Recent Advances in Monitoring Microbial Toxins in Food Samples by HPLC-Based Techniques: A Review
Abstract
:1. Introduction
- Direct contact can occur due to contaminated hands of food handlers or infected animals and contaminated surfaces;
- Cross-contamination can occur due to pathogens transferred from raw foods or utensils used without proper cleaning, as well as to improper storage;
- Water contamination can occur by irrigating crops with contaminated water or using contaminated water during food processing, washing, or cooking;
- Airborne transmission can occur by spreading pathogens through the air in dust particles, water droplets, or poorly maintained or contaminated ventilation systems.
- Soil contamination can be caused by naturally present pathogens or by using untreated manure as fertilizers;
- Human factors, such as poor hygiene or sickness of food handlers, which can transmit pathogens to food through coughing, sneezing, or direct contact;Pests, which can include insects and rodents;
- Contaminated ingredients that could become contaminated during the supply chain.
2. HPLC-Based Methodologies for Microbial Toxin Detection in Food Samples
2.1. Aflatoxins and Other Mycotoxins
2.1.1. HPLC-UV
2.1.2. HPLC-FD
2.1.3. Novel Technologies: HPLC-MS/MS, LC-HRMS, and UPLC-MS/MS
2.2. Bacterial Toxins
2.2.1. HPLC-UV and HPLC-HRMS
2.2.2. UHPLC-MS/MS and Nano-LC-MS/MS
2.3. Cyanotoxins and Harmful Algal Blooms Toxins
2.3.1. HPLC-UV
2.3.2. HPLC-MS and UHPLC-MS
3. Conclusions
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Fungal Toxins (Mycotoxins) | Sample Type and Preparation | HPLC-Based Technique and Chromatographic Conditions | Analytical Parameters | Permissible Limits |
---|---|---|---|---|
Aflatoxins B1, B2, G1, and G2 [50] | Peanut butter 12.5 g of locally made peanut butter samples were combined with 2.5 g of NaCl, and 62.5 mL of 70% methanol was blended and then filtered using a No. 1 Whatman filter. Subsequently, 30 mL of water was added to 15 mL of the filtrate. After this, 15 mL were passed through a solid-phase extraction cartridge and rinsed with 10 mL water. Aflatoxins were eluted with 1 mL of ethanol and then 1 mL of water | HPLC-UV Aflatoxins were separated with a C-18 column with a mobile phase of 40:50:10 methanol-water-acetonitrile solution. The UV detection was carried out at 365 nm, with a flow rate of 0.7 mL min−1. The standards for aflatoxins G2, G1, B2, and B1 had 1, 4, 1, and 4 μg mL−1 concentrations, respectively. | Not validated method Total aflatoxin content ranged between 373.6–6741.6 µg kg−1, and aflatoxin B1 content was 54.3–805.8 µg kg−1 [50] | Sum of B1, B2, G1, and G2 in peanuts: 15 μg kg−1 [47] Sum of B1, B2, G1, and G2 in processed peanuts: 4 μg kg−1 [47] |
Fungal toxins (mycotoxins) | Sample type and preparation | HPLC-based Technique and chromatographic conditions | Analytical parameters | Permissible limits |
Aflatoxins B1, B2, G1, and G2, and M1 [51] | Rice and flour 5 g of powdered sample was dispersed in 10 mL 70:30 methanol-water and sonicated for 20 min. The supernatant was completed to 45 mL with water. Milk 20 mL samples were centrifuged at 5000 rpm for 15 min, filtered with a 0.22 µm syringe filter, and diluted with 25 mL of deionized water. A MOF-based structure was selected as adsorbent in the extraction and pre-concentration of aflatoxins | HPLC-FD A C18 column (150 × 4.6 mm; 5 µm) was used at 40 °C. A sample size of 25 µL was injected, and the mobile phase consisted of 65% methanol and 35% water, with a flow rate of 1.2 mL min−1. | Validated method LOD: 0.009–0.015 ng mL−1 Linearity: 0.05–8 ng mL−1 | Sum of B1, B2, G1, and G2 for cereals: 4 μg kg−1 [47] Sum of B1, B2, G1, and G2 for mixture of spices: 10 μg kg−1 [47] Aflatoxin M1 in milk: 0.05 μg kg−1 [47] |
