Table 1.
Direct electrochemical detection: selectivity via catalysis and/or electrode potential control.
| Dithiocarbamate Pesticides Investigated |
Electrode Surface (Catalyst/Modifier) a |
Real Samples Investigated | Signal Basis b | L.O.D. (Analytical Ranges Reported) |
Ref. |
|---|---|---|---|---|---|
| Ziram | Polished silver solid amalgam electrode | Spiked river waters | SWV | 0.24 µM | [38] |
| Thiram | Hg | CS-DPV peak at −0.55 V vs. Ag/AgCl | 0.12 μM | [39] | |
| Thiram | Rotating gold disk electrode | Commercial formulations; spiked water samples | Ads-LSV, peak at +1.4 to +1.5 V vs. Ag/AgCl | 16 nM | [40] |
| Thiram Disulfiram |
Graphite-PTFE composite electrode | Extracts of spiked strawberry samples | Ads-LSV, peaks at +0.85 V vs. SCE | Thiram: 54 nM (0.2 to 1 µM) Disulfiram: 20 nM (0.2 to 1 µM) |
[41] |
| Thiram Disulfiram |
Graphite-PTFE composite electrode | Spiked tap and well water samples | FIA-CA at +1V vs. Ag/AgCl | Thiram: 43 nM (0.1 to 1 µM) Disulfiram: 20 nM (0.1 to 1 µM) |
[42] |
| Ziram | Hg | Extracts of spiked rice samples | CS-DPV | 32 nM i.e., 10 ppb | [43] |
| Zineb | Hg | AdSV, cathodic peak at −0.455 V vs. Ag/AgCl | 1 nM | [44] | |
| Carbathion, Ferbam, Nabam, Thiram, Thiuram, Zineb, Ziram |
Carbon paste electrode -Fe(II)metallophthalocyanine composite | Ads-LSV | Ranged from 10 nM (carbathion) to 200 nM (Thiuram) | [45] | |
| Nabam | GCE, modified with Co(II) phthalocyanine and carbon ink | LSV, peak at −0.2V vs. Ag/AgCL | 28.8 nM | [46] | |
| Thiram | GCE | Commercial formulations; plant sample extracts exposed to thiram | SWV at +0.34 V vs. Ag/AgCl | n.r. | [47] |
| Carbathion | GCE | CV, peak forming at +1.46 vs. Ag/AgCl | 9.3 μM (132 μM to 224 μM) |
[48] | |
| SWV, peak forming at +1.46 vs. Ag/AgCl | 85 nM (2 μM to 7.7 μM)) |
||||
| FIA-CA potential of +1.3 V vs. Ag/AgCl | 10 nM (1.2 μM to 6 μM) |
||||
| Ziram | Hg | Extracts of spiked vegetable samples | SWV, −1.1V vs. Ag/AgCl. | 23 nM (33 to 328 nM) |
[37] |
| Thiram | Copper-mercury amalgam electrode | Spiked river water samples | CS-SPV, peak between −0.59 and −0.8 V vs. Ag/AgCl | 16 nM | [49] |
| Propineb | Carbon-paste electrode (Cu2+-enriched montmorillonite) | Commercial formulation | Ads-SWV, peak at ~−0.1V vs. SCE | 1 μM | [50] |
| Mancozeb | BDD | PAD at +0.3V vs. Ag/AgCl) | 0.514 µM (40 to 650 µM) |
[36] | |
| Mancozeb | GCE | Commercial formulation | Ads-SWV, peaks forming at −0.7V vs. Ag/AgCl | 7 µM | [51] |
| Ziram | BDD | Spiked river water samples | FIA-CA at +0.55 V | 2.7 nM | [52] |
| Maneb | BDD | River water | DPV peak at +0.9V vs. Ag/AgCl | 24 nM (80 nM to 3 µM) |
[53] |
| Mancozeb | Single-crystal (Au(111) and Au(110) | Ads-LSV, peaks at −0.6 to −0.96V vs. Ag/AgCl | Au(110): 100 nM Au(111): 500 nM |
[54] | |
| Mancozeb | Gold electrode modified with Poly (3,4-ethylene dioxythiophene), multi-walled carbon nanotubes, and gold nanoparticles | Water | CV, anodic peak +0.65 V vs. Ag/AgCl | 5 μM | [55] |
| Thiram | Carbon paste electrode modified with zeolite | Aqueous extracts of fruit juices | DPV, anodic wave at +0.70V vs. Ag/AgCl; | 4 nM (14 nM to 4.2 μM) |
[56] |
| Thiram | Platinum, modified with silver nanoparticles | Tap, canal, and river water | DPV and CV | 0.731 μM or 0.18 ppm | [57] |
| Thiram | GCE (dissolved Zn2+ and Cu2+ cations) | River water | CS-LSV: −1.330 V vs. Ag/AgCl for Zn-Thiram; +0.020V for Cu-Thiram complexes. | n.r. (5 to 50 μM) |
[58] |
1 Where possible, analytical parameters have been standardized: limits of detection and analytical ranges of reported sensitivities are standardized to mol/L (M) units and detection sensitivities of amperometric and voltametric signals (i.e., peak currents and or response currents) were standardized to µA/µM values; a—Electrode surfaces:BDD: Boron-doped diamond; GCE: Glassy carbon electrodes; Hg: Mercury (Drop) Electrodes; PTFE: poly(tetrafluoroethylene); b—Signal basis:Ads-: Adsorptive (prefix); AS—Anodic Stripping (prefix); CS—Cathodic Stripping (prefix); FIA—Flow-injection analysis (prefix);CA: Chronoamperometry CV: Cyclic Voltammetry; DPV—differential pulse voltammetry; LSV: Linear Sweep Voltammetry; PAD: Pulsed Amperometric Detection; SCE: Saturated calomel electrode; SWV: Square-wave voltammetry; IUPAC designations of commercial dithiocarbamates studied in published articles: Carbathion: sodium N-methyldithiocarbamate (also known as metam sodium); Disulfiram: tetraethylthiuram disulfide; Diram: sodium N,N-dimethyldithiocarbamate; Ferbam: iron N,N’-dimethyldithiocarbamate; Maneb: Manganese ethylene-bis-dithiocarbamate; Mancozeb: 1,2-ethanedicarbamic acid, tetrathio- Manganese Zinc ethylene-bis-dithiocarbamate); Metam sodium: sodium N-methyldithiocarbamate; Nabam: sodium N,N’-ethylene-bis-dithiocarbamate; Propineb: Zinc propylene 1,2-bis-dithiocarbamate; Thiram: tetramethylthiuram disulfide; Thiuram: tetraethylthiuram disulfide; Zineb: zinc N,N’-ethylene-bis-dithiocarbamate; Ziram: N,N’-dimethyldithiocarbamate.