time of one year and six months. The significance of such models lies in their capability to assess site-specific reactions to pollutants, thereby enhancing the effectiveness of remediation efforts over time. These experimental findings may offer a novel approach to application of Rn deficit technique and to environmental remediation of persistent organic compounds.

Vertical Light Non-Aqueous Phase Liquid (LNAPL) distribution by Rn prospecting in monitoring wells.

In the frame of a collaboration between the Italian National Research Council (CNR) and Mares s.r.l., a study, about the possibility of determining radon vertical distribution at different soil depths in order to trace light non-aqueous phase liquid (LNAPL) contaminations, was developed. The radon deficit technique, based on the preferential solubility of soil gas radon into non-polar fluids, such as refined hydrocarbons, has been investigated by various theoretical and applied research so far. According to international scientific literature, radon deficit can be used both for geochemical prospection of the spatial irregular NAPL dispersion and for monitoring of remediation activities. Even though it is well known that this type of pollutants can be distributed along the vertical soil profile-firstly due to their density in comparison to water density, and secondly due to fluctuations of shallow aquifers, soil pore size, aging of contamination, and so on-the vertical localization of the plume still represents a scientific challenge. In this article, a method to determine the radon vertical profile is tested and applied to assess the potential use of the radon deficit technique in the vertical detection of pollutant presence for the first time in a fuelling station. Two LNAPL-contaminated sites were selected for a pilot test. Experimental findings seem to support the use of vertical radon geochemical prospection to delimit the depth range of a LNAPL pollution directly. Systematic data collection and modeling may lead to a 3D reconstruction of the dispersion of contaminant in different soil levels.

Radon Hazard in Central Italy: Comparison among Areas with Different Geogenic Radon Potential.

Radon (222Rn) is a natural radioactive gas formed in rocks and soil by the decay of its parent nuclide (238-Uranium). The rate at which radon migrates to the surface, be it along faults or directly emanated from shallow soil, represents the Geogenic Radon Potential (GRP) of an area. Considering that the GRP is often linked to indoor radon risk levels, we have conducted multi-disciplinary research to: (i) define local GRPs and investigate their relationship with associated indoor Rn levels; (ii) evaluate inhaled radiation dosages and the associated risk to the inhabitants; and (iii) define radon priority areas (RPAs) as required by the Directive 2013/59/Euratom. In the framework of the EU-funded LIFE-Respire project, a large amount of data (radionuclide content, soil gas samples, terrestrial gamma, indoor radon) was collected from three municipalities located in different volcanic districts of the Lazio region (central Italy) that are characterised by low to high GRP. Results highlight the positive correlation between the radionuclide content of the outcropping rocks, the soil Rn concentrations and the presence of high indoor Rn values in areas with medium to high GRP. Data confirm that the Cimini-Vicani area has inhalation dosages that are higher than the reference value of 10 mSv/y.

PRE-ANTHROPIC AND PRESENT OUTDOOR GAMMA EQUIVALENT DOSE RATE OF THE HISTORIC CENTER OF ROME (ITALY).

The outdoor gamma background of the historic center of Rome was studied by in situ measurements and average values of the outcropping geological formations. The survey resulted in two maps of dose equivalent rate, related to pre-anthropic and present conditions. Presently, the average of the dose equivalent rate from outdoor gamma-ray field is equal to 0.31 µSv h-1, corresponding to an outdoor annual effective dose equivalent of 0.548 mSv a-1 and to an outdoor excess lifetime cancer risk [International Commission on Radiological Protection (ICRP). Recommendations of the ICRP, 21, 1/3, Publication 60, 1990] of 2.56 × 10-3. The originary radioactivity was enhanced by anthropic action up to a level of health risk comparable to that one deriving by fine particulate matter. The assessment of the evolution and dispersion of the outdoor gamma background offers a new perspective to study the urban architectural evolution. Such a mapping allows us to individuate mitigation actions and neighborhoods in which the monitoring of illicit trafficking of radioactive material can be efficiently tested.

Mapping the geogenic radon potential and radon risk by using Empirical Bayesian Kriging regression: A case study from a volcanic area of central Italy.

