Determination of Urinary Mycotoxin Biomarkers Using a Sensitive Online Solid Phase Extraction-UHPLC-MS/MS Method
In the course of assessing the human exposure to mycotoxins, biomarker-based approaches have proven to be important tools. Low concentration levels, complex matrix compositions, structurally diverse analytes, and the large size of sample cohorts are the main challenges of analytical procedures. For...
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| Format: | Article |
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MDPI AG
2021-06-01
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| Series: | Toxins |
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| Online Access: | https://www.mdpi.com/2072-6651/13/6/418 |
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| author | Jessica Schmidt Benedikt Cramer Paul C. Turner Rebecca J. Stoltzfus Jean H. Humphrey Laura E. Smith Hans-Ulrich Humpf |
| author_facet | Jessica Schmidt Benedikt Cramer Paul C. Turner Rebecca J. Stoltzfus Jean H. Humphrey Laura E. Smith Hans-Ulrich Humpf |
| author_sort | Jessica Schmidt |
| collection | DOAJ |
| description | In the course of assessing the human exposure to mycotoxins, biomarker-based approaches have proven to be important tools. Low concentration levels, complex matrix compositions, structurally diverse analytes, and the large size of sample cohorts are the main challenges of analytical procedures. For that reason, an online solid phase extraction-ultra high-performance liquid chromatography-tandem mass spectrometry (online SPE-UHPLC-MS/MS) method was developed, allowing for the sensitive, robust, and rapid analysis of 11 relevant mycotoxins and mycotoxin metabolites in human urine. The included spectrum of analytes comprises aflatoxin M<sub>1</sub> (AFM<sub>1</sub>), altenuene (ALT), alternariol monomethyl ether (AME), alternariol (AOH), citrinin (CIT) and its metabolite dihydrocitrinone (DH-CIT), fumonisin B<sub>1</sub> (FB<sub>1</sub>), ochratoxin A (OTA), and zearalenone (ZEN) as well as α- and β-zearalenol (α- and β-ZEL). Reliable quantitation was achieved by means of stable isotope dilution, except for ALT, AME and AOH using matrix calibrations. The evaluation of method performance displayed low limits of detection in the range of pg/mL urine, satisfactory apparent recovery rates as well as high accuracy and precision during intra- and interday repeatability. Within the analysis of Zimbabwean urine samples (<i>n</i> = 50), the applicability of the newly developed method was shown. In addition to FB<sub>1</sub> being quantifiable in all analyzed samples, six other mycotoxin biomarkers were detected. Compared to the occurrence rates obtained after analyzing the same sample set using an established dilute and shoot (DaS) approach, a considerably higher number of positive samples was observed when applying the online SPE method. Owing to the increased sensitivity, less need of sample handling, and low time effort, the herein presented online SPE approach provides a valuable contribution to human biomonitoring of mycotoxin exposure. |
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| institution | Directory Open Access Journal |
| issn | 2072-6651 |
| language | English |
| last_indexed | 2024-03-10T10:29:00Z |
| publishDate | 2021-06-01 |
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| series | Toxins |