Aflatoxins B1, B2, G1, and G2 [52] | Merkén spice Sample processing not specified. | HPLC-FD A HPLC-FLD with post-column derivation with a Kobra electrochemical cell (R-Biopharm Rhone, Glasgow, UK) was used. | Validated method LOD: 0.3 ng g−1 LOQ: 1.0 ng g−1 Linearity: 0.6–6.2 ng g−1 (B2 and G2), and 1.96–20 ng g−1 | |
Aflatoxins B1, B2, M1, and M2 [53] | Milk 2.5 mL of sample were defatted by centrifugation at 4000 rpm for 10 min. The sample was then vortex-mixed for 3 min and passed through an in-syringe dispersive micro-solid phase extraction (ISDμSPE) as a sample pretreatment. | HPLC-FD A C18 column Hypersil gold (250 × 4.6 mm; 5 µm) was used at 40°C. The sample size was 25 µL, and the flow rate was 1.2 mL min−1. A gradient was applied using a mobile phase consisting of a mix of 13:74:13 methanol-water-acetonitrile for 6 min, followed by 2 min of a 20:60:20 mix. A 9-min hold followed this, then the initial conditions were restored for 2 min and held until 35 min. The fluorescence detector was set at 360 and 440 nm for excitation and emission wavelengths, respectively. | Validated method LOD: 0.003–0.005 ng mL−1 LOQ: 0.01–0.02 ng mL−1 Linearity: 0.01–1.0 ng mL−1 for Aflatoxins M1, M2, and B2, and 0.02–1.0 ng mL−1 for Aflatoxin B1 | |
Aflatoxins M1 [54] | Raw milk Samples were filtrated with cellulose nitrate 0.45 µm membrane filters and centrifuged. The supernatant was filtered with 13 mm × 0.2 µm microfilters. | HPLC-FD A C18 column (250 × 4.6 mm; 5 µm) and immunoaffinity columns were used to isolate Aflatoxins M1. A fluorescence detector at 365 and 430 nm was used with a flow rate of 1 mL min−1 at room temperature. The mobile phases used were isocratic: (A) methanol, (B) acetonitrile, and (C) water. | Validated method LOD: 11.99 ng kg−1 and 16.95 ng kg−1 for aflatoxins M1 and M2, respectively. Linearity: 0.6–6.2 ng g−1 (B2 and G2), and 1.96–20 ng g−1 (B1, and G1) | |
Aflatoxins B1, B2, G1, and G2. Ochratoxin A [55] | Wheat 50 g of sample were extracted with 100 mL of an 8:2 methanol-water mixture and then filtered. Subsequently, 10 mL of filtrate was diluted with 10 mL of phosphate buffer solution (PBS). | HPLC-FD For aflatoxins, an Inertsil ODS-3C C-18 column (250 × 4.6 mm; 5 μm) was utilized at 40 °C. The sample volume was 100 µL, with a flow rate of 1 mL min−1 and a mobile phase consisting of a 6:2:3 water-acetonitrile-acetic acid mix. Post-column derivatization involved using 350 μL of 4M nitric acid and 120 mg of potassium bromide for every 1000 mL mobile phase. Detection occurred via fluorescence at wavelengths 333 and 460 nm. For Ochratoxin A, a mobile phase comprising 47:51:2 acetonitrile-water-acetic acid was employed. | Validated method LOD: 0.014–0.030 μg kg–1 LOQ: 0.045–0.098 μg kg–1 | Sum of B1, B2, G1, and G2 for cereals: 4 μg kg−1 [47] Sum of B1, B2, G1, and G2 in maize: 10 μg kg−1 [47] All foods ready for human consumption: not exceed 10 μg kg−1 of aflatoxin, of which aflatoxin B1 shall not be more than 5 μg kg−1 [56] Ochratoxin A in unprocessed cereals: 5 μg kg−1 [47] |
Aflatoxins B1, B2, G1, and G2. Ochratoxin A [40] | Processed meat 10 g of minced samples were mixed with 40 mL of a 60:40 acetonitrile-water mix and 0.2 g of NaCl. Then, 4 mL of the mixture were diluted in 44 mL of 2% tween-20-PBS. After that, 0.5 mL of the treated sample was mixed with 0.5 mL of acetonitrile for the cleanup process. | HPLC-FD 100 µL of extract was injected into a C-18 Thermo LC-Si column (250 × 4.6 mm) at 40 °C. The column had a fluorescence detector set at 365 and 435 nm. The mobile phase, consisting of toluene, ethyl acetate, formic acid, and methanol in a 90:5:2.5:2.5, was delivered at a flow rate of 2 mL min−1. | Validated method LOD for aflatoxin B1: 16.5–26.6 µg kg−1 LOD for ochratoxins: 3.8–17 µg kg−1 Linearity: 0.1–20 μg kg−1 | |
