Pressurized Solvent Extraction with Ethyl Acetate and Liquid Chromatography—Tandem Mass Spectrometry for the Analysis of Selected Conazole Fungicides in Matcha
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Sample Preparation
2.3. LC-ESI+-MS/MS Analysis
3. Results
3.1. Cell Design for Pressurized Solvent Extraction of Matcha
3.2. Modifications to the LC-ESI+-MS/MS Analysis
3.3. Method Detection Limits and Calibration
3.4. Matrix Effects and Recoveries of Pressurized Solvent Extraction
4. Discussion
5. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
References
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Target Analyte | Retention Time (min) | Quantitative SRM, Confirmation SRM (Cone Voltage, Collision Energy) | Method Detection Limits with Matrix Matched Standards (mg/kg) |
---|---|---|---|
Benzotriazole | 8.24 | 120→65 (40,17), 120→92 (40,17) | 0.0006 |
Sulfathiazole | 8.46 | 256→155 (20,15), 256→92 (20,25) | 0.002 |
Imazamox | 9.09 | 306→261 (40,20), 306→217 (40,20) | 0.010 |
Sulfamethizole | 9.34 | 271→156 (20,15), 271→92 (20,25) | 0.002 |
Tebuthiuron (thiadiazolylurea herbicide) | 10.48 | 229→172 (25,15), 229→116 (25,25) | 0.001 |
Tricyclazole (benzothiazole fungicide) | 12.06 | 190→163 (35,20), 190→136 (35,25) | 0.002 |
Sulfentrazone | 15.36 | 387→307 (35,20), 389→309 (35,20) | 0.010 |
Imazalil | 15.8 | 297→159 (20,25), 297→201 (20,20) | 0.010 |
Thioconazole | 15.93 | 391→130 (20,20), 391→360 (20,10) | 0.010 |
Azaconazole | 16.71 | 300→159 (30,25), 300→231 (30,15) | 0.001 |
Triadimenol | 18.19 | 296→70 (15,15), 298→70 (15,15), 296→99 (15,10) | 0.002 |
Paclobutrazol (plant growth regulator with triazole moiety) | 18.58 | 294→70 (30,20), 295→70 (25,20), 296→70 (15,15) | 0.010 |
Triticonazole | 19.39 | 318→70 (20,15), 320→70 (20,20) | 0.010 |
Cyproconazole | 19.76 | 292→70 (30,15), 294→70(30,20) | 0.002 |
Hexaconazole | 20.58 | 314→70 (25,20), 316→70(25,20) | 0.010 |
Uniconazole (uniconazole-P) | 20.94 | 292→70 (30,15), 294→70 (30,20) | 0.010 |
Etaconazole | 21.58 | 328→159 (30,25), 330→161 (30,25), 328→187 (30,30) | 0.001 |
Prochloraz | 21.61 | 376→70 (15,25),378→70 (15,25), 376→308 (15,15) | 0.010 |
Myclobutanil | 21.73 | 289→70 (25,15), 291→70 (25,15) | 0.010 |
Triadimefon | 21.73 | 295→70 (25,20), 297→70 (25,20) | 0.002 |
Prothioconazole (analyzed as prothioconazole-desthio) | 21.75 | 314→70 (25,20), 312→70 (25,20), 312→125 (25,20) | 0.005 |
Tebuconazole | 21.94 | 308.5→70 (35,20), 310.5→70 (35,20), 308.5→125 (35,20) | 0.001 |
Bromuconazole | 22.01 | 376→159 (30,25), 378→159 (30,25) | 0.010 |
Penconazole | 22.12 | 284→70 (25,15), 284→159 (25,15) | 0.010 |
Metconazole | 22.15 | 321→70 (30,20), 323→70 (30,20) | 0.010 |
Diniconazole | 22.46 | 326→70(35,25), 328→70(35,25), 326→159 (35,20) | 0.0006 |
