Simultaneous Analysis of 20 Mycotoxins in Grapes and Wines from Hexi Corridor Region (China): Based on a QuEChERS–UHPLC–MS/MS Method
Abstract
:1. Introduction
2. Results and Discussions
2.1. Optimization of MS/MS Parameters and Chromatographic Separation
2.2. Optimization of the QuEChERS Procedure
2.2.1. Selection of Wine/Water Ratio
2.2.2. Selection of Salt Amount and Type
2.2.3. Selection of Clean-Up
2.3. Method Validation
2.3.1. Matrix Effect Evaluation
2.3.2. Calibration Curves, Linearity, LOD and LOQ
2.3.3. Precision and Recovery
2.4. Application to Real Sample
3. Materials and Methods
3.1. Chemicals and Standards
3.2. Optimization of the Extraction Method
3.2.1. The Wine/Water Ratio Optimization
3.2.2. The Amount and Type of Salt Optimization
3.2.3. The Clean-Up Optimization
3.2.4. Optimized QuEChERS Procedure
3.3. Chromatographic and Mass Spectrometric Conditions
3.4. Method Validation Study
3.5. Analysis of Mycotoxins in Grape and Wine Samples
3.6. Data Analysis
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Sample Availability: Samples of the some wines are available from the authors. |
Mycotoxin | Structure | Adduct ion | Precursor Ion (m/z) | Product ion a (m/z) | Fragmentor (V) | Collision Energy (V) |
---|---|---|---|---|---|---|
AFB1 (aflatoxin B1) | | [M + H]+ | 313.0 | 285.2/241.1 | 130 | 20/20 |
AFB2 (aflatoxin B2) | | [M + H]+ | 315.1 | 287.1/269.1 | 130 | 30/30 |
AFG1 (aflatoxin G1) | | [M + H]+ | 329.1 | 243.1/311.1 | 130 | 25/20 |
AFG2 (aflatoxin G2) | | [M + H]+ | 331.1 | 245.1/285.1 | 130 | 30/25 |
AFM1 (aflatoxin M1) | | [M + H]+ | 328.9 | 273.0/228.9 | 165 | 25/50 |
CPA (cyclopiazonic acid) | | [M + H]+ | 337.3 | 196.2/182.1 | 39 | 23/20 |
CTN (citrinin) | | [M + H]+ | 250.9 | 233.0/205.0 | 80 | 15/25 |
DAS (diacetoxyscirpenol) | | [M + NH4]+ | 384.0 | 307.0/247.0 | 65 | 8/10 |
DON (deoxynivalenol) | | [M + H]+ | 297.2 | 281.0/265.0 | 120 | 5/25 |
FB1 (fumonisin B1) | | [M + H]+ | 722.1 | 334.0/352.1 | 100 | 40/35 |
HT-2 (HT-2 toxin) | | [M + Na]+ | 447.3 | 284.8/345.3 | 135 | 20/20 |
MEO (mevinolin) | | [M + H]+ | 405.1 | 199.1/285.1 | 125 | 5/5 |
MPA (mycophenolic acid) | | [M + H]+ | 321.1 | 206.9/274.7 | 90 | 15/15 |
NEO (neosolaniol) | | [M + NH4]+ | 400.0 | 305.0/185.0 | 95 | 10/15 |
OTA (ochratoxin A) | | [M + H]+ | 404.0 | 238.9/357.9 | 127 | 20/10 |
OTB (ochratoxin B) | | [M + H]+ | 369.9 | 205.0/324.0 | 115 | 20/10 |
PCA (penicillic acid) | | [M + H]+ | 170.8 | 153.0/125.0 | 10 | 0/15 |
STE (sterigmatocystine) | | [M + H]+ | 325.0 | 280.9/252.9 | 135 | 35/55 |
T-2 (T-2 toxin) | | [M + NH4]+ | 484.1 | 305.0/215.0 | 115 | 10/18 |
ZEN (zearalenone) | | [M + H]+ | 319.0 | 187.1/184.9 | 70 | 25/40 |
Mycotoxin | Matrix Effect (%)/Recovery (%) (n = 3) | |||||
---|---|---|---|---|---|---|
1:9 | 2:8 | 3:7 | 5:5 | 7:3 | 8:2 | |
AFB1 | −26/94 | 31/116 | 33/101 | 68/84 | 51/69 | 68/64 |
AFB2 | −32/183 | 15/96 | 9/98 | 34/85 | 15/68 | 32/66 |