Fungal toxins (mycotoxins) | Sample type and preparation | HPLC-based Technique and chromatographic conditions | Analytical parameters | Permissible limits |
Aflatoxins B1, B2, G1, and G2 [46] | Wheat, corn, dried fig, or dried coffee beans 5 g of ground sample were mixed with 80% ethanol, filtered, and diluted in phosphate buffer solution (PBS). | HPLC-FD A sample of 50 mL was injected into AflacleanTM immunoaffinity columns at a flow rate of 0.5 mL min−1. The mobile phase consisted of a 60:30:10 water-methanol-acetonitrile solution. Detection was carried out on a UV-Vis at 365 nm. | Validated method LOD: 0.02–0.10 µg kg−1 LOQ: 0.04–0.45 µg kg−1 | Sum of B1, B2, G1, and G2 in corn and dried figs: 10 μg kg−1 [47] Sum of B1, B2, G1, and G2 in peanuts: 15 μg kg−1 [47] Sum of B1, B2, G1, and G2 for cereals: 4 μg kg−1 [47]; Sum of B1, B2, G1, and G2 for processed ground peanuts: 4 μg kg−1 [47] |
Aflatoxins B1, B2, G1, and G2 [57] | Raw peanuts 25 g of peanuts were blended with 125 mL solution containing 70% methanol, 30% water, and 5.0 g of NaCl. The mixture was then filtered and passed through an Aflatest® IAC column. | HPLC-FD A 40 µL sample was injected into a silica column (LC-Si, 5 µm, 25 cm × 4.6 cm) heated to 30°C at a flow rate of 1.5 mL min−1, using a mobile phase consisting of a 1:1 mixture of solution A (toluene-ethyl acetate-methanol 45:3:2 mL) and solution B (toluene-ethyl acetate-formic acid 45:3:2 mL). | Validated method LOQ: 2.0, 0.5, 1.0, and 0.5 ng g−1 for aflatoxins B1, B2, G1, and G2, respectively | |
Aflatoxins B1, B2, G1, and G2 [58] | Rice, flattened rice, sorghum, raw and processed peanut, almond, peanut butter, or wheat-based cookies 12.5 g of peanut samples + 12.5 g of water were mixed. 25 g of other samples were extracted with 80% methanol. | HPLC-FD IMMUNOPREP cleanup cartridges and a C18 column (150 × 4.6 mm; 5.0 µm) were utilized, along with a fluorescence detector set at 362 and 455 nm and a flow rate of 1.8 mL min-1. A gradient of solution A (24:52:21 acetonitrile-methanol-water) and solution B (80:20 methanol-water) was employed. The sample size was 1000 µL, and the process was conducted at 30 °C. | Validated method LOQ for peanut, sorghum, rice, and flattened rice: 0.125 ng g−1. LOQ for peanut butter, almond, and wheat-based cookies: 0.5 ng g−1. Linearity: 0.0125–10 ng g−1 | |
Aflatoxins B1, B2, G1, and G2 [59] | Peanut kernel 50 g of ground sample were mixed with 5 g of NaCl, 200 mL of 80:20 ethanol-water, and 100 mL of n-hexane for 30 min. The mixture was then filtered, and 20 mL of the sample was diluted with 130 mL of deionized water. | HPLC-FD 100 µL of the sample was injected into a reverse-phase C18 column (25 cm × 4.6 mm; 5 μm) at 40°C. The mobile phase consisted of water-methanol-acetonitrile (6:3:2) with 120 µL of potassium bromide and 350 µL of 4 N nitric acid. The flow rate was set at 1 mL min−1 with FARLIB® used as the post-column derivatization cell. A fluorescence detector was employed at 352 nm and 435 nm. | Validated method LOD: 0.06–0.15 µg kg−1 LOQ: 0.20–0.50 µg kg−1 Linearity: 0.4–7.2, 0.08–1.44, 0.4–7.2, and 0.08–1.44 μg L−1 for aflatoxins B1, B2, G1, and G2, respectively | |
Fungal toxins (mycotoxins) | Sample type and preparation | HPLC-based Technique and chromatographic conditions | Analytical parameters | Permissible limits |
