Radiometric dating of Light Non-Aqueous Phase Liquids (LNAPLs) dispersed in soil: A low environmental impact tool for natural resource restorations and protection

Non-polar liquids released in environment cause a long-term soil and groundwater contamination. The costs associated with a multi-year remediation are high and the uncertainty in the allotment of legal responsibilities could defer the decontamination planning. Therefore, a reliable method to assess the residence time of spilled Non-Aqueous Phase Liquids (NAPLs) in soil is highly needed. In this paper, a method, using low environmental radioactivity and radiometric dating, is described and applied to real contaminations. After being alpha-recoiled from 232Th in soils,228Ra accumulates in light NAPLs, generating 228Th. A disequilibrium clock, based on ?-spectrometric determination of the ratio 228Th/228Ra, was conceived to measure the residence time of LNAPL pollutants in a soil. The pollutant extraction and ?-counting procedures are described. This approach inverts the role played by pollutants and contaminated matrixes, because the flux of alpha recoil from soil generates in pollutants a reliable model of "closed system", which is preserved in LNAPLs due to the peculiar properties of non-polar liquids. All case studies are sited in Italy and have been supported by preliminary lab tests. Dating tests of 15 samples (including LNAPLs, contaminated soils and oil socks) were performed, in most cases, blindly. Then, the results were compared to historical data about contaminations. A good correlation between test results and site history was generally obtained. But an increasing error has to be considered in old contaminations due to the nonlinear nature of disequilibrium time equation. Other reasons of discrepancies, due to system opening, include the use of surfactants, the presence of significant amount of MnO2 in soil and the interactions of different spillages. The outcomes of this research evidence the possibility to precisely date the contamination both in soil and in non-polar liquids, offering a potential tool to settle legal disputes. Further studies could broad and improve the applicability of the method.