Development of a LC–MS/MS Method for the Simultaneous Determination of the Mycotoxins Deoxynivalenol (DON) and Zearalenone (ZEA) in Soil Matrix
Abstract
:1. Introduction
2. Results and Discussion
2.1. LC–MS/MS Optimization
2.2. Extraction Steps
2.3. Method Performance
2.3.1. Linearity
2.3.2. Recovery and Matrix Effect
2.3.3. Aging
2.3.4. Routine Limit of Detection and Quantification
2.3.5. Validation at Natural Concentration Levels
3. Conclusions
4. Materials and Methods
4.1. Chemicals and Reagents
4.2. Soil Samples
4.3. Testing of Different Extraction Methods and Solvents
4.4. Soil Preparation and Extraction Method
4.5. Chromatographic Separation and Quantification
4.6. Method Performance
4.6.1. Linearity
4.6.2. Recovery and Matrix Effect
4.6.3. Aging
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
- Wild, C.P.; Hudson, G.J.; Sabbioni, G.; Chapot, B.; Hall, A.J.; Wogan, G.N.; Whittle, H.; Montesano, R.; Groopman, J.D. Dietary intake of aflatoxins and the level of albumin-bound aflatoxin in peripheral blood in The Gambia, West Africa. Cancer Epidem. Biomar. 1992, 1, 229–234. [Google Scholar]
- Wolfarth, F.; Schrader, S.; Oldenburg, E.; Weinert, J.; Brunotte, J. Biological control of the phytopathogenic fungus Fusarium culmorum and its mycotoxin deoxynivalenol by earthworms. Soil Biol Biochem 2011, 43, 1858–1865. [Google Scholar] [CrossRef]
- Marin, S.; Ramos, A.J.; Cano-Sancho, G.; Sanchis, V. Mycotoxins: Occurrence, toxicology, and exposure assessment. Food Chem. Toxicol. 2013, 60, 218–237. [Google Scholar] [CrossRef]
- Zain, M.E. Impact of mycotoxins on humans and animals. J. Saudi Chem. Soc. 2011, 15, 129–144. [Google Scholar] [CrossRef] [Green Version]
- Zheng, Z.; Humphrey, C.W.; King, R.S.; Richard, J.L. Validation of an ELISA test kit for the detection of total Aflatoxins in grain and grain products. Mycopathologia 2005, 159, 255–263. [Google Scholar] [CrossRef]
- Tola, M.; Kebede, B. Occurrence, importance and control of mycotoxins: A review. Cogent Food Agric. 2016, 2, 779. [Google Scholar] [CrossRef]
- Alshannaq, A.; Yu, J.H. Occurrence, Toxicity, and Analysis of Major Mycotoxins in Food. ISDE 2017, 13, 632. [Google Scholar] [CrossRef] [Green Version]
- Miraglia, M.; De Santis, B.; Brera, C. Climate change: Implications for mycotoxin contamination of foods. J. Biotechnol. 2008, 136, 715–716. [Google Scholar] [CrossRef]
- Tirado, M.; Clarke, R.; Jaykus, L.-A.; McQuatters-Gollop, A.; Frank, J. Climate change and food safety: A review. Food Res. Int. 2010, 43, 1745–1765. [Google Scholar] [CrossRef]
- Paterson, R.R.M.; Lima, N.; Taniwaki, M.H. Coffee, mycotoxins and climate change. Food Res. Int. 2014, 61, 1–15. [Google Scholar] [CrossRef]
- Reddy, K.R.N.; Nurdijati, S.B.; Salleh, B. An overview of plant-derived products on control of mycotoxigenic fungi and mycotoxins. Asian J. Plant Sci. 2010, 9, 126. [Google Scholar] [CrossRef] [Green Version]
- Rotter, B.A.; Prelusky, D.B.; Pestka, J.J. Toxicology of deoxynivalenol (vomitoxin). J. Toxicol. Environ. 1996, 48, 134. [Google Scholar]