Aflatoxins B1, B2, G1, and G2 [60] | Rice Samples were treated with a magnetic covalent organic framework. | HPLC-MS and HPLC-MS/MS HPLC method not available. A G1315B diode array detector with 500 nL and 10 mm pathlength coupled to a single quadrupole mass spectrometer with an electrospray ionization source was used. An ESI mode was chosen for instrument performance. The capillary voltage was set at 3000 V, and the analyte ionization voltage was 150 eV. N2 was employed as nebulizing gas at 35 psig with a drying flow of 12 L min−1 at 350 °C. | Validated method LOD: 0.0188–0.1250 μg kg−1 LOQ: 0.037567–0.3750 μg kg−1 Linearity: 0.375–20 μg kg−1 | Sum of B1, B2, G1, and G2 in rice: 10 μg kg−1 [47] Sum of B1, B2, G1, and G2 for cereals: 4 μg kg−1 [47] All foods ready for human consumption should not exceed 10 μg of aflatoxin, of which aflatoxin B1 shall not be more than 5 μg kg−1 [56] Ochratoxin A in unprocessed cereals: 5 μg kg−1 [47] |
Aflatoxins B1, B2, G1, and G2 [37] | Commercial rice 20 g of ground sample were spiked at 1.43 µg kg−1, and then 100 mL of an 80:20 methanol-water solution was added. The mixture was stirred at 950 rpm for 1 h. After sedimentation, the supernatant was centrifuged at 5000 rpm for 45 min. Next, 7 mL of the treated sample was diluted with 43 mL PBS and filtered through a syringe filter. | HPLC-MS and HPLC-MS/MS A C18 column was used (15 × 0.3 mm; 4 µm). The sample size was 10 µL, with a flow rate of 10 µL min−1. The column was coupled to a diode array and a single quadrupole mass spectrometer. The mobile phase comprised a mixture of formic acid 0.05% and acetonitrile. Diode array and mass spectrometer detectors (cHPLC-DAD/MS) Model 1100 Series, (Agilent Technologies, Madrid, Spain) were used. Also, a G1315B diode array detector (Agilent Technologies, Madrid, Spain) with 500 nL and 10 mm pathlength coupled to a single quadrupole mass spectrometer with an electrospray ionization source (Model 6120 Series, Agilent Technologies) were used. Positive ESI mode was used, the capillary voltage was set at 3000 V, and analyte ionization voltage at 150 eV. N2 was employed as nebulizing gas at 35 psig with a drying flow of 12 Lmin−1 at 350 °C. | Validated method LOD: 0.0967–0.3267 µg kg−1 LOQ: 0.3167–1.0667 µg kg−1 Linearity: 1–25 µg L−1 for all analytes | |
Aflatoxins B1, B2, G1, and G2 [61] | Cultured fish Fish muscle and liver samples were extracted by an ultrasound-assisted extraction procedure using a 60:40 acetonitrile-0.1 M KH2PO4 aqueous buffer (pH 6.0) mixture. | HPLC-MS and HPLC-MS/MS Sample size: 20 μL, flow rate of 60 μL min−1, mobile phase: 0.1:99.9 formic acid-methanol. A 3200 Q TRAP LC/MS/MS (ABSciex, Concord, Canada) with an electrospray ionization source was used, ions spray voltage (IS), 5500 kV; ion source temperature of 300 °C; N2 as nebulizer gas and curtain gas, 40 psi; N2 as collision gas. | Validated method LOD: 0.2967–0.61 μg kg−1 [61] | |
Aflatoxins B1, B2, G1, and G2. Ochratoxin A and B. Enniatins A, B, A1, and B1 [62] | Maize Samples were treated with a magnetic covalent organic framework. | HPLC-MS and HPLC-MS/MS A C18 column was used (100 × 3 mm; 1.8 µm) at 40°C. The sample size was 2 µL and detected through a triple-quadrupole mass spectrometer. Mobile phase: gradient mixture of Solvent A (100% acetonitrile) and B (0.1:99.9 formic acid-5 mmol L−1 ammonium formate), flow rate of 0.4 mL min−1. An Agilent 6460 triple-quadrupole mass spectrometer equipped with an electrospray ionization source was used. Mode, positive multiple reaction monitoring (MRM+); drying gas temperature of 300 °C; sheath gas temperature of 250 °C; drying gas flow rate of 5 L min−1; sheath gas flow rate, 10 L min−1; nebulizer pressure of 45 psi; capillary voltage of 3500 V; and nozzle voltage of 0 V. High-purity N2 was used as the drying gas. | Validated method LOD: 0.0267–1.67 µg kg−1 LOQ: 0.07–5.57 µg kg−1 Linearity: 0.05–20 μg kg−1 |
Bacterial Toxins | Sample Type and Preparation | HPLC-Based Technique and Chromatographic Conditions | Analytical Parameters | Permissible Limits |