AFG1 | −27/193 | 13/86 | 16/69 | 47/81 | 31/76 | 44/76 |
AFG2 | −12/182 | 26/92 | 25/81 | 42/89 | 13/50 | 26/49 |
AFM1 | −58/63 | −60/72 | −57/71 | −64/84 | −68/71 | −69/76 |
CPA | −13/124 | −27/88 | −24/81 | −37/88 | −33/79 | −30/63 |
CTN | 53/84 | 37/88 | 50/89 | 54/94 | 61/88 | 68/85 |
DAS | 312/84 | 289/90 | 325/90 | 357/96 | 413/88 | 435/89 |
DON | 177/73 | 6/36 | 9/72 | −21/115 | −33/148 | −18/240 |
FB1 | −93/109 | −92/94 | −94/108 | −93/101 | −93/91 | −92/74 |
HT-2 | 30/95 | 7/110 | 19/102 | 48/88 | 28/81 | 22/116 |
MEO | 113/62 | 97/61 | 67/73 | 89/84 | 0/85 | 7/77 |
MPA | −23/116 | −7/90 | −24/107 | 8/81 | −11/88 | 19/68 |
NEO | −8/71 | −43/90 | −41/74 | −51/86 | −57/80 | −56/75 |
OTA | −14/120 | 1/106 | −31/126 | −1/106 | −16/111 | 29/74 |
OTB | 76/87 | 64/90 | 84/85 | 81/91 | 85/87 | 92/84 |
PCA | −48/105 | −45/90 | −59/115 | −43/83 | −61/102 | −46/70 |
STE | −33/196 | −7/145 | −16/175 | 31/115 | 11/116 | 51/92 |
T-2 | 556/78 | 455/100 | 508/95 | 496/105 | 532/94 | 541/94 |
ZEN | −25/104 | −14/98 | −27/115 | 3/89 | −11/79 | 12/67 |
Mycotoxin | Matrix Effect (%)/Recovery (%) (n = 3) | |||||||
---|---|---|---|---|---|---|---|---|
A a | B | C | D | E | F | G | H | |
AFB1 | −26/100 | 31/118 | 33/89 | 68/100 | 51/89 | 68/87 | 53/107 | 55/89 |
AFB2 | −32/120 | 15/103 | 9/113 | 34/104 | 15/124 | 32/74 | 11/99 | 31/87 |
AFG1 | −27/113 | 13/109 | 16/108 | 47/101 | 31/102 | 44/84 | 33/104 | 37/88 |
AFG2 | −12/117 | 26/115 | 25/117 | 42/117 | 13/112 | 26/100 | 23/108 | 22/85 |
AFM1 | −71/46 | −72/56 | −73/68 | −72/65 | −73/83 | −73/79 | −71/80 | −71/88 |
CPA | −26/52 | −26/78 | −33/92 | −32/94 | −21/98 | −32/116 | −30/109 | −17/94 |
CTN | 46/55 | 52/64 | 53/69 | 47/78 | 48/93 | 46/93 | 47/87 | 40/93 |
DAS | 118/68 | 176/72 | 187/82 | 198/85 | 221/93 | 209/92 | 209/89 | 198/92 |
DON | −59/158 | −74/257 | −59/120 | −62/134 | −67/95 | −75/80 | −39/77 | −46/84 |
FB1 | −94/100 | −93/99 | −93/98 | −92/86 | −94/85 | −94/134 | −94/74 | −95/101 |
HT-2 | 31/98 | 15/102 | 44/96 | 33/94 | 33/103 | 36/90 | 46/89 | 21/100 |
MEO | −15/89 | −33/93 | −6/102 | −26/117 | −20/123 | −21/113 | −32/88 | −21/90 |
MPA | −35/66 | −31/66 | −39/73 | −40/86 | −32/92 | −39/97 | −35/105 | −24/94 |
NEO | −53/54 | −53/63 | −53/73 | −51/72 | −49/85 | −58/89 | −51/85 | −53/91 |
OTA | −29/67 | −20/57 | −28/65 | −33/77 | −27/80 | −35/87 | −5/97 | 3/92 |
OTB | 74/57 | 80/66 | 79/73 | 75/79 | 76/86 | 78/83 | 76/90 | 77/90 |
PCA | −52/76 | −58/80 | −64/77 | −69/127 | −68/103 | −72/96 | −14/110 | 6/89 |
STE | −33/59 | −31/59 | −29/58 | −26/65 | −15/68 | −21/70 | −50/112 | −44/102 |
T-2 | 370/43 | 375/57 | 359/69 | 307/85 | 297/104 | 283/103 | 278/95 | 291/93 |
ZEN | −31/62 | −33/64 | −39/69 | −38/79 | −35/88 | −38/89 | −46/100 | −40/95 |
Mycotoxin | Calibration | R2 | Linear Range (μg/L) | LOD (μg/L) | LOQ (μg/L) |
---|---|---|---|---|---|
AFB1 | y = 5.6980x + 0.1230 | 0.9990 | 5–200 | 0.25 | 0.75 |
AFB2 | y = 33.0713x + 116.2999 | 0.9993 | 1.25–50 | 0.13 | 0.39 |
