Suspect screening candidate exposure biomarkers of acetyl tributyl citrate and acetyl triethyl citrate after human oral administration

Acetyl tributyl citrate (ATBC) and acetyl triethyl citrate (ATEC) are widely used as plasticizers, but their metabolites as exposure biomarkers for biomonitoring, as well as approximate human metabolic pathways, are not well understood. This study addresses this knowledge gap by conducting suspect s...

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Main Authors: Eu-Kyung Jo, Jinhyun Kwon, Daeho Kang, Junho Jeon, Younglim Kho, Mi-Yeon Shin, Sungkyoon Kim
Format: Article
Language:English
Published: Elsevier 2024-11-01
Series:Environment International
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Online Access:http://www.sciencedirect.com/science/article/pii/S0160412024006482
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author Eu-Kyung Jo
Jinhyun Kwon
Daeho Kang
Junho Jeon
Younglim Kho
Mi-Yeon Shin
Sungkyoon Kim
author_facet Eu-Kyung Jo
Jinhyun Kwon
Daeho Kang
Junho Jeon
Younglim Kho
Mi-Yeon Shin
Sungkyoon Kim
author_sort Eu-Kyung Jo
collection DOAJ
description Acetyl tributyl citrate (ATBC) and acetyl triethyl citrate (ATEC) are widely used as plasticizers, but their metabolites as exposure biomarkers for biomonitoring, as well as approximate human metabolic pathways, are not well understood. This study addresses this knowledge gap by conducting suspect screening to propose specific metabolites in human urine as potential biomarkers of exposure and explore their kinetic profiles. Ten volunteers were administered deuterium labeled ATBC (ATBC-d3) and seven received ATEC or deuterium labeled ATEC (ATEC-d3), with urine samples collected over 48 h post-administration. Employing ultra-performance liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry (UPLC-qTOF/MS), six metabolites of ATBC were consistently detected, including (OH)3-ATBC-d3, ADBC-d3, OH-ADBC-d3, DBC, OH-DBC, and OH-DBA. For ATEC, four metabolites were identified: ADEC-d3, AMEC-d3, OH-ADEC-d3, and DEC. Based on their high detection frequency, relative response, and specificity to their parent compounds, ADBC-d3 and OH-ADBC-d3 were identified as promising candidate biomarkers for ATBC exposure, while ADEC-d3 emerged as a suitable biomarker for ATEC. Estimated urinary elimination half-lives ranged from 1.0 to 9.9 h for ATBC metabolites and 1.6 to 3.0 h for ATEC metabolites. One-compartment kinetic modeling provided preliminary insights into metabolite kinetics. This research advances the understanding of ATBC and ATEC metabolism in humans, providing a foundation for future exposure assessments and toxicological studies. The identified biomarkers and preliminary metabolic profiles offer valuable starting points for biomonitoring and risk assessment of these alternative plasticizers.
