| | Matrix | Analytes | Extraction | Clean-up step | LC conditions | Chromatographic column | Sensitivity (μg/kg) | References | | LOD | LOQ |
| | Maize | NIV
DON
FUS-X
ADONs
3ADON
DAS
HT2
T2
ZON/ZAN | CH3CN-H2O (84 : 16, v/v) | Clean-up columns, MycoSep® #226 and #227 from Romer Labs® | (i) Eluent A H2O-CH3OH (80 : 20, v/v), eluent B H2O-CH3OH (10 : 90, v/v), both containing 5 mM NH4CH3COO-
(ii) Gradient: 0.5 min 0% eluent B, linear gradient to 100% eluent B to 4.5 min, 100% eluent B to 7 min, 7.1 min 0% eluent B, reequilibration 3 min, total run 10 min | Thermo Electronaquasil® RP-18 column | 3.7
0.8
1.6
0.9
3.8
0.3
1.0
0.3
0.9 | 18.3
2.7
5.6
3.5
13.4
1.1
3.5
0.8
3.2 | [86] |
| | Wheat and maize | 18 trichothecene mycotoxins
(i) Type-A trichothecenes (T-2, HT-2, T-2 triol, T-2 tetraol, DAS, MAS, NEO, DacVOL, and VOL)
(ii) Type-B trichothecenes (DON, 3-acDON, 15-acDON, NIV, and FUSX)
(iii) Type-D trichothecenes (SG, SH, RA, and VA) | Dilute and shoot | MycoSep®-226 | (i) Eluent A CH3OH-H2O-CH3COOH (10 : 89 : 1, v/v/v), eluent B CH3OH-H2O-CH3COOH (97 : 2 : 1, v/v/v), both containing 5 mM NH4CH3COO-
(ii) Gradient 2 min at 100% eluent A, linear increase to 100% eluent B within 12 min, held at 100% eluent B for 3 min, reequilibration at 100% eluent A for 4 min, total run 19 min | Gemini® C18 column, 150 × 4.6 mm i.d., 5 μm particle size, equipped with a C18 4 × 3 mm i.d. security guard cartridge (all from Phenomenex, Torrance, CA, US) | [0.064–0.41]
[0.092–0.70]
[0.20–0.38] | [0.22–1.4]
[0.31–2.2]
[0.67–1.3] | [145] |
| | Maize, durum wheat, corn flakes, and maize crackers | DON
AFG2
AFG1
AFB2
AFB1
FB1
FB2
OTA
HT-2
T-2
ZEA | 2-step extraction: (1) H2O; (2) CH3OH. Evaporation and redissolution in PBS before IAC | AOFZDT2TM column at 1-2 drops per second; the column was then washed with 20 mL | (i) Eluent A H2O, eluent B CH3OH, both containing 0.5% CH3COOH and 1 mM NH4CH3COO-
(ii) Gradient 3 min at 20% eluent B, jump to 40% eluent B, linear increase to 63% eluent B within 35 min, 63% eluent B for 11 min, reequilibration at 20% eluent B for 10 min, total run 59 min | Gemini1 C18 column (150 mm, 2 mm, 5 mm particles; Phenomenex, Torrance, CA, USA), preceded by a Gemini C18 guard column (4 mm, 2 mm, 5 mm particles) | 4.2
0.8
0.4
0.3
0.6
1.1
0.4
0.6
1.9
1.5
0.7 | n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d | [52] |
| | Various foods and feed | ATB1
ATB2
ATG1
ATG2
ATM1
T-2
HT-2
VCG
CTN
OTA
3-ADON
15-ADON
FX
ZON
NIV
DON | CH3CN-H2O (84 : 16, v/v) | Mycosep #226 and #228 Aflazon+ multifunctional cartridges | (i) Eluent A ESI+ 10 mM NH4CH3COO-, ESI− 0.1% 0.1% (v/v) aqueous NH3, eluent B CH3OH
(ii) Gradient initially 20% eluent B, linear increase from 5.5 to 85% eluent B, 100% eluent B within 0.3 min, reequilibration for 2 min at 20% eluent B, total run 10 min | UPLCBEH C18 column (1.7 μm, 100 mm × 2.1 mm i.d., Waters) | 0.003
0.003
0.003
0.006
0.003
0.060
0.006
0.006
0.101
0.064
0.182
0.182
0.152
0.091
0.182
0.212 | 0.01
0.01
0.01
0.02
0.01
0.20
0.02
0.02
0.35
0.21
0.60
0.60
0.50
0.30
0.60
0.70 | [146] |
| | Rice, corn, wheat, rye, oat, barley, infant cereals, soya, and corn gluten | AflB1
AflB2
AflG1
AflG2
DON
NIV
15-AcDON
FUSX
NEO
HT-2
T-2
FB1
FB2
ZON
OTA | QuEChERS | n-hexane (5 mL) under agitation and centrifugation | (i) Eluent A 0.15% (v/v) HCOOH+ 10 mM NH4HCOO-, eluent B 0.05% HCOOH (v/v) in CH3OH