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Toxoflavin and fervenulin [81] | Rice bran oil, sweet potato starch, distiller’s yeast, Tremella fuciformis Berk, rice noodles, and fermented corn flour 1.0 g of rice bran oil was extracted twice with 6 mL of methanol. The mixture was then centrifuged at 10,000 rpm for 5 min. The other samples (were weighed and extracted in an ultrasonic bath for 10 min with 10 mL of extraction solvent. For Tremella fuciformis Berk and distiller’s yeast, methanol was used as the extraction solvent, while sweet potato starch, rice noodle, and fermented corn flour were extracted using 0.1:99.9 formic acid–water. These mixtures were then centrifuged at 10,000 rpm for 10 min. Subsequently, all samples were filtered and loaded into SPE cartridges. 6 different SPE cartridges and 6 solvents were tried, with the Oasis HLB having the best recovery, using methanol. | UHPLC-MS/MS A C18 column (150 × 2.1 mm; 5 μm) was used at 35 °C with a mobile phase consisting of 0.1% formic acid (v/v, solvent A) and methanol (solvent B). The flow rate was 0.4 mL/min. Gradient elution was programmed as follows: 0 min, 12% B; 1.00 min, 12% B; 2.50 min, 90% B; 5.00 min, 90% B; 5.01 min, 12% B; 10.00 min, 12% B. The injection volume was 5 μL. An Agilent 6460 triple quadrupole mass spectrometry (Yishun, Singapore) was used. The mass spectrometry was operated in the multiple reaction monitoring (MRM) mode with positive electrospray ionization (ESI+). Ion source conditions were as follows: N2 as drying gas, temperature of 350 °C; drying gas (N2) flow rate of 11 L min−1; nebulizer gas pressure, 3.4 × 105 Pa; capillary voltage, 4000 V. | Validated method LOD: 12–60 μg kg−1 LOQ: 40–200 μg kg−1 Linearity for toxoflavin: 20–1000 μg L−1 Linearity for fervenulin: 40–1000 μg L−1 | Not specified. |
Bongkrekic and isobongkrekic acids [77] | Rice noodles A 2.0 g sample was mixed with 20 mL of acidic water (pH 4.4) and sonicated for 20 min. The sample solution was then filtered. Subsequently, 81 mg of magnetic nanotubes were added to the filtrate and vortex-mixed for 4.2 min. The magnetic nanotubes were isolated using a strong magnet, and the supernatant was discarded. The magnetic sorbent was eluted thrice with 0.5 mL of acetonitrile containing 1% formic acid. The eluate was collected and dried using a nitrogen stream at 40°C. The residue was diluted to 1.0 mL with a 50% acetonitrile aqueous solution and filtered using a 0.22 μm filter. | HPLC-Orbitrap HRMS technology with magnetic halloysite nanotubes A C18 column (150 × 2.1 mm; 2.6 μm) was used at 35 °C. The mobile phase was used in a gradient elution program consisting of a 0.1% formic acid water solution (A) and acetonitrile (B). The gradient elution program was as follows: 0–3 min, 50% B to 70% B; 3–3.6 min, 70% B to 95% B; 3.6–5.5 min, 95% B; 5.5–5.6 min, 95% B to 50% B; 5.6–7.0 min, 50% B. The flow rate was 0.3 mL min−1, and the injection volume was 5 μL. An HPLC-Orbitrap HRMS (Thermo Fisher Scientific, Germany) was used. Flow rates of sheath gas, auxiliary gas, and sweep gas were set at 45, 8, and 0 arbitrary units, respectively. The spray voltage was set at −3.0 kV. Mass range (m/z) was 100–600. The capillary and auxiliary gas heater temperatures were 320 °C and 350 °C, respectively. | Validated method LOD: 0.3 μg kg−1 LOQ: 1.0 μg kg−1 Linearity: 2–200 μg L−1 | Bonkrekik acid: fatal for humans at 1.0–1.5 mg orally [78] |
Algal and Cyanobacterial Toxins (Cyanotoxins) | Sample Type and Preparation | HPLC-Based Technique and Chromatographic Conditions | Analytical Parameters | Permissible Limits |
---|---|---|---|---|
