Evaluation of novel biomass-derived materials as binding layers for determining labile mercury in water by diffusive gradient in thin-films technique

Abstract

In this work, several binding gels were successfully prepared in Diffusive Gradient in Thin-film (DGT) that targeted the inclusion of novel biomass-derived materials for the determination of the labile fraction of mercury (Hg) in water. First, five biomass-derived materials were tested and the descending order as a function of the average percentage of Hg removal in solution was feathers > biochar > cork > canola meal > rice husk. The best two materials were treated and pulverized into powder to be embedded in a hydrogel; and so, feathers were pyrolyzed preserving the sulfur contained in their keratin structure (FBC), and biochar (BC) was modified and pyrolyzed with sublimated sulfur (SBC) to increase the Hg sorption sites in its structure. Analysis by Energy Dispersive X-ray fluorescence (EDXRF) spectrometry confirmed that the different pyrolysis procedures increased sulfur absorption successfully. The efficiency of the new gels (BC, SBC and FBC) in agarose was evaluated by comparative Hg uptake tests, showing a larger efficacy in the following order: SBC > BC > FBC. To assess the suitability of their application in freshwater environments, novel DGT devices were also evaluated to determine their diffusion coefficients (D). This test was conducted under controlled laboratory conditions, with particular focus on the potential competence of trace elements (Mn, Cu, Zn, Ni, Pb, Cd and As), which are commonly present in natural waters affected by mining. A stronger linear relationship between the Hg uptake by binding layers and the deployment time were obtained for the DGT devices with SBC (R² = 0.948) vs. BC (R² = 0.885). Therefore, the D obtained for Hg were 8.94 × 10^-6 cm² s^-1 for DGT-SBC and 5.12 × 10^-6 cm² s^-1 for DGT-BC devices at 25 °C, both within the same order of magnitude reported by previous studies. The good performance obtained by DGT-SBC devices is a promising result and indicates the potential for valorization of waste materials in the DGT technique.

Keywords: Binding gel; Biochar; Biomass-derived material; Diffusive gradients in thin films; Feathers; Labile mercury; Pyrolysis.