Abstract

Problem statement: Physical and chemical properties of soil, groundwater and pollutants deeply influenced the type and the strength of sorption phenomena involving hydrophobic organic contaminants: Soil fraction of organic carbon (foc) and cation exchange capacity, groundwater pH and pollutants hydrophobicity were with undoubtedly the predominant issues. Approach: In this study an experimental study of the sorption of phenol and 2-nitrophenol on three soils was performed considering three initial pH values, with the aim to evaluate the soil/pollutant interactions as a function of the relative abundance of the neutral contaminants and phenolate species and of the solid phase properties. Results: The considered soil samples (a silty clay, a silt and a sand coming from northern Italy) underwent to a physical and chemical characterization: Particle-size, mineralogical and chemical analyses were performed. The experimental data coming from some batch tests, carried employing aqueous phases containing different concentrations of phenol and 2-nitrophenol at initial pH values equal to 4, 7 and 10, were fitted by means of several isotherm models. Three Dual Mode Models (DMM), employing different isotherm models to represent the sorption of the neutral and the anionic species of the pollutants, were evaluated by the researchers to simulate the sorption of phenol and 2-nitrophenol in the examined conditions. Conclusion: The soil/contaminant interaction mechanisms determining the isotherm shapes were discussed: foc appeared to be the main issue, although the nitro-group was able to promote sorption. In all considered soil samples and at all initial pH values, the highest foc (found in the silty soil) and the presence of the nitro-group determined the highest amounts of pollutant transferred on the solid phase. The two DMMs proposed by the researchers, implying nonlinearity, showed a higher reliability in simulating experimental data compared to a DMM based on linear sorption isotherms. Main sorption mechanisms were controlled by the partitioning of neutral pollutants in soil organic matter, but also the interactions between the pollutants, both in phenolate and in neutral forms and the soil mineral surface played a primary role.

Highlights

  • The factors supervising sorption of Hydrophobic Organic Contaminants (HOCs) depend on the physical and chemical properties of the soil, of the pollutants and of the groundwater

  • The most important limit of LFERs is the assumption that the sorption is due exclusively to the partitioning of the un-dissociated pollutant in soil organic fraction, ignoring adsorption and they aren’t able to explain the nonlinearity of sorption phenomena

  • The calculation of the coefficients KD, theoretical(1) and KD, theoretical(2) presumes a neglectable difference between the values referred to pH 4 and the ones referred to pH 7, because both LFERs (Eq 1 and 2) don’t consider the adsorption of the un-dissociated phenols and the pH dependence of these processes

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Summary

Introduction

The factors supervising sorption of Hydrophobic Organic Contaminants (HOCs) depend on the physical and chemical properties of the soil, of the pollutants and of the groundwater. The Soil Organic Matter (SOM) content is the predominant issue: Considering the sorption of HOCS on soils characterized by an appreciable amount of organic carbon (foc>0.001), absorption is commonly assumed to be the main interaction mechanism. Both linear and nonlinear isotherms have been reported to describe the absorption of HOCs: The homogeneous ideal structure of the SOM is a concept exceeded and the heterogeneity of the SOM has been demonstrated[1,2]. The most abundant are the silanolic groups

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