Soil organic matter (SOM) significantly impacts the detection accuracy of Cd2+ and Pb2+ using square wave anodic stripping voltammetry (SWASV) due to the complexation of SOM to heavy metal ions (HMIs), thereby attenuating SWASV signals. This study explored an effective pretreatment method that combined low-pressure ultraviolet (LPUV) photolysis with the ZnO/g-C3N4 photocatalyst, activating the photocatalyst to generate highly oxidative •OH radicals and O2•- radicals, which effectively disrupted this complexation, consequently restoring the electroactivity of HMIs and achieving high-fidelity SWASV signals. The parameters of the LPUV-ZnO/g-C3N4 photocatalytic system were meticulously optimized, including the pH of photolysis, duration of photolysis, g-C3N4 mass fraction, and concentration of the photocatalyst. Furthermore, the ZnO/g-C3N4 photocatalyst was thoroughly characterized, with an in-depth investigation on the synergistic interaction between ZnO and g-C3N4 and the mechanisms contributing to the restoration of SWASV signals. This synergistic interaction effectively separated charge carriers and reduced charge transfer resistance, enabling photogenerated electrons (e-) from the conduction band of g-C3N4 to be quickly transferred to the conduction band of ZnO, preventing the recombination of e- and hole (h+) and generating more radicals to disrupt complexation and restore the SWASV signals. Finally, the analysis of HMIs in real soil extracts using the proposed pretreatment method demonstrated high detection accuracy of 94.9% for Cd2+ and 99.8% for Pb2+, which validated the feasibility and effectiveness of the proposed method in environmental applications.

Present work reports, the development of a novel electrochemical sensor based on a diazonium-coupling reaction and covalent attachment of the -NH2 group of cysteamine (Cyst) on screen-printed carbon electrode (SPCE), for simultaneous determination of Pb(II) and Cd(II). Initially, the in-situ generated 4-carboxyphenyl (4-CP) diazonium salt was electro-grafted to generate 4-CP/SPCE, followed by covalent bonding of terminal carboxylic group of 4-CP with -NH2 group of Cyst to give Cyst/4-CP/SPCE. The modified electrode showed an enhanced selectivity and sensitivity toward the quantification of Pb(II) and Cd(II) using square wave anodic stripping voltammetry (SWASV) without mutual interference. Under optimal experimental conditions, the newly designed sensor showed a wide linear range of 0.01 µM to 0.7 µM. The limit of detection (LOD) obtained was 0.882 nM (0.09 ppb) and 0.65 nM (0.134 ppb) for Cd(II) and Pb(II), respectively. The modified SPCE exhibited good stability, selectivity, and reproducibility. Furthermore, the sensor was successfully applied for the determination of Pb(II) and Cd(II) ions in water samples which illustrated excellent recoveries in different spiked samples and the results were in line with the standard ICP-AES analysis.

A novel cost-effective disposable porous graphene electrode (P-GE) modified with bismuth nanoneedles (nano-BiNDs) is proposed as a \"mercury-free\" sensor for detecting heavy metals through smartphone-assisted electrochemical sensing. The P-GE was fabricated using screen-printing. Nano-BiNDs were generated on the P-GE by potentiostatic electrodeposition. Using an optimal potential of -1.20 V (vs. pseudo-Ag/AgCl) and a deposition time of 200 s, the nano-BiNDs had an average length and width of 189 ± 5 nm and 20 ± 2 nm, respectively. The analytical performances of the fabricated sensing platform were demonstrated by detecting Cd2+ and Pb2+ using square-wave anodic stripping voltammetry (SWASV) under optimized conditions. In the optimal conditions, the fabricated sensor exhibited sharp, well-defined stripping peaks for Cd2+ and Pb2+ with excellent peak-to-peak separation. The linear detection ranges were from 0.01 to 50 μg mL-1 for Cd2+ and 0.006-50 μg mL-1 for Pb2+. The detection limits for Cd2+ and Pb2+ were 3.51 and 2.10 ng mL-1, respectively. The developed portable sensor demonstrated high sensitivity, good repeatability, reproducibility, and anti-interference properties. The proposed portable sensor quantified Cd2+ and Pb2+ in commercial seaweed products with good accuracy, consistent with the results obtained using the standard ICP-OES method.