- Curtui, V.; Brockmeyer, A.; Dietrich, R.; Kappenstein, O.; Klaffke, H.; Lepschy, J.; Märtlbauer, E.; Schneider, E.; Seidler, C.; Thielert, G.; et al. Deoxynivalenol in Lebensmitteln. Mycotoxin Res. 2005, 21, 83–88. [Google Scholar] [CrossRef]
- Pestka, J.J. Deoxynivalenol. Toxicity, mechanisms and animal health risks. JAFST 2007, 137, 283–298. [Google Scholar] [CrossRef]
- Ueno, Y. Trichothecenes: Chemical, biological, and toxicological aspects. Science 1983, 15, 135–146. [Google Scholar]
- Sobrova, P.; Adam, V.; Vasatkova, A.; Beklova, M.; Zeman, L.; Kizek, R. Deoxynivalenol and its toxicity. Interdiscip. Toxicol. 2010, 3, 94–99. [Google Scholar] [CrossRef] [PubMed]
- Hughes, D.M.; Gahl, M.J.; Graham, C.H.; Grieb, S.L. Overt signs of toxicity to dogs and cats of dietary deoxynivalenol. Anim. Sci. J. 1999, 77, 693–700. [Google Scholar] [CrossRef] [PubMed]
- Yoshizawa, T.; Takeda, H.; Ohi, T. Structure of a novel metabolite from deoxynivalenol, a trichothecene mycotoxin, in animals. Agric. Biol. Chem. 1983, 47, 2133–2135. [Google Scholar] [CrossRef]
- Bhatnagar, D.; Yu, J.; Ehrlich, K.C. Toxins of filamentous fungi. Chem. Immunol. 2002, 81, 167–206. [Google Scholar] [PubMed]
- Hussein, H.S.; Brasel, J.M. Toxicity, metabolism, and impact of mycotoxins on humans and animals. Toxicology 2001, 167, 101–134. [Google Scholar] [CrossRef]
- Yazar, S.; Omurtag, G.Z. Fumonisins, trichothecenes and zearalenone in cereals. Int. J. Mol. Sci. 2008, 9, 2062–2090. [Google Scholar] [CrossRef]
- Richard, J.L. Some major mycotoxins and their mycotoxicosis—An overview. Int. J. Food Microbiol. 2007, 119, 3–10. [Google Scholar] [CrossRef]
- Bennett, J.W.; Klich, M. Mycotoxins. CMR 2003, 16, 497–516. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- De Santis, B.; Debegnach, F.; Gregori, E.; Russo, S.; Marchegiani, F.; Moracci, G.; Brera, C. Development of a LC–MS/MS Method for the Multi-Mycotoxin Determination in Composite Cereal-Based Samples. Toxins 2017, 9, 169. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Mortensen, G.K.; Strobel, B.W.; Hansen, H.C.B. Determination of zearalenone and ochratoxin A in soil. Anal. Bioanal. Chem. 2003, 376, 98–101. [Google Scholar] [CrossRef] [PubMed]
- Mortensen, G.K.; Stroble, B.W.S.; Hansen, C.B.H. Degradation of zearalenone and ochratoxin A in three Danish agricultural soils. Chemosphere 2006, 62, 1673–1680. [Google Scholar] [CrossRef] [PubMed]
- Muñoz, K.; Schmidt-Heydt, M.; Stoll, D.; Diehl, D.; Ziegler, J.; Geisen, R.; Schaumann, G.E. Effect of plastic mulching on mycotoxin occurrence and mycobiome abundance in soil samples from asparagus crops. Mycotoxin Res. 2015, 31, 191–201. [Google Scholar] [CrossRef] [PubMed]
- Hartmann, N.; Erbs, M.; Forrer, H.-R.; Vogelgsang, S.; Wettstein, F.E.; Schwarzenbach, R.P.; Bucheli, T.D. Occurrence of Zearalenone on Fusarium graminearum Infected Wheat and Maize Fields in Crop Organs, Soil, and Drainage Water. Environ. Sci. Technol. 2008, 42, 5455–5660. [Google Scholar] [CrossRef]
