Electrochemical detection of selected heavy metals in water: a case study of African experiences.

The safety of water resources throughout the globe has been compromised by various human activities and climate change over the last decades. Consequently, the world is currently confronted with a severe shortage of water supply and a water safety crisis, amidst a growing population. With poor environmental regulations, indiscriminate budding of urban slums, poverty, and a lack of basic knowledge of hygiene and sanitation, the African water supply has been critically threatened by different organic and inorganic contaminants, which results in several health issues. Inorganic pollutants such as heavy metals are particularly of interest because they are mostly stable and non-biodegradable. Therefore, they are not easily removed from water. In different parts of the continent, the concentration of heavy metals in drinking water far exceeds the permissible level recommended by the World Health Organization (WHO). Worse still, this problem is expected to increase with growing population, industrialization, urbanization, and, of course, corruption of government and local officials. Most of the African population is ignorant of the standards of safe water. In addition, the populace lack access to affordable and reliable technologies and tools that could be used in the quantification of these pollutants. This problem is not only applicable to domestic, but also to commercial, communal, and industrial water sources. Hence, a global campaign has been launched to ensure constant assessment of the presence of these metals in the environment and to promote awareness of dangers associated with unsafe exposure to them. Various conventional spectroscopic heavy metal detection techniques have been used with great success across the world. However, such techniques suffer from some obvious setbacks, such as the cost of procurement and professionalism required to operate them, which have limited their applications. This paper, therefore, reviews the condition of African water sources, health implications of exposure to heavy metals, and the approaches explored by various indigenous electrochemists, to provide a fast, affordable, sensitive, selective, and stable electrochemical sensors for the quantification of the most significant heavy metals in our water bodies.

Electrochemical Characterization and Detection of Lead in Water Using SPCE Modified with BiONPs/PANI.

The need for constant assessment of river water qualities for both aquatic and other biological survival has emerged a top priority, due to increasing exposure to industrial pollutants. A disposable screen print carbon electrode was modified with a conductive polymer (PANI) and Zn and/or Cu oxides NPs, obtained through bioreduction in citrus peel extracts (lemon and orange), for ultra-sensitive detection of PB2+, in the Crocodile River water sample. The synthesized materials were characterized with Fourier-transform infra-red spectroscopy (FTIR), ultra-violet visible spectroscopy (UV-Vis), and scanning electron microscopy (SEM). The SPC-modified electrodes designated as SPCE/LPE/BiONPs/PANI and SPCE/OPE/BiONPs/PANI were characterized using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) and eventually deployed in the electrochemical detection of PB2+ in water using square wave voltammetry (SWV) technique. The electrochemical responses of the modified electrodes for both CV and EIS in 0.1 M HCl demonstrated enhanced performance relative to the bare SPCE. A detection and quantification limit of 0.494 ppb and 1.647 were obtained at SPCE/LPE/BiONPs/PANI, respectively, while a detection and quantification limit of 2.79 ppb and 8.91 ppb, respectively, were derived from SPCE/OPE/BiONPs/PANI. The relative standard deviations (RSD) for SPC electrode at a 6.04 µM PB2+ analyte concentration was 4.76% and 0.98% at SPCE/LPE/BiONPs/PANI and SPCE/LPE/BiONPs/PANI, respectively. The effect of copper, zinc, iron, cobalt, nickel, and magnesium on the stripping peaks of PB2+ at SPCE/OPE/BiONPs/PANI, showed no significant change except for cobalt, with about 17.67% peak current drop. The sensors were assessed for possible determination of PB2+ in spiked river water samples. The average percentage recovery and RSD calculated were 94.25% and 3.74% (n = 3) at SPCE/LPE/BiONPs/PANI and, 96.70% and 3.71% (n = 3) at SPCE/OPE/BiONPs/PANI, respectively. Therefore, the fabricated sensor material could be used for environmental assessment of this highly toxic heavy metal in the aquatic system.

Green synthesis of copper oxide nanoparticles using extracts of Solanum macrocarpon fruit and their redox responses on SPAu electrode.