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spelling doaj-art-63cdbe6ba44a4ef494ca0d68f4bd87462025-08-20T02:32:41ZengElsevierEnvironment International0160-41202024-11-0119310906210.1016/j.envint.2024.109062Suspect screening candidate exposure biomarkers of acetyl tributyl citrate and acetyl triethyl citrate after human oral administrationEu-Kyung Jo0Jinhyun Kwon1Daeho Kang2Junho Jeon3Younglim Kho4Mi-Yeon Shin5Sungkyoon Kim6Graduate School of Public Health, Seoul National University, Seoul, South KoreaGraduate School of Public Health, Seoul National University, Seoul, South KoreaDepartment of Environmental Engineering, Changwon National University, Gyeongsangnam-do, South KoreaDepartment of Environmental Engineering, Changwon National University, Gyeongsangnam-do, South Korea; School of Smart and Green Engineering, Changwon National University, Gyeongsangnam-do, South KoreaDepartment of Health, Environment and Safety, Eulji University, Seongnam, South KoreaGraduate School of Public Health, Seoul National University, Seoul, South Korea; Office of Dental Education, School of Dentistry, Seoul National University, Seoul, South Korea; Corresponding authors at: Graduate School of Public Health, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 08826, South Korea.Graduate School of Public Health, Seoul National University, Seoul, South Korea; Institute of Health and Environment, Graduate School of Public Health, Seoul National University, Seoul, South Korea; Corresponding authors at: Graduate School of Public Health, Seoul National University, 1 Gwanak-ro, Gwanak-gu, Seoul 08826, South Korea.Acetyl tributyl citrate (ATBC) and acetyl triethyl citrate (ATEC) are widely used as plasticizers, but their metabolites as exposure biomarkers for biomonitoring, as well as approximate human metabolic pathways, are not well understood. This study addresses this knowledge gap by conducting suspect screening to propose specific metabolites in human urine as potential biomarkers of exposure and explore their kinetic profiles. Ten volunteers were administered deuterium labeled ATBC (ATBC-d3) and seven received ATEC or deuterium labeled ATEC (ATEC-d3), with urine samples collected over 48 h post-administration. Employing ultra-performance liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry (UPLC-qTOF/MS), six metabolites of ATBC were consistently detected, including (OH)3-ATBC-d3, ADBC-d3, OH-ADBC-d3, DBC, OH-DBC, and OH-DBA. For ATEC, four metabolites were identified: ADEC-d3, AMEC-d3, OH-ADEC-d3, and DEC. Based on their high detection frequency, relative response, and specificity to their parent compounds, ADBC-d3 and OH-ADBC-d3 were identified as promising candidate biomarkers for ATBC exposure, while ADEC-d3 emerged as a suitable biomarker for ATEC. Estimated urinary elimination half-lives ranged from 1.0 to 9.9 h for ATBC metabolites and 1.6 to 3.0 h for ATEC metabolites. One-compartment kinetic modeling provided preliminary insights into metabolite kinetics. This research advances the understanding of ATBC and ATEC metabolism in humans, providing a foundation for future exposure assessments and toxicological studies. The identified biomarkers and preliminary metabolic profiles offer valuable starting points for biomonitoring and risk assessment of these alternative plasticizers.http://www.sciencedirect.com/science/article/pii/S0160412024006482Alternative plasticizerOral administrationUltra-performance liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry (UPLC-qTOF/MS)Suspect screeningToxicokinetic modelExposure biomarker
spellingShingle Eu-Kyung Jo
Jinhyun Kwon
Daeho Kang
Junho Jeon
Younglim Kho
Mi-Yeon Shin
Sungkyoon Kim
Suspect screening candidate exposure biomarkers of acetyl tributyl citrate and acetyl triethyl citrate after human oral administration
Environment International
Alternative plasticizer
Oral administration
Ultra-performance liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry (UPLC-qTOF/MS)
Suspect screening
Toxicokinetic model
Exposure biomarker
title Suspect screening candidate exposure biomarkers of acetyl tributyl citrate and acetyl triethyl citrate after human oral administration
title_full Suspect screening candidate exposure biomarkers of acetyl tributyl citrate and acetyl triethyl citrate after human oral administration
title_fullStr Suspect screening candidate exposure biomarkers of acetyl tributyl citrate and acetyl triethyl citrate after human oral administration
title_full_unstemmed Suspect screening candidate exposure biomarkers of acetyl tributyl citrate and acetyl triethyl citrate after human oral administration
title_short Suspect screening candidate exposure biomarkers of acetyl tributyl citrate and acetyl triethyl citrate after human oral administration
title_sort suspect screening candidate exposure biomarkers of acetyl tributyl citrate and acetyl triethyl citrate after human oral administration
topic Alternative plasticizer
Oral administration
Ultra-performance liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry (UPLC-qTOF/MS)
Suspect screening
Toxicokinetic model
Exposure biomarker
url http://www.sciencedirect.com/science/article/pii/S0160412024006482
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