Cyanobacteria Microcystin-LR and anatoxin-A [85] | Food supplements containing microalgae The samples were extracted three times using 2.5 mL of a 75:25 methanol-water mixture at 60 °C. After extraction, the samples were dried in a Speedvac and reconstituted in 900 mL of methanol. Then, the reconstituted samples were transferred to 2 mL Eppendorf vials equipped with a cellulose-acetate filter (Corning Costar Spin-X centrifuge tube filters) and centrifuged for 5 min at 16,000× g. | HPLC-MS 20 mL of sample were loaded onto a C18 column (150 × 4.6 mm; 5 mm). The mobile phase consisted of water with 0.1% formic acid as eluent A and acetonitrile with 0.1% formic acid as eluent B. The elution program was as follows: 0–2 min at 30% B, a linear increase of B between 2 and 6 min, 6–12 min at 90% B, and a 5-min post-run at 30% B. The flow rate was maintained at 0.5 mL min−1, and the procedure was conducted at 40 °C. A hybrid mass spectrophotometer Agilent Q-TOF 6550, with an ionization source JetStream electrospray + i-Funnel. MS operated in the positive mode and N2 was used as the drying and collision gas. The quadrupole was operated in the unit mode and four spectra/s were recorded. | Not validated method Concentrations of toxins in samples from 0.002 ± 0.0001 µg g−1–0.034 ± 0.002 µg g−1 | Mycrocistin: 1 μg g−1 [93] |
Cyanobacteria 27 cyanotoxins [86] | Spirulina, Aphanizomenon flos-aquae, Chlorella, and kelp algal dietary supplement samples The samples were extracted twice with 5 mL of methanol + 0.1 M formic acid. The mixture was vortexed for 30 s and then placed in an ultrasonic bath for 15 min. After that, the supernatant was collected following centrifugation at 6000 rpm for 10 min. The supernatants were then treated with 100 mg of graphitized carbon black for clean-up. The resulting mixture was filtered using PES (0.2 μm) and evaporated at 45 °C. Subsequently, the samples were homogenized in 3 mL of water for 5 min in an ultrasonic bath. An aliquot was filtered using PES (0.2 μm). Finally, an oxidation step was performed using 340 μL potassium permanganate 0.4 M, 380 μL sodium periodate 0.35 M, and potassium carbonate 1 M to adjust the pH to 9 [86] | HPLC-MS and HPLC-HRMS 1 mL of sample was applied to a C18 online SPE column (20 × 2.1 mm; 12 μm), and then transferred to a HypersilTM Gold C18 HPLC column (100 × 2.1 mm; 1.9 μm). For individual microcystins: UHPLC-HRMS, Thermo Q-Exactive Orbitrap was used. A heated electrospray ionization interface (HESI-II) operated in positive mode was used for analyte ionization. The ionization spray voltage was set at +3500 V; capillary temperature was set at 350 °C; the vaporizer temperature was set at 250 °C; sheath gas and auxiliary gas flow were set at 60 and 15 arbitrary units, respectively. For total microcystins: UHPLC-MS/MS, Thermo TSQ Quantiva was used. An SPE column Hypersyl Gold aQ C18 (20 × 2.1 mm; 12 μm) was used, and the analytical column Hypersil Gold C18 (50 mm × 2.1 mm, 1.9 μm particle size | Validated method LOD: 0.1–35 ng g−1 LOQ: 0.3–105 ng g−1 Linearity: 10–1000 ng g−1 | |
Algae Paralytic shellfish toxins [94] | Stomach content and liver samples from dead kelp gulls, Magellanic penguins, Papua penguins, and imperial cormorants, along with zooplankton, squat lobsters, Fuegian sprat, and seabirds Samples from DGLTM ** were extracted with cold 0.04 M acetic acid and sonicated 1 min at 4 s intervals. Samples were pre-treated with C18 SPE columns activated with methanol. [94] | HPLC-UV A C18 column (25 cm × 4.6 mm; 5–10 µm), at 40 °C, rate flow of 1.0–1.5 mL min−1. The mobile phase was a mixture of 100:899:1 acetonitrile-water- trifluoroacetic acid. | Not validated method LOD: 400 μg Kg−1 LOQ: 3–8 pmol mL −1 | For paralytic shellfish toxins: 80 mg STX eq/100 g [92] |