Epoxiconazole | 22.46 | 330→121 (25,20), 332→121 (25,20), 330→123 (25,20) | 0.010 |
Tetraconazole | 22.46 | 372→159 (30,25), 372→70 (30,25) | 0.010 |
Biteranol | 22.73 | 338→99 (15,15), 338→269 (15,15) | 0.002 |
Propiconazole | 22.73 | 342→159 (30,25), 342→69 (30,25) | 0.010 |
Flusilazole | 22.94 | 316→165 (30,25), 316→248 (30,15) | 0.0006 |
Fenbuconazole | 23.12 | 337→70 (30,20), 337→125 (30,20) | 0.001 |
Tebufenozide (insecticide) | 23.12 | 353→133 (12,17), 353→297 (12,17) | 0.002 |
Difenoconazole | 23.64 | 406→251 (30,25), 408→253 (30,25) | 0.010 |
Etoxazole | 25.02 | 360→57 (35,25), 360→141 (35,30), 360→177.5 (35,20) | 0.010 |
Propiconazole-phenyld3 (internal standard) | 22.80 | 347→164 (50,25), 349→166 (50,25), 347→69 (50,25), 349→69 (50,25) | NA |
Target Analyte (SRM) | Recovery, Spiked at 0.01 mg/kg 1 (Average ±SD, n = 4 ) | % Matrix Effect | Detected Concentration in Matcha (mg/kg) 2 |
---|---|---|---|
Selected Analytes with MS Signal Suppression or Soft Enhancement | |||
Tebuthiuron (229→172) | 80.7 ± 4.70 | −19% | ND |
Sulfentrazone (387→307) | 64.0 ± 18.3 | −35% | ND |
Triadimenol (296→70) | 109.5 ± 11.7 | −32% | ND |
Paclobutanil (295→70) | 51.8 ± 14.0 | −38% | ND |
Cyproconazole (292→70) | 69.3 ± 12.9 | −37% | ND |
Uniconazole (292→70) | 23.9 ± 12.9 | −29% | ND |
Myclobutanil (291→70) | 84.9 ± 38.3 | −53% | ND |
Triadimenfon (295→70) | 96.1 ± 34.6 | −44% | ND |
Hexaconazole (314→70) | 12.1 ± 19.8 | −75% | ND |
Prothioconazole-desthio (314→70) | 69.2 ± 29.2 | −54% | 0.0035 |
Flusilazole (316→165) | 40.4 ± 28.9 | 6% | 0.0024 |
Propiconazole (342→159) | 41.9 ± 25.0 | −54% | ND |
Etaconazole (330→161) | 49.1 ± 11.3 | −5% | ND |
Azaconazole (300→159) | 32.3 ± 11.0 | −33% | ND |
Difenconazole (406→251) | 20.4 ± 87.9 | −47% | ND |
Analytes with Severe Signal Enhancement | |||
Diniconazole (326→70) | 21.5 ± 5.40 | 102% | ND |
Fenbuconazole (337→70) | 29.9 ± 8.10 | 81% | ND |
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Raina-Fulton, R.; Mohamad, A.A. Pressurized Solvent Extraction with Ethyl Acetate and Liquid Chromatography—Tandem Mass Spectrometry for the Analysis of Selected Conazole Fungicides in Matcha. Toxics 2018, 6, 64. https://doi.org/10.3390/toxics6040064
Raina-Fulton R, Mohamad AA. Pressurized Solvent Extraction with Ethyl Acetate and Liquid Chromatography—Tandem Mass Spectrometry for the Analysis of Selected Conazole Fungicides in Matcha. Toxics. 2018; 6(4):64. https://doi.org/10.3390/toxics6040064
Chicago/Turabian StyleRaina-Fulton, Renata, and Aisha A. Mohamad. 2018. "Pressurized Solvent Extraction with Ethyl Acetate and Liquid Chromatography—Tandem Mass Spectrometry for the Analysis of Selected Conazole Fungicides in Matcha" Toxics 6, no. 4: 64. https://doi.org/10.3390/toxics6040064