| spelling | doaj.art-1c9ffc39f874464985a7319fa7433bf02023-11-21T23:45:12ZengMDPI AGToxins2072-66512021-06-0113641810.3390/toxins13060418Determination of Urinary Mycotoxin Biomarkers Using a Sensitive Online Solid Phase Extraction-UHPLC-MS/MS MethodJessica Schmidt0Benedikt Cramer1Paul C. Turner2Rebecca J. Stoltzfus3Jean H. Humphrey4Laura E. Smith5Hans-Ulrich Humpf6Institute of Food Chemistry, Westfälische Wilhelms-Universität Münster, Corrensstraße 45, 48149 Münster, GermanyInstitute of Food Chemistry, Westfälische Wilhelms-Universität Münster, Corrensstraße 45, 48149 Münster, GermanyMaryland Institute for Applied Environmental Health, School of Public Health, University of Maryland, College Park, MD 20742, USAGoshen College, 1700 S. Main Street, Goshen, IN 46526, USADepartment of International Health, Johns Hopkins Bloomberg School of Public Health, Baltimore, MD 21205, USADepartment of Population Medicine and Diagnostics, Cornell University, Ithaca, NY 14850, USAInstitute of Food Chemistry, Westfälische Wilhelms-Universität Münster, Corrensstraße 45, 48149 Münster, GermanyIn the course of assessing the human exposure to mycotoxins, biomarker-based approaches have proven to be important tools. Low concentration levels, complex matrix compositions, structurally diverse analytes, and the large size of sample cohorts are the main challenges of analytical procedures. For that reason, an online solid phase extraction-ultra high-performance liquid chromatography-tandem mass spectrometry (online SPE-UHPLC-MS/MS) method was developed, allowing for the sensitive, robust, and rapid analysis of 11 relevant mycotoxins and mycotoxin metabolites in human urine. The included spectrum of analytes comprises aflatoxin M<sub>1</sub> (AFM<sub>1</sub>), altenuene (ALT), alternariol monomethyl ether (AME), alternariol (AOH), citrinin (CIT) and its metabolite dihydrocitrinone (DH-CIT), fumonisin B<sub>1</sub> (FB<sub>1</sub>), ochratoxin A (OTA), and zearalenone (ZEN) as well as α- and β-zearalenol (α- and β-ZEL). Reliable quantitation was achieved by means of stable isotope dilution, except for ALT, AME and AOH using matrix calibrations. The evaluation of method performance displayed low limits of detection in the range of pg/mL urine, satisfactory apparent recovery rates as well as high accuracy and precision during intra- and interday repeatability. Within the analysis of Zimbabwean urine samples (<i>n</i> = 50), the applicability of the newly developed method was shown. In addition to FB<sub>1</sub> being quantifiable in all analyzed samples, six other mycotoxin biomarkers were detected. Compared to the occurrence rates obtained after analyzing the same sample set using an established dilute and shoot (DaS) approach, a considerably higher number of positive samples was observed when applying the online SPE method. Owing to the increased sensitivity, less need of sample handling, and low time effort, the herein presented online SPE approach provides a valuable contribution to human biomonitoring of mycotoxin exposure.https://www.mdpi.com/2072-6651/13/6/418mycotoxinbiomonitoringurineonline solid phase extractionmetaboliteHPLC-MS/MS |
| spellingShingle | Jessica Schmidt Benedikt Cramer Paul C. Turner Rebecca J. Stoltzfus Jean H. Humphrey Laura E. Smith Hans-Ulrich Humpf Determination of Urinary Mycotoxin Biomarkers Using a Sensitive Online Solid Phase Extraction-UHPLC-MS/MS Method Toxins mycotoxin biomonitoring urine online solid phase extraction metabolite HPLC-MS/MS |
| title | Determination of Urinary Mycotoxin Biomarkers Using a Sensitive Online Solid Phase Extraction-UHPLC-MS/MS Method |
| title_full | Determination of Urinary Mycotoxin Biomarkers Using a Sensitive Online Solid Phase Extraction-UHPLC-MS/MS Method |
| title_fullStr | Determination of Urinary Mycotoxin Biomarkers Using a Sensitive Online Solid Phase Extraction-UHPLC-MS/MS Method |
| title_full_unstemmed | Determination of Urinary Mycotoxin Biomarkers Using a Sensitive Online Solid Phase Extraction-UHPLC-MS/MS Method |
| title_short | Determination of Urinary Mycotoxin Biomarkers Using a Sensitive Online Solid Phase Extraction-UHPLC-MS/MS Method |
| title_sort | determination of urinary mycotoxin biomarkers using a sensitive online solid phase extraction uhplc ms ms method |
| topic | mycotoxin biomonitoring urine online solid phase extraction metabolite HPLC-MS/MS |
| url | https://www.mdpi.com/2072-6651/13/6/418 |
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