Modelling biogeochemical reactions triggered by graphene's addition in a fertilized calcareous sandy soil

Luigi Alessandrino; Nicolò Colombani; Micòl Mastrocicco

doi:10.1016/j.scitotenv.2023.165558

Modelling biogeochemical reactions triggered by graphene's addition in a fertilized calcareous sandy soil

Sci Total Environ. 2023 Nov 10:898:165558. doi: 10.1016/j.scitotenv.2023.165558. Epub 2023 Jul 15.

Authors

Luigi Alessandrino¹, Nicolò Colombani², Micòl Mastrocicco¹

Affiliations

¹ DiSTABiF - Department of Environmental, Biological and Pharmaceutical Sciences and Technologies, Campania University "Luigi Vanvitelli", Via Vivaldi 43, 81100 Caserta, Italy.
² SIMAU - Department of Materials, Environmental Sciences and Urban Planning, Marche Polytechnic University, Via Brecce Bianche 12, 60131 Ancona, Italy. Electronic address: n.colombani@univpm.it.

PMID: 37459980
DOI: 10.1016/j.scitotenv.2023.165558

Abstract

Graphene production has dramatically increased in the last years and new ways to recycle this engineered material need to be investigated. To this purpose, a reactive model network was developed using PHREEQC-3 code to quantify the relevant biogeochemical reactions induced by graphene scraps' incorporation in a calcareous sandy soil. The numerical model was calibrated versus a complete dataset of column experiments in water saturated conditions using two different fertilizers, a synthetic NPK fertilizer and fertigation water produced in a wastewater treatment plant. Column experiments consisted of 50 cm columns filled with a mixture of graphene scraps (0.015 % dry weight) and soil in the first 10 cm, while the remaining 40 cm had only soil. The model performance was tested using classical statistical indices (R², Modelling Efficiency, and Index of Agreement), resulting to be satisfactory. Besides, a simple sensitivity analysis via the perturbation of relevant parameters showed a low degree of uncertainty. The main outcome of this study was the quantification of the increased denitrification rate triggered by graphene incorporation into the soil. Moreover, graphene incorporation substantially increased soil CEC and DOC sorption capacity, demonstrating a good adsorption capacity for ammonium and organic compounds, thus decreasing nutrients leaching that represents a major concern related to agricultural practice. Indeed, Graphene incorporation increased by 40 % the CEC in the first 10 cm of the CSG_NPK column (2.50e^-02 mol/L) respect to the CS_NPK column (1.75e^-02 mol/L) and increased it by 150 % in the first 10 cm of the CSG_FW column (2.50e^-02 mol/L) in comparison with the CS_FW column 1.00e^-02 (mol/L). pH fluctuations were most likely due to the precipitation of Ca₅(PO₄)₃OH, indeed the consumption of H⁺ ions could have triggered the pH lowering during the experiment. These results could be relevant for future graphene applications as a soil improver or as suitable material to enhance soil bioremediation in order to include graphene in a circular economy loop.

Keywords: Column experiments; Denitrification; Numerical model; Nutrients leaching; Reactive transport.