The environmental behavior of arsenic (As) has garnered significant attention due to its hazardous nature. The fate of As often couples with sulfide, thus co-detecting arsenic and sulfide on-site is crucial for comprehending their geochemical interactions. While electrochemical methods are suitable for on-site chemical analysis, there currently exists no electrode capable of simultaneously detecting both arsenic and sulfide. To address this, we developed a dual-metal electrode consisting of iron oxide-encased carbon cloth loaded with gold nanoparticles (Au/FeOx/CC) using the electrochemical deposition method. This electrode enables square wave stripping voltammetry (SWASV) binary detection of As and sulfide. Comparison experiments reveal that the reaction sites for sulfide primarily reside on FeOx, while the interface synergy of iron oxide and gold nanoparticles enhances the response to arsenite (AsIII). Arsenate (AsV) is directly reduced to As0 on Fe0, obviating the need for an external reducing agent. The electrode achieves detection limits of 1.5 μg/L for AsV, 0.25 μg/L for AsIII, and 11.6 μg/L for sulfide at mild conditions (pH 7.8). Field validation was conducted in the Tengchong geothermal hot spring region, where the electrochemical method exhibited good correlation with the standard methods: Total As (r = 0.978 vs. ICP-MS), AsIII (r = 0.895 vs. HPLC-ICP-MS), and sulfide (r = 0.983 vs. colorimetric method). Principal component analysis and correlation analysis suggest that thioarsenic, could potentially be positive interferents for AsIII. However, this interference can be anticipated and mitigated by monitoring the abundance of sulfide. The study provides new insights and problems for the electrochemical detection of coexisted As and sulfide.

Exposure to thallium (Tl), a noxious heavy metal, poses significant health risks to both humans and animals upon ingestion. Therefore, monitoring Tl levels in the environment is crucial to prevent human exposure and reduce the risk of developing severe health problems. This paper presents the development of a highly sensitive Tl ions sensor through surface modification of a glassy carbon electrode with a nanocomposite comprising MnO2 magnetic sepiolite and multi-walled carbon nanotubes (MnO2@Fe3O4/Sep/MWCNT/GCE). Multiple methodologies were employed to assess the performance of the newly developed sensor. By employing square wave anodic stripping voltammetry (SWASV) to optimize the measurement conditions, notable enhancements were observed in the stripping peak currents of Tl (I) on the MnO2@Fe3O4/Sep/MWCNT/GCE surface. The effectiveness of the nanocomposite in facilitating electron transfer between the Tl (I) ions (guest) and the electrode (host) was demonstrated from the enhanced signals observed at the different modified electrode surfaces under optimal conditions. The developed sensor displayed a wide linear range of 0.1-1500 ppb for Tl (I) and a low detection limit of 0.03 ppb for Tl (I). It was found to be selective for Tl (I) ions while remaining unaffected by interfering non-target ions in the presence of the target ions. Despite its simple preparation procedure, the modified electrode exhibited high stability and excellent reproducibility for measuring Tl (I). The outstanding electroanalytical performances of the MnO2@Fe3O4/Sep/MWCNT/GCE electrode enabled its successful use as an ultrasensitive sensor for determining trace amounts of Tl in environmental samples.

In this study, a new carbon paste electrode modified with a laboratory-synthesized ligand, N1-hydroxy-N1,N2-diphenylbenzamidine (HDPBA) and multi-walled carbon nanotubes (MWCNTs) (HDPBA‒MWCNTs/CPE) has been developed. The modified electrode was applied for preconcentration and voltammetric determination of zinc ions (Zn(II)) by square wave anodic stripping voltammetry (SWASV). The preconcentration of Zn(II) on the electrode surface was performed in 0.1 M Brinton Robinson (B-R) buffer solution (pH 6) at an applied potential of -1.30 V versus Ag/AgCl for 120 s, followed by stripping in the positive potential scan of the SWASV after a quit time of 10 s. Under optimized experimental conditions, the proposed electrode exhibited a wider linear dynamic response for Zn(II) in a concentration range of 0.02-10.00 μM with a detection limit of 2.48 nM. This is due to the excellent metal-chelation property of the ligand, and the good conductivity and large surface area of MWCNTs which significantly improved the sensing performance of the nanocomposite modified electrode. The selectivity of the electrode was studied by evaluating the interference effects of various foreign ions on the peak current of Zn(II). The method exhibited high reproducibility with a relative standard deviation (RSD) of 3.1%. The present method was applied for the determination of zinc ions in water samples. The recovery values in the tested samples were found to be 98.50-106.0%, indicating a good accuracy of the proposed electrode. Furthermore, the electrochemical behavior of HDPBA in acetonitrile and aqueous solutions has been studied.

