Determination of Pesticides in Water Using Carbon Voltammetric Sensors
At a Glance
Section titled âAt a Glanceâ| Metadata | Details |
|---|---|
| Publication Date | 2025-07-15 |
| Journal | Chemické listy |
| Authors | Zuzana KramplovĂĄ, Jana BlaĆĄkoviÄovĂĄ, Andrea PurdeĆĄovĂĄ |
| Institutions | University of Ss. Cyril and Methodius in Trnava, University Library in Bratislava |
| Analysis | Full AI Review Included |
Technical Documentation & Analysis: Carbon Voltammetric Sensors for Pesticide Detection
Section titled âTechnical Documentation & Analysis: Carbon Voltammetric Sensors for Pesticide DetectionâExecutive Summary
Section titled âExecutive SummaryâThis review confirms that voltammetric techniques utilizing carbon-based electrodes offer a highly sensitive, rapid, and cost-effective alternative to conventional chromatographic methods for environmental monitoring of electroactive pesticide residues.
- Core Material Validation: Boron-Doped Diamond Electrodes (BDDE) are highlighted as the superior working electrode material due to their exceptional stability, chemical inertness, and wide potential window (up to 3 V), enabling the detection of both oxidative and reductive analytes.
- High Sensitivity Achieved: Voltammetric sensors, particularly when employing Differential Pulse Voltammetry (DPV) and Square-Wave Voltammetry (SWV), achieved Limits of Detection (LOD) in the picomolar (pM) and nanomolar (nM) range, meeting or exceeding stringent regulatory requirements (e.g., EU MRL of 0.1 ”g l-1).
- Enhanced Performance through Modification: To overcome limitations of bare electrodes (e.g., GCE), researchers successfully utilized advanced surface modifications, including metal nanoparticles (Au, Pt, Pd), carbon nanomaterials (rGO, MWCNTs), and biological components (enzymes, MIPs).
- Key Applications: BDDE sensors were successfully applied for the detection of critical pesticides such as 2,4-D, Aclonifen, Bentazon, and Methiocarb in complex matrices (river, lake, and tap water).
- Operational Advantages: Carbon electrochemical sensors facilitate online monitoring and require minimal sample pre-treatment (often just filtration), significantly speeding up environmental analysis compared to traditional methods.
- 6CCVD Value Proposition: 6CCVD specializes in the high-quality MPCVD diamond materials (SCD and PCD) required for replicating and advancing this research, offering custom BDD substrates optimized for electrochemical sensing.
Technical Specifications
Section titled âTechnical SpecificationsâThe following hard data points were extracted from the review, focusing on the performance metrics and material requirements for high-sensitivity pesticide detection.
| Parameter | Value | Unit | Context |
|---|---|---|---|
| BDDE Potential Window | Up to 3 | V | Wide electrochemical range, dependent on electrolyte (Section 3.1) |
| EU MRL (Individual Pesticide) | 0.1 | ”g l-1 | Maximum Residue Limit in water for human consumption (Section 1) |
| LOD (Malathion) | 3.27 x 10-15 | M | DPV using highly modified GCE (AChE/Ag@Ti3C2Tx/GCE) |
| LOD (Methyl-Parathion) | 1.4 x 10-15 | M | CV using highly modified SPE (AChE/N-MAL-CD/SPE) |
| LOD (Aclonifen) | 1.15 | nM | DPV using GCE modified with Gadolinium Niobate (GdNbO4) Nanoparticles |
| LOD (AtrazĂn) | 10 | nM | SWV using Bare BDDE in river water (Table IV) |
| LOD (Diuron) | 0.035 | ”M | DPV using BDDE with cross-linked PVI (Table III) |
| LOD (Paraoxon-ethyl) | 0.003 | ”M | LSV using Pd NP/BN HJ/GCE (Table II) |
| BDDE Surface Requirement | Low Affinity | N/A | Mechanical or electrochemical surface treatment often not required between measurements (Section 3.1) |
Key Methodologies
Section titled âKey MethodologiesâThe research relies on advanced electrochemical techniques and sophisticated material engineering to achieve ultra-low detection limits.
- Electrochemical Techniques: The primary detection methods are pulse voltammetries:
- Differential Pulse Voltammetry (DPV) and Square-Wave Voltammetry (SWV) are preferred for quantitative analysis due to their superior sensitivity and selectivity compared to Cyclic Voltammetry (CV) and Linear-Sweep Voltammetry (LSV).
- Square-Wave Adsorptive Stripping Voltammetry (SWAdSV) is used to incorporate a pre-concentration step via adsorption, further lowering the LOD.
- Working Electrode Materials: The review focuses on carbon-based materials, with BDDE being the most robust choice due to its stability and wide potential window. Other materials include Glassy Carbon (GCE), Carbon Paste (CPE), and various forms of Graphene (GR, GO, rGO).