(ii) Gradient: 0% eluent B at 1 min, linear increase to 100% eluent B until 15 min, 100% eluent B for 5 min, reequilibration at 0% eluent B for 5 min, total run 25 min | ZorbaxBonus-RP column 150 mm 2.1 mm i.d., 3.5 μm, equipped with a ZorbaxRB C8 guard column 12.5 mm, 2.1 mm i.d., 5 μm (both from Agilent Technologies, Geneva, Switzerland) | n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d | [1–10]
[1–10]
[1–10]
[1–10]
[50–250]
[100–500]
[50–250]
[25–125]
[25–125]
[25–125]
[25–125]
[5–25]
[50–250]
[50–250]
[50–250]
[0.50–2.5] | [130] |
| | Barley | 3ADON, 15ADON, DON, DON-3-Glc, FUS-X, NIV, HT2, T2, DAS, NEO, AFs, OTA, FBs, STER, ZEN, penitrem A, BEA, Alternaria toxins, ergot alkaloids | QuEChERS (2 g sample, 10 mL 0.1% HCOOH in H2O, 3 min shaking, 10 mL CH3CN, 3 min shaking, 4 g MgSO4, 1 g NaCl, shaking) | C18-SPE clean-up procedure was performed with Oasis HLB cartridges (150 mg) from Waters (Milford, MA, USA) | (i) Eluent A H2O with 5 mM NH4HCOO- and 0.1% HCOOH, eluent B CH3OH
(ii) Gradient: start with 5% eluent B, increase to 50% eluent B in 6 min, increase to 95% eluent B within 4 min, keep until 15 min of the run, reequilibration at 5% eluent B for 3 min | Acquity UPLC HSS T3 analytical column (100 mm, 2.1 mm i.d., 1.8 mm; Waters, Milford, MA, USA) | n.d | n.d | [133] |
| | Barley and barley products | T-2, HT-2, T-2 triol, T-2 tetraol, DAS, NEO, DON, NIV, 3-AcDON, 15-AcDON, FUS-X | Acetonitrile : water (84/16) | A MycoSep® column (no. 226, CoringSystem Diagnostix, Germany) | A binary linear gradient was applied which consisted of eluent A (methanol + 5 mmol/l ammonium formate) and eluent B (water + 5 mmol/l ammonium formate) with a total flow rate of 0.4 ml/min: 0 min 95% B, 11 min 95% B, 22 min 35% B, 26 min 35% B, 27 min 95% B, 35 min 95% B | Synergi™ polar-RP® 150 × 2 mm, 4 μm (Phenomenex, Aschaffenburg, Germany) | [0.02–2.25] | n.d | [53] |
| | Cereal and cereal products | NIV
DON
AFB1
AFB2
AFG1
AFG2
DAS
FB1
FB2
HT-2
T-2
OTA
BEA | Extraction with matrix solid-phase dispersion (MSPD) method | — | The gradient that started at 100% A (5 mM ammonium formate in water) and 0% B (5 mM ammonium formate in methanol) increased linearly to 100% B in 10 min, followed by a linear decrease to 80% B in 5 min, then to 70% B in 10 min. Afterwards, the initial conditions were maintained for 5 min. | GeminiNX C18 (150 mm, 4.6 mm I.D., 5 μm particle size) analytical column supplied by Phenomenex (Barcelona, Spain), preceded by aguard column C18 (4 mm, 2 mm I.D.) | n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d | 85.24
31.25
0.25
1.50
0.25
0.75
5.00
83.33
83.75
35.5
12.50
3.00
1.00 | [136] |
| | Maize, wheat, rye, oat, oat flakes, and flours (maize, wheat, rye, and oat) | MON | Acetonitrile/water (84/16) | 1M hydrochloric acid from n exchanger material (SAX). The SAX column (Bond Elut-SAX, 500 mg, 3 mL) (Agilent Technologies, Böblingen, Germany) | Solvent A: 1% formic acid in methanol, and solvent B: 1% formic acid in water. The detection was set to 260 nm. An isocratic run at 20% A was performed for 10 min at a flow rate of 250 μL/min. An isocratic run at 95% A was used for 10 min | A 150 mm × 2.1 mm i.d., 5 μm, Synchronis HILIC with a 10 mm × 2.1 mm i.d. guard column (Thermo Scientific, Dreieich, Germany),a 150 mm × 2.1 mm i.d., 3.5 μm | 0.7 | 2.5 | [99] |