A detailed geochemical study on radon related to local geology was carried out in the municipality of Celleno, a little settlement located in the eastern border of the Quaternary Vulsini volcanic district (central Italy). This study included soil-gas and terrestrial gamma dose rate survey, laboratory analyses of natural radionuclides (238U, 226Ra, 232Th, 40K) activity in rocks and soil samples, and indoor radon measurements carried out in selected private and public dwellings. Soil-gas radon and carbon dioxide concentrations range from 6 to 253 kBq/m3 and from 0.3 to11% v/v, respectively. Samples collected from outcropping volcanic and sedimentary rocks highlight: significant concentrations of 238U, 226Ra and 40K for lavas (151, 150 and 1587 Bq/kg, respectively), low concentrations for tuffs (126, 123 and 987 Bq/kg, respectively), and relatively low for sedimentary rocks (108, 109 and 662 Bq/kg, respectively). Terrestrial gamma dose rate values range between 0.130 and 0.417 µSv/h, being in good accordance with the different bedrock types. Indoor radon activity ranges from 162 to 1044 Bq/m3; the calculated values of the annual effective dose varied from 4.08 and 26.31 mSv/y. Empirical Bayesian Kriging Regression (EBKR) was used to develop the Geogenic Radon Potential (GRP) map. EBKR provided accurate predictions of data on a local scale developing a spatial regression model in which soil-gas radon concentrations were considered as the response variable; several proxy variables, derived from geological, topographic and geochemical data, were used as predictors. Risk prediction map for indoor radon was tentatively produced using the Gaussian Geostatistical Simulation and a soil-indoor transfer factor was defined for a 'standard' dwelling (i.e., a dwelling with well-defined construction properties). This approach could be successfully used in the case of homogeneous building characteristics and territory with uniform geological characteristics.

(212)Pb as tracer for PM deposition on urban vegetation.

(212)Pb concentration in outdoor air is closely correlated with fine suspended particulate matter in the atmosphere. Thanks to this association, this isotope can be used to trace the sinking processes of particulate matter due to the vegetation, also providing accurate estimations of the deposition velocity on foliar surfaces. This approach is particularly effective in areas with high thoron fluxes and, consequently, high (212)Pb fluxes from soil. The contribution of vegetation to the improvement of air quality (AQImp) in the municipality area (MA) of Rome (Latium, Italy), almost entirely located on Th-enriched volcanic soils, was estimated by studying (212)Pb deposition velocity on the grasses (0.9-2.5mm·s(-1)) and on the most common tree classes, namely conifers (1.5-15mm·s(-1)), evergreen (1-4mm·s(-1)) and deciduous (0.2-1.5mm·s(-1)). (212)Pb activity in outdoor air was determined by gamma spectrometry after air pumping with accumulation on cellulose filters and after collection on artificial electrostatically charged surfaces (ECS). The high (212)Pb activity values obtained from this analysis (0.90±0.6Bqm(-3) and 0.58±0.15Bqm(-3), respectively near and far from the soil) are consistent both with the average regional thoron flux from volcanic soils (2.9·10(4)Bqm(-2)·h(-1)) and with the thoron flux measured in the volcanic soils of the study area. Thoron and (212)Pb fluxes were also measured both in laboratory and in the field under different soil moisture conditions. The total AQImp for the period from September 2014 to September 2015, calculated after the classification of the MA of Rome into six classes of vegetation, provided a value of 0.20 corresponding to 2.3 Tons per day of removed PM10. The role of grasslands in the PM10 removal, the contribution of the vegetation to the improvement of AQImp and the possibility of improving the sinking efficiency of green areas by increasing conifer trees coverage were also highlighted.

Bioaccessible selenium in Italian agricultural soils: Comparison of the biogeochemical approach with a regression model based on geochemical and pedoclimatic variables.

Biogeochemical mapping of selenium in Italian agricultural soils was accomplished by measuring the Se concentration of representative samples of wheat grains from 71 provinces. The range of the concentration values averaged on a provincial basis was 7-245 ng Se g(-1). A multiple regression model based on six geochemical and pedoclimatic variables was developed to interpret the observed data and to predict Se concentration of wheat in areas where analytical data were missing and in the different Italian soil regions. The statistical model explained only part of the observed variance, but succeeded in identifying Se-enriched as well as Se-depleted areas with an acceptable level of agreement with the biogeochemical map based on measured Se in wheat. Furthermore, the model showed that within the range of concentrations measured in Italian soils, Se-bioaccessibility is controlled not only by the Se content of the soil parent rocks, but also by their overall geochemical nature (carbonatic vs. silicatic) and by pedoclimatic variables (temperature and rain intensity excursions) related to fluctuations of soil moisture and pH. Overall, several Se-marginal and Se-deficient areas were identified on the Italian territory. The implications of these findings for public health are discussed briefly.

A methodology for assessing the maximum expected radon flux from soils in northern Latium (central Italy).

Northern Latium (Italy) is an area where the Rn risk rate is potentially high because of the extensive outcropping of Neogene U-rich volcanics and the presence of major active tectonic lineaments. The lack of data on Rn risk rates in that area, which is undergoing major urban and industrial development, has prompted this study. It proposes a methodology to evaluate the maximum potential diffusive Rn flux from soils based on the measurement of (226)Ra, (232)Th and (40)K activities by gamma-ray spectrometry, and the measurement of main soil parameters influencing the Rn emanation. This methodology provides a simple, reliable and low-cost tool for drawing up radon flux maps useful to both public planners and private individuals, who want to operate safely in the study area. The proposed methodology may also be applied to other geographic areas outside the prescribed study area.