AFG1 | y = 71.1585x + 249.3916 | 0.9988 | 5–200 | 0.25 | 0.75 |
AFG2 | y = 10.0093x + 4.5423 | 0.9991 | 1.25–50 | 0.06 | 0.18 |
AFM1 | y = 4.4951x + 3.7299 | 0.9995 | 5–200 | 0.1 | 0.3 |
CPA | y = 3.1361x − 13.8214 | 0.9987 | 5–200 | 0.25 | 0.75 |
CTN | y = 923.0092x + 1433.5419 | 0.9995 | 5–200 | 0.1 | 0.3 |
DAS | y = 0.8656x − 1.8377 | 0.9980 | 5–200 | 0.1 | 0.3 |
DON | y = 0.8969x + 3045.7580 | 0.9971 | 5–200 | 5 | 15 |
FB1 | y = 0.4647x − 0.9568 | 0.9994 | 5–200 | 1 | 3 |
HT-2 | y = 0.0326x + 0.1858 | 0.9963 | 5–200 | 10 | 30 |
MEO | y = 1.6624x − 4.5656 | 0.9992 | 5–200 | 0.1 | 0.3 |
MPA | y = 6.9560x − 16.4431 | 0.9993 | 5–200 | 0.1 | 0.3 |
NEO | y = 42.1866x + 72.9181 | 0.9994 | 5–200 | 0.1 | 0.3 |
OTA | y = 3.6812x − 6.8163 | 0.9998 | 5–200 | 0.1 | 0.3 |
OTB | y = 195.8790x + 507.8370 | 0.9991 | 5–200 | 0.1 | 0.3 |
PCA | y = 10.5717x + 34.0765 | 0.9993 | 5–200 | 1 | 3 |
STE | y = 5.9077x − 0.9029 | 0.9999 | 5–200 | 0.1 | 0.3 |
T-2 | y = 1.0423x − 2.7770 | 0.9983 | 5–200 | 0.25 | 0.75 |
ZEN | y = 0.5345x − 0.5351 | 0.9992 | 5–200 | 1 | 1 |
Area | Total Number of Samples | Number of Samples with Mycotoxins Detected | ||||
---|---|---|---|---|---|---|
PCA a | MPA | CPA | FB1 | ZEN | ||
Jiayuguan | 3 | - | 1 (9.27) | 3 (2.94–7.44) | - | - |
Zhangye | 9 | 9.04 | 2 (0.10–0.68) | - | - | - |
Wuwei | 24 | 11.71 | 2 (0.10–81.26) | 5 (0.11–0.17) | 1 (0.84) | 2 (0.29–0.36) |
Year | Total Number of Samples | Number of Samples with Mycotoxins Detected | ||||
---|---|---|---|---|---|---|
OTA a | MPA | CPA | AFB2 | ZEN | ||
2007 | 1 | - | 1 (1.37) | - | - | - |
2008 | 1 | - | - | - | - | - |
2009 | 2 | - | 2 (1.37–1.53) | - | - | - |
2010 | 2 | - | 1 (1.53) | - | 1 (0.10) | - |
2011 | 2 | - | 1 (1.45) | - | - | - |
2012 | 2 | - | 2 (1.60) | - | - | - |
2013 | 3 | - | 2 (1.45–1.60) | 1 (3.72) | - | - |
2014 | 9 | 1 (1.27) | 6 (1.45–2.31) | 1 (3.90) | 1 (0.10) | 2 (1.82–1.85) |
2015 | 14 | 1 (1.27) | 5 (1.37–2.31) | 3 (2.71–4.62) | - | 1 (1.82) |
2016 | 6 | - | - | - | - | - |
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Zhang, B.; Chen, X.; Han, S.-Y.; Li, M.; Ma, T.-Z.; Sheng, W.-J.; Zhu, X. Simultaneous Analysis of 20 Mycotoxins in Grapes and Wines from Hexi Corridor Region (China): Based on a QuEChERS–UHPLC–MS/MS Method. Molecules 2018, 23, 1926. https://doi.org/10.3390/molecules23081926
Zhang B, Chen X, Han S-Y, Li M, Ma T-Z, Sheng W-J, Zhu X. Simultaneous Analysis of 20 Mycotoxins in Grapes and Wines from Hexi Corridor Region (China): Based on a QuEChERS–UHPLC–MS/MS Method. Molecules. 2018; 23(8):1926. https://doi.org/10.3390/molecules23081926
Chicago/Turabian StyleZhang, Bo, Xia Chen, Shun-Yu Han, Min Li, Teng-Zhen Ma, Wen-Jun Sheng, and Xia Zhu. 2018. "Simultaneous Analysis of 20 Mycotoxins in Grapes and Wines from Hexi Corridor Region (China): Based on a QuEChERS–UHPLC–MS/MS Method" Molecules 23, no. 8: 1926. https://doi.org/10.3390/molecules23081926