| | Maize | FMs | Water/methanol (30/70) | Sep-Pak C18 cartridges | Gradient elution was performed using bidistilled water (eluent A) and acetonitrile (eluent B), both acidified with 0.2% formic acid: initial condition at 100% A, 0–5 min isocratic step, 5–30 min linear gradient to 100% B, 30–35 min isocratic step, 35-36 min linear gradient to 100% A and reequilibration step at 100% A for 14 min (total analysis time: 50 min) | A 250 × 2.1 mm i.d., 5 mm, XTerra C18; the flow rate was 0.2 ml/min | 20 | n.d | [156] |
| | Cereals and cereal products (wheat, wheat-based noodles, rice, rice-based noodles, and corn) | NEO
DAS
T-2
HT-2
DON
NIV
15-ac-DON
FUSX | QuEChERS method | — | Mobile phase A consists of 1% acetic acid and 5 mM ammonium acetate in water and mobile phase B consisted of 1% acetic acid and 5 mM ammonium acetate in methanol. The gradient was changed to 80% mobile phase B over 10 min, and then maintained for 3 min. After 13 min of run time, the gradient was returned to 30% mobile phase B over 1 min | ZORBAX Eclipse XBD-C18, 2.1 mm, 100 mm, 1.8 mm (P.N. 928700-902) column | 0.02
0.02
0.05
0.02
0.045
0.05
0.02
0.04 | n.d
n.d
n.d
n.d
n.d
n.d
n.d
n.d | [152] |
| | Cereals (rice, wheat, oat, barley, and maize) | Acetonitrile/water/acetic acid (79/20/1) | AFs, OTA, ZEN, DON, FB1, FB2, T-2, HT-2 | — | Different proportions of mobile phase consisted of methanol or acetonitrile and acetic acid (0-1%), different flow rates (0.2-0.3 mL/min) | A column, 150 mm, 4.6, 3 μm particle size C18 columns (Thermo Scientific, CA, USA) | [10−5–0.02] | [2×10−5–0.04] | [87] |
| | Wheat | NIV
DON
FUSX
15-AcDON
3-AcDON
DAS
NEO
HT-2
T-2
ZEN
α-ZOL
β-ZOL | Acetonitrile/water (84/16) | A SecurityGuard™ cartridge C18 (4.0 3.0 mm i.d. 5 μm). | Mobile phase A consisted of an H2O/CH3OH/CH3COOH mixture (89 : 10 : 1, v/v/v) containing 5 mM ammonium acetate, while mobile phase B: H2O/CH3OH/CH3COOH mixture (2 : 97 : 1, v/v/v) containing 5 mM ammonium acetate. The following gradient was applied: initial condition 55% B; 0–3 min, 70% B; 3–8 min, 100% B; 8–11 min constant at 100% B; 11–13 min returning to the initial conditions and maintain during 2 min 55% B. | Phenomenex (Castel Maggiore, Italy) Gemini C18 (150 mm, 2.0 mm, i.d. 5 μm particle size, 110A) | 5.5
1
5.5
2
2
2
5.5
2
3
1.5
1.5
2 | 15
10
20
10
10
10
20
6
8
5
5
2.5 | [143] |
| | Maize and other cereals (sorghum, millet, rice, sesame, wheat, infant food, cuscus, cornflakes, and cookies) | AFB1, AFB2, AFG1, AFG2, AFM1, FB1, FB2, FB3, OTA, DON, NIV, ZEN, MON, CIT, ENA, ENA1, ENB, ENB1, ENB2, BEA, STC | Acetonitrile/water/acetic acid (79/20/1) | — | Both eluents contained 5 mM ammonium acetate and were composed of methanol/water/acetic acid 10 :89 : 1 (v/v/v; eluent A) or 97 : 2 : 1 (eluent B), respectively. After an initial time of 2 min at 100% A, the proportion of B was increased linearly to 100% within 12 min, followed by a hold-time of 3 min at 100% B and 4 min column reequilibration at 100% A | A Gemini C18 column, 150 × 4.6 mm, 5 μm particle size, equipped with a C18 4 × 3 mm guard cartridge, all from Phenomenex (Torrance, CA, USA). | [0.005–250] | n.d | [157] |