- Hartmann, N.; Erbs, M.; Wettstein, F.E.; Hoerger, C.C.; Schwarzenbach, R.P.; Bucheli, T.D. Quantification of Zearalenone in Various Solid Agroenvironmental Samples Using D6-Zearalenone as the Internal Standard. J. Agric. Food Chem. 2008, 56, 2926–2932. [Google Scholar] [CrossRef]
- Gromadzka, K.; Waśkiewicz, A.; Świetlik, J.; Bocianowski, J.; Goliński, P. Possible way of zearalenone migration in the agricultural environment. Plant Soil Environ. 2015, 61, 358–363. [Google Scholar] [CrossRef] [Green Version]
- Kögel-Knaber, I.; Amelung, W. Dynamics, Chemistry, and Preservation of Organic Matter in Soils. In Treatise on Geochemistry, 2nd ed.; Holland, H.D., Turekian, K.K., Eds.; Elsevier: Oxford, UK, 2014; Volume 12, pp. 157–215. [Google Scholar]
- Morrison, D.E.; Robertson, B.K.; Alexander, M. Bioavailability of aged DDT, DDE, DDD, and dieldrin in soil. Environ. Sci. Technol. 2000, 34, 709–713. [Google Scholar] [CrossRef]
- Förster, M.; Laabs, V.; Lamshöft, M.; Pütz, T.; Amelung, W. Analysis of aged sulfadiazine residues in soils using microwave extraction and liquid chromatography tandem mass spectrometry. Anal. Bioanal. Chem. 2008, 391, 1029–1038. [Google Scholar] [CrossRef] [Green Version]
- Hatzinger, P.B.; Alexander, M. Effect of chemicals in soil on their biodegradability and extractability. Environ. Sci. Technol. 1995, 29, 537–545. [Google Scholar] [CrossRef]
- Verma, J.; Johri, T.S.; Swain, B.K.; Ameena, S. Effect of graded levels of aflatoxin, ochratoxin and their combinations on the performance and immune response of broilers. Br. Poult. Sci. 2004, 45, 512–518. [Google Scholar] [CrossRef]
- Capriotti, A.L.; Caruso, G.; Cavaliere, C.; Foglia, P.; Samperi, R.; Laganà, A. Multiclass mycotoxin analysis in food, environmental and biological matrices with chromatography/mass spectrometry. Mass Spectrom. Rev. 2010, 31, 466–503. [Google Scholar] [CrossRef] [PubMed]
- Serrano, A.B.; Capriotti, A.L.; Cavaliere, C.; Piovesana, S.; Samperi, R.; Ventura, S.; Laganà, A. Development of a rapid LC–MS/MS method for the determination of emerging Fusarium mycotoxins enniatins and beauvericin in human biological fluids. Toxins 2015, 7, 3554–3571. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Rahmani, A.; Jinap, S.; Soleiman, F. Qualitative and Quantitative Analysis of Mycotoxins. Compr. Rev. Food Sci. Food Saf. 2009, 8, 202–251. [Google Scholar] [CrossRef]
- De Pereira, V.L.; Fernandes, J.O.; Cunha, S.C. Mycotoxins in cereals and related foodstuffs: A review on occurrence and recent methods of analysis. Trends Food Sci. Technol. 2014, 36, 96–136. [Google Scholar] [CrossRef]
- Alef, K.; Nannipieri, P. Methods in Applied Soil Microbiology and Biochemistry, 2nd ed.; Academic Press: London, UK, 1995. [Google Scholar]
Mycotoxin | Retention Time (min) | Precursor Ion (m/z) | Product Ions (m/z) | Collision Energy (V) | Cone Voltage (V) |
---|---|---|---|---|---|
DON | 2.92 | 297 [M + H]+ | 175.1/203.2 | 28/11 | 22 |
13C15-DON | 2.92 | 312 [M + H]+ | 186.5 | 29 | 22 |
ZEA | 7.40 | 319 [M + H]+ | 185.1/186.9 | 23/15 | 22 |
13C18-ZEA | 7.40 | 337 [M + H]+ | 168.2 | 32 | 22 |
Sample | SOC (g/kg) | Clay (%) | Silt (%) | Sand (%) | Major Reference Soil Group |