Algal and cyanobacterial toxins (cyanotoxins) | Sample type and preparation | HPLC-based Technique and chromatographic conditions | Analytical parameters | Permissible limits |
Algae Okadaic acid [95] | Shellfish 0.9 mL of methanol was added to the samples, vortex-mixed, and sonicated. The resulting supernatants were centrifuged at 8000 rpm for 5 min. The extracts were then adjusted to a volume of 2 mL. Next, 2.5 M sodium hydroxide was added, and the mixture was incubated at 70 °C for 1 h. After cooling, an equivalent amount of hydrochloric acid was added, and the solution was filtered using a 0.22 µm filter. Finally, 6 mL of methanol and 6 mL of water were added. | HPLC-UV A C18 column with a UV-vis detector was used at 200 nm, with a flow rate of 2 mL min-1, an injection volume of 20 µL, and a mobile phase 35:65 (water-acetonitrile). | Validated method LOD: 4.55 × 10−3 ng mL−1 [95] | Okadaic acid, dinophysis toxins, and pecteno-toxins together: 160 mg OA equivalents kg−1 [92] |
Algae Domoic acid [96] | Mollusks 4 g of shredded and homogenized samples were mixed with 16 mL of solvent extraction (1:1 methanol-water solution), homogenized for 3 min at 10,000 rpm, then centrifuged for 10 min at 4000 rpm. | HPLC-UV A C18 column (250 × 4.6 mm; 5 μm) was used with a flow rate of 1 mL min−1, a detection wavelength of 242 nm, an injection volume of 20 μL, and an oven temperature for the column of 40 °C. | Validated method LOD: 0.05 mg kg−1 | Domoic acid: 20 µg g−1 of tissue [91] |
Algae Okadaic acid, yessotoxin, pectenotoxin, and azaspiracid [97] | Processed food Deionized water was added (30% of the weighted sample), and 5 mL of the sample was diluted with 5 mL of ultrapure water. | HPLC-MS and UHPLC-MS The sample was loaded into an SPE cartridge and eluted with 2 mL of methanol and 3% ammonium hydroxide. Later, it was passed through a C18 column (100 × 2.1 mm; 1.7 µm) with detection by MS/MS at 40 °C. The injection volume was 5 µL with a flow rate of 0.2 mL min−1. Different gradients of solution A (water) and B (acetonitrile), both with 0.04% v/v of ammonium hydroxide, were used, starting at B 20%, then B 85%, B 98%, and finally B 20%. A triple quadrupole mass spectrometer TSQ-Endura (Thermo Fisher Scientific, Waltham, MA, USA), equipped with a heated electrospray source (H-ESI II) operating in both positive (ESI+) and negative mode (ESI−). N2 was used as sheath and auxiliary gas, while Argon was used as collision gas. The optimized parameters were: capillary voltage (3500 V in ESI+ and 2700 V in ESI−), sheath gas flow rate (30 arbitrary units), auxiliary gas flow rate (10 arbitrary units), ion transfer tube temperature (270 °C), vaporizer temperature (240 °C) and collision gas pressure (2.5 mTorr). | Validated method LOQ: 3–8 µg kg−1 | Okadaic acid, dinophysis toxins and pecteno-toxins together: 160 mg Okadaic Acid (OA) equivalents kg−1 [92] Yessotoxins: 1 mg YTX equivalents kg−1 [92] Azaspiracid: 160 µg kg−1 [92] |
Algal and cyanobacterial toxins (cyanotoxins) | Sample type and preparation | HPLC-based Technique and chromatographic conditions | Analytical parameters | Permissible limits |
Algae Cyclic imine analogues spirolide, gymnodimine, and pinnatoxin groups [98] | Mussel and oysters 1 g samples were extracted using 9 mL of methanol, vortex-mixed for 3 min, and centrifuged at 3400× g for 8 min at 20 °C. The resulting supernatants were then filtered through a 0.2 µm nylon filter. | HPLC-MS and UHPLC-MS A C18 column (50 × 2.1 mm; 1.7 µm) was used at 30 °C with an injection volume of 2 µL and flow rates of 0.4–0.6 mL min−1. Various mobile phases were used, and 1 mM ammonium fluoride in methanol had the best signal intensity. A Xevo-TQ-S triple quadrupole mass spectrometer (MS/MS) with electrospray ionization was used, with a 150 °C source temperature, 600 °C desolvation temperature, 1100 L/Hr desolvation gas flow, 150 L/Hr cone gas flow and a 1.0 kV capillary voltage. | Validated method LOD: 0.01–16.5 µg kg−1 LOQ: 0.03–55 µg kg−1 Linearity: 0.1–80 µg kg−1, 0.1–40 µg kg−1, 0.4–40 µg kg−1, 0.1–20 µg kg−1, and 1–320 µg kg−1 for PnTx-E and PnTx-F, PnTx-G and 20-Me-SPX-G, GYM-A and 13-desMe-SPX-C, 13,19-didesMe-SPX C, and 12-Me-GYM toxins, respectively | Not regulated [99] |