| | Breakfast and infant cereals | FB1, FB2, FB3 | Acetonitrile/water (85/15) | A C18 security guard cartridge (4 mm × 2 mm i.d., 5 μm), both Phenomenex (Madrid, Spain) | The sing gradient elution with water as mobile phase A and methanol as mobile phase B, both containing 0.5% formic acid. After an isocratic step of 65% B for 3 min, it was gradually increased to 95% B in 4 min and held constant for 3 min. Afterwards, the initial conditions were maintained for 10 min | A Luna C18 analytical column (150 mm × 4.6 mm i.d., 5 μm) Phenomenex (Madrid, Spain) | n.d | n.d | [158] |
| | Barley, maize breakfast cereals, and peanuts | AFB1
AFB2
AFG1
AFG2
FB1
FB2
FB3
DON
ZEN
HT2
T2
OTA | CH3CN-H2O-CH3COOH (79.5 : 20 : 0.5, v/v/v). Evaporation and redissolution in PBS before IAC | | (i) Eluents A H2O, eluent B CH3OH, both containing 5 mM NH4CH3COO-
(ii) Gradient 5% eluent B increased to 50% eluent B in 1 min, linear increase to 100% eluent B within 6 min, 100% eluent B to 8 min, at 8.1 min initial conditions 5% eluent B, reequilibration at 5% eluent B for 2 min, total run 10 min | | 0.05
0.05
0.05
0.05
5
5
5
1
1
0.5
0.5
0.1 | 0.1
0.1
0.1
0.1
10
10
10
5
5
1
1
0.25 | [159] |
| | Maize and maize-beer | 69 mycotoxins | Extraction with many solvents (ACN/water/glacial acetic acid 79 : 20 : 1, v/v/v) | — | (i) Two eluting solvents (eluent A and eluent B) that each contained 5 mM ammonium acetate were prepared using MeOH/water/glacial acetic acid (10 : 89 : 1, v/v/v) (eluent A) and (97 : 2 : 1, v/v/v) (eluent B)
(ii) After an initial time of 2 min at 100% eluent A, the proportion of eluent B was increased linearly to 50% within 2–5 min and to 100% within 5–14 min, followed by a holding-time of 4 min at 100% eluent B and 2.5 min column reequilibration at 100% eluent A | A Gemini C18 column (Phenomenex, Torrance, CA, US). | [0.05–0.14] | [3–41] | [92] |
| | Maize and cereal-based products | AFB1
AFB2
AFG1
AFG2
DON
FB1
FB2
HT2
OTA
T2
ZEN | Raw extract | — | (i) Eluent A H2O–HCOOH (99.9 : 0.1, v/v), eluent B CH3OH–HCOOH (99.9 : 0.1, v/v) both containing 5 mM NH4HCOO-
(ii) Gradient: 0.5 min at 30% eluent B, linear increase to 100% eluent B in 7.5 min, hold at 100% eluent B for 1.5 min, at 9.6 min back to 30% eluent B, reequilibration at 30% eluent B for 2 min, total run 11.5 min | A ZORBAX RRHD Eclipse Plus C18 (100 × 2.1 mm, 1.8 μm) column from Agilent Technologies | 0.04
0.04
0.2
0.1
3.4
1.4
1.3
0.8
0.1
0.1
1.2 | 0.1
0.1
0.1
0.4
1
4.3
3.9
2.5
0.4
0.2
2.9 | [160] |
| | Barley, malt, oat, wheat, and maize | DON
3-ADON
15-ADON
HT2
T2
BEA
FUSX
NIV
ZEA | CH3CN-H2O (84 : 16, v/v), | — | (i) Eluent A H2O-HCOOH (99.9 : 0.1, v/v), eluent B CH3OH-HCOOH (99.9 : 0.1, v/v); gradient ESI− 2 min at 10% eluent B, linear increase to 99% eluent B in 6 min, hold at 99% eluent B for 7.5 min, for 2 min back to 10% eluent B, reequilibration at 10% eluent B for 9.5 min, total run 25 min; ESI+ 2 min at 10% eluent B, linear increase to 87% eluent B in 6 min, hold at 87% eluent B for 7 min, increase to 100% eluent B in 5 min, hold at 100% eluent B for 3.5 min, for 2 min back to 10% eluent B, reequilibration at 10% eluent B for 9.5 min. | A Shimadzu LC-20A Prominence system (Shimadzu, Kyoto, Japan) using a Hydrosphere RP-C18 column (150 × 3.0 mm2, S-3 μm, 12 nm, YMC Europe GmbH, Dinslaken, Germany). | 0.9
1.7
4.6
0.1
0.2
0.3
5
5
0.5 | 2.6
13.5
13.5
0.2
0.5
0.7
3.1
2.9
1.5 | [95] |
|
|