Fruitful achievements on electrochemical detection toward Pb(II) have been achieved, and their good performance is generally attributed to the adsorption property of nanomaterials. However, the design of sensing interfaces from the electronic structure and electron transfer process is limited. Here, Co@Co3O4 acquired an ultra-high detection sensitivity of 103.11 µA µM-1 toward Pb(II), outperforming the results previously reported. The interfacial oxygen atoms build an electron bridge for Co activating Co3O4. Particularly, new energy levels of oxygen atoms were generated and matched with that of Pb(II). The strong orbital coupling effect between O and Pb makes the Co@Co3O4 sensitive and selective toward Pb(II). Compared with Co metal and Co3O4, Pb(II) got more electrons from Co@Co3O4, and longer Pb-O bonds were formed, allowing more Pb(II) to be catalyzed and reduced. Also, the superior stability and reproducibility of electrochemical detection make electrodes practicably. This work reveals that metals can stimulate intrinsically catalytic activity of their metal oxides, with the generation of orbit energy levels that match to a specific analyte. It provides a promising strategy for constructing sensitive and selective sensing interfaces toward ultra-low concentration analyte in body fluid and other complex samples.

There is a huge demand for rapid, reliable and low-cost methods for the analysis of heavy metals in drinking water, particularly in the range of sub-part per billion (ppb). In the present work, we describe the preparation, characterization and analytical performance of the disposable sensor to be employed in Square Wave Anodic Stripping Voltammetry (SWASV) for ultra-trace simultaneous determination of cadmium and lead. The electrode consists of graphene paper-perfluorosulfonic ionomer-bismuth nano-composite material. The electrode preparation implies a key step aimed to enhance the Bi3+ adsorption into nafion film, prior to the bismuth electro-deposition. Finely dispersed bismuth nanoparticles embedded in the ionomer film are obtained. The electrode was characterized by Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDX), Atomic Force Microscopy (AFM), X-ray Photoelectron Spectroscopy (XPS) and Electrochemical Impedance Spectroscopy (EIS). The electrode shows a linear response in the 5-100 ppb range, a time-stability tested up to almost three months, and detection limits up to 0.1 ppb for both Pb2+ and Cd2+. The electrode preparation method is simple and low in cost and the obtained analytical performance is very competitive with the state of art for the SWASV determination of Pb2+ and Cd2+ in solution.

In this work, we explore the protection with Nafion of commercial sputtered-bismuth screen-printed electrodes (BiSPSPEs), to improve its ability for on-site determination of Cd(II) and Pb(II) ions in ambient water samples. The modified screen-printed platform was coupled with a miniaturized cell, in combination with a battery-operated stirring system and a portable potentiostat operated by a laptop for decentralized electrochemical measurements using Square-Wave Anodic Stripping Voltammetry (SWASV). We also describe a detailed electrode surface characterization by microscopy and surface analysis techniques, before and after the modification with Nafion, to get insight about modification effect on signal size and stability. Optimization of the chemical composition of the medium including the optimization of pH, and instrumental parameters, resulted in a method with detection limits in the low ng/mL range (3.62 and 3.83 ng·mL-1 for Cd and Pb respectively). Our results show an improvement of the sensitivity and stability for Nafion-protected BiSPSPEs in pH = 4.4 medium, and similar or lower detection limits than comparable methods on commercial BiSPSPEs. The values obtained for Pb(II) and Cd(II) in natural water samples agreed well with those obtained by the much more costly Inductively Coupled Plasma Mass Spectrometry, ICP-MS, technique as a reference method (recoveries from 75% to 111%).

Au nanoparticles decorated mesoporous MnFe₂O₄ nanocrystal clusters (MnFe₂O₄/Au hybrid nanospheres) were used for the electrochemical sensing of As(III) by square wave anodic stripping voltammetry (SWASV). Modified on a cheap glass carbon electrode, these MnFe₂O₄/Au hybrid nanospheres show favorable sensitivity (0.315 μA/ppb) and limit of detection (LOD) (3.37 ppb) toward As(III) under the optimized conditions in 0.1 M NaAc-HAc (pH 5.0) by depositing for 150 s at the deposition potential of -0.9 V. No obvious interference from Cd(II) and Hg(II) was recognized during the detection of As(III). Additionally, the developed electrode displayed good reproducibility, stability, and repeatability, and offered potential practical applicability for electrochemical detection of As(III) in real water samples. The present work provides a potential method for the design of new and cheap sensors in the application of electrochemical determination toward trace As(III) and other toxic metal ions.