New Electrochemical Sensor for Hg(II) Trace Detection in Natural Waters: Electrode Functionalization with Gold Nanoparticles and Diazonium Salts
Authors: Fezai Fatma , Gros Pierre , Meireles Martine , Evrard David 
Published: February 2020

Mercury (Hg) represents a growing environmental and health major concern. It originates from natural sources and mainly from anthropogenic processes and it is widely distributed in the natural media. According to the last Global Mercury Assessment (2013), annual global emissions from both sources were estimated to be from 5,000 to 8,000 metric tons per year. Among the different mercury species released to the environment, methylmercury (MeHg) is considered as the most toxic form due to its ability to bioaccumulate, being then threatening even at very low concentrations.Its presence depends onHg(II) bioavailability and global amount.This explains the urgent need to ensure a continuous Hg(II) monitoring. Many efforts have been made in order to develop reliable systems able to deliver quick data and to comply with low detection limits, in accordance with the threshold value delivered by the World Health Organization (1µg L-1/ 5 nM).
Spectroscopic techniques such as CV-AFS and CV-AAS are routinely used for Hg(II) determination. Although these methods can afford good sensitivity and low concentrations determination, they require sample preparation step, complex procedures and expensive material, which limits their use for on-site measurements. In this context, electrochemical sensors present excellent candidates for in situ Hg(II) trace analysis, taking in account their numerous advantages compared to spectroscopic techniques: easier handling, simple procedure, low energy consuming, low cost material and portability. In this work, we will propose a new electrochemical approach aiming to conceive and optimize an electrochemical Hg(II) sensor. The method consists in the functionalization of a glassy carbon electrode (GC) with gold nanoparticles (AuNPs) and Diazonium Salts. The main idea is to combine the interesting properties of both AuNPs and Diazonium salts. AuNPs were chosen for their electrocatalytic effect, large surface area, mass transport enhancement and for the strong affinity to mercury which will improve the sensor sensitivity. On the other hand, diazonium salts are used to improve the sensor stability by anchoring the AuNPs to the GC surface. First, nanometricorganic layer were grafted of the polished GC surface, by electrochemical reduction of 1.5 mM4-thiophenol diazonium (SH) using Constant Potential Electrolysis (CPE) in 0.1 M HCl solution at -0.55 V for 300 seconds. Electrochemical characterization performed by Cyclic Voltammetry (CV) and redox probes (ferricyanide and hexaamineruthenium(III)) revealed a total suppression of the signal, confirming the formation of a continuous blocking layer. This was confirmed by Atomic Force Microscopy (AFM)used to estimate the layer thickness, which was found to be 4 nm. Second, AuNPs were electrodeposited, for the first time, onto the diazonium multilayer by CPE in NaNO3 solution containing 0.25 mM HAuCl4for 300 seconds. Once more, redox probes were used to characterize the resulting interface and a total signal restauration and enhancement was observed after AuNPs electrodeposition, which highlights the effective AuNPs onto the organic layers. Field emission gun scanning microscopy (FEG-SEM) was used to provided further evidence and to quantify particle size and density of the AuNPs deposits. Both size and density are dependent on the CPE duration. Small homogeneous AuNPs with 27±3 nm average diameter and 158 NPs/µm2density were observed when the CPE was carried out during 300 seconds, while larger particles with 63±6 nm average diameter and lower density (63 NPs/µm2) were obtained when a longer CPE duration (600 seconds) is used. Finally, AuNPs were activated by cyclic voltammetry in H2SO4 prior to Hg(II) detection in order to homogenize the surface and to rearrange the crystallographic plans of the AuNPs. Herein, the well-known gold oxides reduction peak was observed and used to calculate the electroactive surface area (ESA) of the functionlized electrode.
The electrochemical response of the final generated GC/SH/AuNPs interface towards Hg(II) was recorded by Square Wave Anodic Stripping Voltammetry (SWASV) in 0.01 M HCl solution containing different amounts of Hg(II). The SWASV procedure consists on the Hg(II) preconcentration at the electrode surface followed by the preconcentrated Hg(0) reoxidation in Hg(II). Under optimized conditions, and for a preconcentration time of 300 seconds, a well-defined peak, corresponding to Hg(0) reoxidation, was observed around 0.5 V/ECS. The sensor showed a linearity range from 1 up to 10 nM and allowed to reach picomolar level. The stability in HCl, phosphate buffer and air was also studied over several weeks: Once a week, the activation procedure was performed and followed by Hg(II) determination in order to evaluate the analytical performances of the sensor over time. Finally, Hg(II) detection assays were conducted in natural water samples collected from different sampling points.

Figure 1