TY - JOUR
T1 - Determination of urinary mycotoxin biomarkers using a sensitive online solid phase extraction‐uhplc‐ms/ms method
AU - Schmidt, Jessica
AU - Cramer, Benedikt
AU - Turner, Paul C.
AU - Stoltzfus, Rebecca J.
AU - Humphrey, Jean H.
AU - Smith, Laura E.
AU - Humpf, Hans Ulrich
N1 - Funding Information:
Funded by the Bill & Melinda Gates Foundation (OPP1021542 and OPP1066264), the United Kingdom Department for International Development (DFID/UKAID); Wellcome Trust (093768/Z/10/Z, 108065/Z/15/Z and 203905/Z/16/Z); Swiss Agency for Development and Cooperation; US National Institutes of Health (2R01HD060338‐06); and UNICEF (PCA‐2017‐0002).
Publisher Copyright:
© 2021 by the authors. Licensee MDPI, Basel, Switzerland.
PY - 2021
Y1 - 2021
N2 - 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 M1 (AFM1), altenuene (ALT), alternariol monomethyl ether (AME), alternariol (AOH), citrinin (CIT) and its metabolite dihydrocitrinone (DH‐CIT), fumonisin B1 (FB1), 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 repeata-bility. Within the analysis of Zimbabwean urine samples (n = 50), the applicability of the newly developed method was shown. In addition to FB1 being quantifiable in all analyzed samples, six other mycotoxin biomarkers were detected. Compared to the occurrence rates obtained after ana-lyzing 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 expo-sure.
AB - 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 M1 (AFM1), altenuene (ALT), alternariol monomethyl ether (AME), alternariol (AOH), citrinin (CIT) and its metabolite dihydrocitrinone (DH‐CIT), fumonisin B1 (FB1), 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 repeata-bility. Within the analysis of Zimbabwean urine samples (n = 50), the applicability of the newly developed method was shown. In addition to FB1 being quantifiable in all analyzed samples, six other mycotoxin biomarkers were detected. Compared to the occurrence rates obtained after ana-lyzing 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 expo-sure.
KW - Biomonitoring
KW - HPLC‐ MS/MS
KW - Metabolite
KW - Mycotoxin
KW - Online solid phase extraction
KW - Urine
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U2 - 10.3390/toxins13060418
DO - 10.3390/toxins13060418
M3 - Article
C2 - 34208182
AN - SCOPUS:85108654695
SN - 2072-6651
VL - 13
JO - Toxins
JF - Toxins
IS - 6
M1 - 418
ER -