Algae: Phycotoxins and cyanotoxins [100] | Fresh and salt waters: 500 mL samples were acidified to pH 3 with formic acid. | HPLC-MS and UHPLC-MS: Samples were loaded onto an SPE cartridge at a flow rate of 5 mL min−1. The analytes were eluted using methanol with 1% formic acid. Subsequently, a C18 column (150 × 2.1 mm; 3.5 µm) preceding a pre-column C18, both maintained at 30 °C, was employed. A gradient was performed using solvent A (water) and solvent B (acetonitrile), containing 0.5% formic acid. The gradient involved a change from 95% A to 2% A with corresponding changes in B, at a flow rate of 0.2 mL min−1 and an injection volume of 10 µL. | LOD: 0.3–29 ng L−1 LOQ: 1–88 ng L−1 Linearity: 2.5–250 µg L−1 | For phycotoxins (domoic and okadaic acids): Okadaic acid, dinophysis toxins and pecteno-toxins together: 160 mg OA equivalents kg−1 [92] Domoic acid: 20 µg g−1 of tissue [91] For cyanotoxins (microcystin): 1 μg g−1 [93] |
Algae: Azaspiracids, brevetoxins, okadaic acid group, and domoic acid [101] | Mussels: Homogenized samples were extracted with different acetic acid and methanol concentrations. Then, the extracts were loaded in C18 SPE cartridges. | HPLC-MS and UHPLC-MS: An ODS-3 C18 column (150 × 2.1 mm; 3 µm) was used at 40 °C, with a 2 µL injection volume and a flow rate of 0.2 mL min−1. The mobile phase comprised 0.1% aqueous formic acid (A) and acetonitrile (B). A linear gradient of 5–60% B, 60–70% B, and 90% B was used to separate lipophilic biotoxins. A 10% solution of B was utilized to analyze domoic acid. | LOD: 0.002–0.017 mg kg−1 LOQ: 0.007–0.058 mg kg−1 Detection range: 0.008–0.2 mg Kg−1 to 0.06–6 mg kg−1 | For azaspiracid: 160 µg kg−1 [92] Brevetoxins: not regulated [99] Okadaic acid, dinophysis toxins and pecteno-toxins together: 160 mg OA equivalents kg−1 [92] Domoic acid: 20 µg g−1 of tissue [91] |
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Quintanilla-Villanueva, G.E.; Sánchez-Álvarez, A.; Núñez-Salas, R.E.; Rodríguez-Delgado, M.M.; Luna-Moreno, D.; Villarreal-Chiu, J.F. Recent Advances in Monitoring Microbial Toxins in Food Samples by HPLC-Based Techniques: A Review. Analytica 2024, 5, 512-537. https://doi.org/10.3390/analytica5040035
Quintanilla-Villanueva GE, Sánchez-Álvarez A, Núñez-Salas RE, Rodríguez-Delgado MM, Luna-Moreno D, Villarreal-Chiu JF. Recent Advances in Monitoring Microbial Toxins in Food Samples by HPLC-Based Techniques: A Review. Analytica. 2024; 5(4):512-537. https://doi.org/10.3390/analytica5040035
Chicago/Turabian StyleQuintanilla-Villanueva, Gabriela Elizabeth, Araceli Sánchez-Álvarez, Raisa Estefanía Núñez-Salas, Melissa Marlene Rodríguez-Delgado, Donato Luna-Moreno, and Juan Francisco Villarreal-Chiu. 2024. "Recent Advances in Monitoring Microbial Toxins in Food Samples by HPLC-Based Techniques: A Review" Analytica 5, no. 4: 512-537. https://doi.org/10.3390/analytica5040035
APA StyleQuintanilla-Villanueva, G. E., Sánchez-Álvarez, A., Núñez-Salas, R. E., Rodríguez-Delgado, M. M., Luna-Moreno, D., & Villarreal-Chiu, J. F. (2024). Recent Advances in Monitoring Microbial Toxins in Food Samples by HPLC-Based Techniques: A Review. Analytica, 5(4), 512-537. https://doi.org/10.3390/analytica5040035