In this work, CuO nanoparticles (NPs) were prepared from the aqueous extracts of Solanum macrocarpon fruit by using the conventional heating (CuO(h) NPs) and microwave irradiation (CuO(m) NPs) methods. The synthesized nanoparticles were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD). The SEM analysis revealed that the CuO NPs from both routes contained essentially smooth surfaces, and displayed some degree of agglomeration. The TEM analysis confirmed some spherical morphology with mean particle sizes of 35.60 ± 6.24 nm and 47.14 ± 6.18 nm for the CuO(h) and CuO(m) NPs respectively. While the CuO(m) NPs possessed a single-phase consistent with the face cantered cubic structure of copper oxide, the CuO(h) NPs showed some extra peaks attributed to Cu2O NPs as secondary phase. Electrochemical studies were conducted in order to evaluate the electrochemical properties of the NPs. The responses of a gold screen-printed electrode surface treated with both NPs showed that their redox behaviours on (Fe(CN)6)3-/4- probe and KCl electrolytes vary significantly. In (Fe(CN)6)3-/4- probe, the SPAuE/CuO(h) showed enhanced electrochemical response relative to the bare, while the SPAuE/CuO(m) showed a lower current response than the bare. However, in the KCl electrolye, the SPAuE/CuO(h) and SPAuE/CuO(m) were highly electroactive and demonstrated peak current magnitude that was about 26.5 and 83.38 times higher than that of the bare. In this KCl medium, the magnitude of the oxidation peak current of Cu2+ for SPAuE/CuO(m) was about 3 times higher than that of SPAuE/CuO(h). The percentage contraction in redox coordinates between the 1st and 10th scans in both electrodes were 3.88 and 19.28% for SPAuE/CuO(h) and SPAuE/CuO(m) respectively. Thus, the choice of green synthesis route could be exploited in different fields where green NPs is desired.

Green Wastes Mediated Zinc Oxide Nanoparticles: Synthesis, Characterization and Electrochemical Studies.

Zinc Oxide (ZnO) nanoparticles were prepared using a simple green synthesis approach in an alkaline medium, from three different extracts of citrus peels waste. The synthesized nano-crystalline materials were characterized by using ultraviolet-visible spectroscopy (UV-vis), x-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), energy-dispersive x-ray spectroscopy (EDS), environmental scanning electron microscopy (ESEM), and transmission electron microscopy (TEM). UV-vis analysis of the nanoparticles showed broad peaks around 360 nm for the ZnO NPs (Zinc oxide nanoparticles) from three citrus peels' extracts. ZnO NPs exhibited Zn-O band close to 553 cm-1, which further verified the formation of the ZnO NPs. A bandgap of 3.26 eV, 3.20 eV and 3.30 eV was calculated for the ZnO NPs from grape (ZnO NPs/GPE), lemon (ZnO NPs/LPE), and orange (ZnO NPs/OPE) peels extract, respectively. The average grain sizes of the ZnO nanoparticles were evaluated to be 30.28 nm, 21.98 nm, and 18.49 nm for grape (ZnO NPs/GPE), lemon (ZnO NPs/LPE), and orange (ZnO NPs/OPE) peel extract, respectively. The surface morphology and sizes of the nanoparticle were confirmed by ESEM and TEM analysis, respectively. Furthermore, the zeta potential of the as-prepared ZnO NPs from OPE, LPE, and GPE was -34.2 mV, -38.8 mV, and -42.9 mV, respectively, indicating the high stability of the nanoparticles. Cyclic voltammetric properties of the synthesized nanoparticles were investigated across extracts, and the results showed that the citrus peels extracts (CPE) mediated ZnO NPs modified screen plate carbon (SPC/ ZnO NPs/CPE) electrodes exhibited enhanced catalytic properties when compared with the bare SPCE. The electroactive areas computed from the enhancement of the bare SPCE was approximately three times for SPCE/ ZnO NPs/LPE, and SPCE/ZnO NPs/GPE, and two times for SPCE/ZnO NPs/OPE, higher than that of the bare SPCE. Comparison across the extracts suggested that the catalytic properties of the nanoparticles were unique in ZnO NPs from GPE.