- Surface Modification Strategies: To enhance sensitivity, selectivity, and stability, electrodes are modified using:
- Nanomaterials: Metal nanoparticles (Au, Pt, Pd, Cu), metal oxides (TiO2, Fe3O4, MnO2), and carbon nanomaterials (MWCNTs, Carbon Dots, Nanodiamonds (ND)).
- Polymers and Biological Components: Molecularly Imprinted Polymers (MIPs), enzymes (e.g., Acetylcholinesterase, AChE), Nafion, and cross-linked polymers (PVI, PVCL).
- Simultaneous Detection: BDDEâs wide potential window allows for the simultaneous determination of multiple pesticides (e.g., Diuron, 2,4-D, Tebuthiuron) in a single scan, provided their oxidation peaks do not overlap.
- Environmental Matrices: Sensors were validated using real-world samples, including river water, lake water, tap water, and soil extracts, demonstrating practical applicability for environmental analysis.
6CCVD Solutions & Capabilities
Section titled â6CCVD Solutions & Capabilitiesâ6CCVD is uniquely positioned to supply the high-performance diamond materials necessary to replicate and advance the cutting-edge research detailed in this review. Our MPCVD diamond substrates are engineered for the demanding requirements of electrochemical sensing.
Applicable Materials
Section titled âApplicable MaterialsâThe research explicitly validates the use of Boron-Doped Diamond Electrodes (BDDE). 6CCVD offers BDD in both Single Crystal and Polycrystalline formats, optimized for electrochemical applications.
| 6CCVD Material | Key Advantage for Pesticide Sensing | Relevant Research Application |
|---|---|---|
| Heavy Boron-Doped SCD | Ultra-low background current, highest purity, and lowest noise floor for ultimate sensitivity (Ra < 1 nm polishing available). | High-precision DPV/SWV measurements requiring maximum signal-to-noise ratio. |
| Heavy Boron-Doped PCD | Large area capability (up to 125 mm wafers) for high-throughput sensor arrays and industrial scale-up. | Manufacturing of multi-electrode arrays for simultaneous, online monitoring of multiple pesticides. |
| BDD Thin Films | SCD/PCD films available from 0.1 ”m thickness, ideal for integration onto custom substrates or micro-electromechanical systems (MEMS). | Creating modified electrodes (e.g., BDDE with cross-linked PVI) where precise film thickness is critical. |
Customization Potential
Section titled âCustomization PotentialâThe complexity of the sensor modifications (nanoparticles, polymers, enzymes) requires highly customizable substrates and integration services, which are 6CCVD specialties.
- Custom Dimensions and Geometry: 6CCVD provides custom plates and wafers up to 125 mm (PCD) and substrates up to 10 mm thick, allowing researchers to move beyond standard lab sizes (GCE, CPE) to develop scalable sensor platforms.
- Precision Thickness Control: We offer precise control over the BDD layer thickness (0.1 ”m to 500 ”m) to optimize conductivity and minimize material cost for specific sensor designs.
- Integrated Metalization Services: Many high-performance sensors rely on integrated metal contacts (e.g., Au, Pt, Pd, Ti) for electrical connection or as nucleation sites for modification layers. 6CCVD offers in-house metalization capabilities, ensuring clean, high-adhesion contacts directly on the diamond surface.
- Surface Termination Engineering: We can deliver BDD substrates with specific surface terminations (e.g., hydrogen-terminated for hydrophobic adsorption or oxygen-terminated for covalent functionalization) to optimize the binding of polymeric or biological modifiers (MIPs, enzymes) used in the reviewed studies.
Engineering Support
Section titled âEngineering Supportâ6CCVDâs in-house PhD team are experts in MPCVD growth and diamond surface chemistry. We provide authoritative professional support to accelerate your research:
- Material Selection Consultation: Assistance in selecting the optimal diamond type (SCD vs. PCD) and boron doping level to maximize the potential window and minimize background current for specific voltammetric techniques (DPV/SWV).
- Modification Integration: Guidance on pre-treatment protocols and surface functionalization techniques to ensure robust adhesion and optimal performance of advanced modification layers (e.g., rGO, enzyme immobilization) for pesticide sensing projects.
For custom specifications or material consultation, visit 6ccvd.com or contact our engineering team directly.
View Original Abstract
Electrochemical methods, especially voltammetry, offer a promising alternative to conventional chromatographic techniques for the determination of electroactive pesticides in water samples. This review article summarizes current knowledge on voltammetric detection techniques (cyclic voltammetry (CV), linear-sweep voltammetry (LSV), differential pulse voltammetry (DPV), square-wave voltammetry (SWV)) and carbon-based electrode materials (e.g., boron-doped diamond electrode (BDDE), glassy carbon electrode (GCE), carbon paste electrode (CPE)). Special attention is given to the advantages of each technique, electrode surface modifications, and achieved analytical parameters. Due to their high sensitivity, ease of use, and potential for online monitoring, carbon-based electrochemical sensors can serve as an efficient tool for environmental analysis of pesticide residues.