---|---|---|---|---|---|
Ascheberg * | 6.1 | 69 | 28 | 4 | clay |
Auweihler * | 4.3 | 1 | 3 | 96 | sand |
Berrenrath * | 18.9 | 16 | 75 | 7 | silt loam (silt) |
Frankenforst * | 21.2 | 34 | 36 | 30 | silty clay loam (mix) |
Lüttewitz ** | 20.6 | 14 | 83 | 3 | silt loam |
Rackwitz ** | 20.5 | 14 | 53 | 33 | silt loam |
RA ± RSDr (%) | ||||
---|---|---|---|---|
ACN * | H2O/ACN ** | MeOH/H2O * | ACN/H2O/AcOH ** | |
(80:20) | (90:10) | (79:20:1) | ||
Ultrasonic bath for 1 h | ||||
DON | 56 ± 21 | 68 ± 8 | 69 ± 4 | 85 ± 5 |
ZEA | 51 ± 5 | 69 ± 9 | 67 ± 5 | 86 ± 4 |
shaking for 24 h | ||||
DON | 46 ± 21 | 65 ± 12 | 64 ± 8 | 69 ± 9 |
ZEA | 42 ± 19 | 49 ± 5 | 65 ± 6 | 71± 5 |
accelerated solvent extraction | ||||
DON | 26 ± 10 | 30 ± 11 | 32 ± 9 | 35 ± 8 |
ZEA | 31 ± 3 | 24 ± 6 | 42 ± 5 | 43 ± 6 |
Pressurized solvent extraction | ||||
DON | 27 ± 8 | 32 ± 9 | 36 ± 7 | 38 ± 8 |
ZEA | 23 ± 6 | 34 ± 5 | 32 ± 8 | 43 ± 7 |
Mycotoxin | Concentration Ranges | R2 and p-Value (***) | ||||
---|---|---|---|---|---|---|
Neat Solvent Mixture A/B (50:50) | Sand | Clay | Silt | Mix | ||
DON | 1–100 ng/mL | 0.9983 *** | 0.9894 *** | 0.9895 *** | 0.9924 *** | 0.9967 *** |
ZEA | 0.5–100 ng/mL | 0.9996 *** | 0.9944 *** | 0.9886 *** | 0.9928 *** | 0.9926 *** |
Soil Texture | DON | ZEA | |
---|---|---|---|
sand | LOQ (ng/g) | 1 | 0.5 |
RA (%) | 86 | 83 | |
SSE (%) | 88 | 82 | |
RE (%) | 98 | 102 | |
RSDr (%) | 8 | 7 | |
clay | LOQ (ng/g) | 1 | 0.5 |
RA (%) | 87 | 85 | |
SSE (%) | 90 | 89 | |
RE (%) | 97 | 96 | |
RSDr (%) | 6 | 8 | |
silt | LOQ (ng/g) | 1 | 0.5 |
RA (%) | 85 | 82 | |
SSE (%) | 86 | 83 | |
RE (%) | 99 | 99 | |
RSDr (%) | 9 | 6 | |
mix | LOQ (ng/g) | 1 | 0.50 |
RA (%) | 83 | 82 | |
SSE (%) | 83 | 84 | |
RE (%) | 100 | 98 | |
RSDr (%) | 8 | 9 |
Apparent Recovery after 0 days (%) | ||||
Mycotoxin | sand | clay | silt | mix |
DON | 85.65 | 87.28 | 84.77 | 83.19 |
ZEA | 83.41 | 85.39 | 81.78 | 82.01 |
Apparent Recovery after 28 days at 8 °C (%) | ||||
Mycotoxin | sand | clay | silt | mix |
DON | 84.56 | 87.78 | 85.57 | 82.67 |
ZEA | 84.44 | 86.47 | 87.94 | 87.47 |
Apparent Recovery after 28 days stored at 21 °C (%) | ||||
Mycotoxin | sand | clay | silt | mix |
DON | 85.12 | 87.23 | 84.89 | 83.34 |
ZEA | 86.98 | 86.65 | 84.44 | 82.34 |
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Kappenberg, A.; Juraschek, L.M. Development of a LC–MS/MS Method for the Simultaneous Determination of the Mycotoxins Deoxynivalenol (DON) and Zearalenone (ZEA) in Soil Matrix. Toxins 2021, 13, 470. https://doi.org/10.3390/toxins13070470
Kappenberg A, Juraschek LM. Development of a LC–MS/MS Method for the Simultaneous Determination of the Mycotoxins Deoxynivalenol (DON) and Zearalenone (ZEA) in Soil Matrix. Toxins. 2021; 13(7):470. https://doi.org/10.3390/toxins13070470
Chicago/Turabian StyleKappenberg, Arne, and Lena Marie Juraschek. 2021. "Development of a LC–MS/MS Method for the Simultaneous Determination of the Mycotoxins Deoxynivalenol (DON) and Zearalenone (ZEA) in Soil Matrix" Toxins 13, no. 7: 470. https://doi.org/10.3390/toxins13070470