Accumulation and colloidal mobilization of trace heavy metals in soil irrigated with treated wastewater

Reuse of treated wastewater for agricultural purposes is worldwide accepted and practiced to face water scarcity and save high quality resources. Although such practice has undoubtable advantages and is certainly more sustainable respect to the use of fresh water, it is not exempt from severe concerns related to the potential impact on the receiving soil and on the crops of potentially harmful pollutants contained in the reused water at trace levels. Among these pollutants, trace heavy metals (HMs) play a primary role due to their spread presence in the used water and to their persistence once released in the environment. The fate of HMs in the soils can be hardly predicted as mechanisms of mobility through soils are extremely diverse and related to highly complex simultaneous phenomena and chemical equilibria. HMs, in fact, as many other contaminants, are not only partitioned between the solid immobile and the water mobile phases. Indeed, colloids and nanoparticles act as a third mobile phase, with their own rheological properties and velocity. This latter aspect has been one of the main focus of the thesis. In details the thesis describes the results of several experiments conducted irrigating the OECD standard soil with real and/or synthetic wastewater, containing HMs in trace. For each test a specific soil (e.g. varying the organic matter content) and wastewater composition (e.g. varying the metals concentration, the salinity, the organic matter content, or testing real treated wastewaters) has been chosen in order to evaluate the effects of different conditions on the overall HMs fate. The increase of soil organic matter from 2,5 to 10% linearly enhanced the mobility of Cd, Cu and Ni up to a maximum mobility increase of 35.6, 43.7 and 49.19 % for Cd, Cu and Ni, respectively. In most experiments metals accumulated in the top soil layer (0.5 - 1 cm). Nevertheless peaks of contamination were detected at different depths in the soil deeper layers and at different leaching time in the leachates depending on the metal and on the soil and wastewater characteristics. Peaks of metals in the leachate appeared simultaneously with release of organic matter and/or release of silicates, demonstrating outstanding involvement of colloids in metals transport. Sodium concentration (20mM) decidedly reduced colloidal mobilization whereas more than 95 % of the influent metal was detected in the top layer despite the soil organic matter content. Salinity displayed different effects. The irrigation with real treated wastewater with quite high content of Ca and Mg (111 and 134 mg/L, respectively) resulted in higher average release of silicon from the soil inorganic matrix (8.2 mg/L) compared to the low salinity artificial wastewater (1.9 mg/L). Consequently higher mobilization of Cd, Cu, Ni and Zn was observed when the soil was irrigated with real treated wastewater. An advanced spectroscopical characterization of the leachates was performed to identify such colloidal aggregates. The observation of 3D excitation-emission matrix demonstrated in all the leachates samples the presence of fulvic (230-450 nm ex-em fluorescence area) and humic (330-445 nm ex-em) substances. In this context, a novel analytical method was developed to quantify phenolic substances in soil matrices allowing the monitoring of humic matter migration in soil profiles. The novel method was more accurate and more precise respect to the traditional one, allowing to obtain higher recovery of total phenols in peat soil (15.5 % increase) with a decrease of the coefficient of variation (30.1% decrease). Organic water soluble colloids were extracted from the peat used to prepare the OECD standard soil and characterized. Results of size exclusion chromatography highlighted the supramolecular structure of the extracted organic matter. Such structure was further confirmed through fluorescence and 1H-NMR spectroscopy