Analysis of phenoxyacetic acid herbicides as biomarkers in human urine using liquid chromatography triple quadrupole mass spectrometry.
(2008) In Rapid Communications in Mass Spectrometry 22(2). p.143-150- Abstract
- Phenoxyacetic acids are widely used herbicides. The toxicity of phenoxyacetic acids is debated, but high-level exposure has been shown to be hepatotoxic as well as nephrotoxic in animal studies. An inter-species difference in toxic effects has been found, with dogs particularly susceptible. In this study a method using liquid chromatography/triple quadrupole mass spectrometry (LC/MS/MS) is described for the analysis of 4-chloro-2-methylphenoxyacetic acid (MCPA), and its metabolite 4-chloro-2-hydroxymethylphenoxyacetic acid (HMCPA), 2,4-dichlorophenoxyacetic acid (2,4-D), and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in human urine. The urine samples were treated by acid hydrolysis to degrade possible conjugations. The sample preparation... (More)
- Phenoxyacetic acids are widely used herbicides. The toxicity of phenoxyacetic acids is debated, but high-level exposure has been shown to be hepatotoxic as well as nephrotoxic in animal studies. An inter-species difference in toxic effects has been found, with dogs particularly susceptible. In this study a method using liquid chromatography/triple quadrupole mass spectrometry (LC/MS/MS) is described for the analysis of 4-chloro-2-methylphenoxyacetic acid (MCPA), and its metabolite 4-chloro-2-hydroxymethylphenoxyacetic acid (HMCPA), 2,4-dichlorophenoxyacetic acid (2,4-D), and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in human urine. The urine samples were treated by acid hydrolysis to degrade possible conjugations. The sample preparation was performed using solid-phase extraction. Analysis was carried out using selected reaction monitoring (SRM) in the negative ion mode. Quantification of the phenoxyacetic acids was performed using [2H3]-labeled MCPA and 2,4-D as internal standards. The method was linear in the range 0.05-310 ng/mL urine and has a within-run precision of 2-5%. The between-run precision in lower concentration ranges was between 6-15% and between 2-8% in higher concentration ranges. The limit of detection was determined to 0.05 ng/mL. The metabolites in urine were found to be stable during storage at -20°C. To validate the phenoxyacetic acids as biomarkers of exposure, the method was applied in a human experimental oral exposure to MCPA, 2,4-D and 2,4,5-T. Two healthy volunteers received 200 µg of each phenoxyacetic acid in a single oral dose followed by urine sampling for 72 h post-exposure. After exposure, between 90 and 101% of the dose was recovered in the urine. In the female subject, 23%, and in the male subject 17%, of MCPA was excreted as HMCPA. (Less)
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https://lup.lub.lu.se/record/1144029
- author
- Lindh, Christian LU ; Littorin, Margareta LU ; Amilon, Åsa LU and Jönsson, Bo A LU
- organization
- publishing date
- 2008
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Rapid Communications in Mass Spectrometry
- volume
- 22
- issue
- 2
- pages
- 143 - 150
- publisher
- John Wiley & Sons Inc.
- external identifiers
-
- wos:000252678200009
- pmid:18059043
- scopus:38549139085
- ISSN
- 1097-0231
- DOI
- 10.1002/rcm.3348
- language
- English
- LU publication?
- yes
- id
- ea16c7b0-b08d-4f13-b6e1-eec533464e98 (old id 1144029)
- date added to LUP
- 2016-04-01 12:10:57
- date last changed
- 2022-01-26 23:58:38
@article{ea16c7b0-b08d-4f13-b6e1-eec533464e98, abstract = {{Phenoxyacetic acids are widely used herbicides. The toxicity of phenoxyacetic acids is debated, but high-level exposure has been shown to be hepatotoxic as well as nephrotoxic in animal studies. An inter-species difference in toxic effects has been found, with dogs particularly susceptible. In this study a method using liquid chromatography/triple quadrupole mass spectrometry (LC/MS/MS) is described for the analysis of 4-chloro-2-methylphenoxyacetic acid (MCPA), and its metabolite 4-chloro-2-hydroxymethylphenoxyacetic acid (HMCPA), 2,4-dichlorophenoxyacetic acid (2,4-D), and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in human urine. The urine samples were treated by acid hydrolysis to degrade possible conjugations. The sample preparation was performed using solid-phase extraction. Analysis was carried out using selected reaction monitoring (SRM) in the negative ion mode. Quantification of the phenoxyacetic acids was performed using [2H3]-labeled MCPA and 2,4-D as internal standards. The method was linear in the range 0.05-310 ng/mL urine and has a within-run precision of 2-5%. The between-run precision in lower concentration ranges was between 6-15% and between 2-8% in higher concentration ranges. The limit of detection was determined to 0.05 ng/mL. The metabolites in urine were found to be stable during storage at -20°C. To validate the phenoxyacetic acids as biomarkers of exposure, the method was applied in a human experimental oral exposure to MCPA, 2,4-D and 2,4,5-T. Two healthy volunteers received 200 µg of each phenoxyacetic acid in a single oral dose followed by urine sampling for 72 h post-exposure. After exposure, between 90 and 101% of the dose was recovered in the urine. In the female subject, 23%, and in the male subject 17%, of MCPA was excreted as HMCPA.}}, author = {{Lindh, Christian and Littorin, Margareta and Amilon, Åsa and Jönsson, Bo A}}, issn = {{1097-0231}}, language = {{eng}}, number = {{2}}, pages = {{143--150}}, publisher = {{John Wiley & Sons Inc.}}, series = {{Rapid Communications in Mass Spectrometry}}, title = {{Analysis of phenoxyacetic acid herbicides as biomarkers in human urine using liquid chromatography triple quadrupole mass spectrometry.}}, url = {{http://dx.doi.org/10.1002/rcm.3348}}, doi = {{10.1002/rcm.3348}}, volume = {{22}}, year = {{2008}}, }