Fast determination of urinary S-phenylmercapturic acid (S-PMA) and S-benzylmercapturic acid (S-BMA) by column-switching liquid chromatography–tandem mass spectrometry

Schettgen, Thomas; Musiol, A.; Alt, A.; Kraus, Thomas

doi:10.1016/j.jchromb.2008.01.024

Cited by 72 publications

(48 citation statements)

References 37 publications

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“…Although numerous methods for the quantification of different MAs by LC-MS/MS have been reported in the recent past, the majority of those assays target a rather small set of up to six MAs [8,17,[20][21][22][24][25][26]. In addition, many of these methods lack the capability of quantifying MAs from environmental exposures in low levels.…”

Section: Discussionmentioning

confidence: 99%

Analysis of 18 urinary mercapturic acids by two high-throughput multiplex-LC-MS/MS methods

et al. 2015

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Mercapturic acids (MAs) are metabolic end products formed from conjugates between glutathione and electrophilic compounds. MAs are, therefore, suitable biomarkers of exposure to toxicants, which are either electrophiles by themselves or metabolized to electrophilic intermediates. We developed and validated two LC-MS/MS methods which allow the complementary, rapid, and sensitive determination of MAs derived from acrolein, acrylamide, acrylonitrile, benzene, 1,3-butadiene, crotonaldehyde, N,N-dimethylformamide, ethylene, ethylene oxide, vinyl chloride, propylene oxide, styrene, toluene as well as methylating and ethylating agents. Since separate determinations of single or small groups of MAs are time-consuming and expensive, we multiplexed several individual methods into two LC-MS/MS methods covering 18 individual mercapturic acids. Method validation according to FDA guidelines showed excellent results in terms of robustness, accuracy, and sensitivity of the methods. Moreover, the use of a minimal, simple, and straightforward sample cleanup procedure further accelerated the analytical workflow, which allows a time- and cost-efficient analysis of up to 18 MAs derived from various toxicants in environmental levels. The methods were applied to urine samples derived from a strictly diet-controlled clinical study, including 25 smoking and 25 non-smoking subjects. Significant increase in the urine concentrations in smokers as compared to non-smokers (p < 0.01; Student t test) was observed for 13 individual MAs. Moreover, a dose dependence was obtained for the majority of the analytes. In conclusion, the newly developed assays represent a powerful tool for the fast and reliable quantification of 18 MAs in clinical studies. A first method application suggests several suitable biomarkers for nine relevant toxicants in tobacco smoke.

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Section: Discussionmentioning

confidence: 99%

Analysis of 18 urinary mercapturic acids by two high-throughput multiplex-LC-MS/MS methods

et al. 2015

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“…The success of this approach is mainly due to the low limit of detection achieved with our newly developed analytical method for the quantification of urinary S-PMA (Schettgen et al, 2008).…”

Section: Discussionmentioning

confidence: 99%

“…Determination of Urinary S-PMA Urinary S-PMA was determined as described earlier using an automated column-switching LC/MS/MS-method (Schettgen et al, 2008). In short, 1 ml of urine was transferred to a 1.8-ml HPLC-vial, spiked with d 5 -labelled S-PMA as internal standard and acidified with formic acid to pH 2.…”

Section: Study Populationmentioning

confidence: 99%

“…Our earlier study has developed a highly sensitive and specific on-line LC/MS/MS-method with column-switching that allows the determination of urinary S-PMA resulting from environmental benzene exposures (Schettgen et al, 2008). In this study, we have applied this method to 128 urine samples of a convenience sample of the German general population with no known occupational exposure to benzene and used these data to estimate their individual daily intake (DI) of this environmental carcinogen.…”

Section: Introductionmentioning

confidence: 99%

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A biomarker approach to estimate the daily intake of benzene in non-smoking and smoking individuals in Germany

Schettgen

Ochsmann

Alt

et al. 2009

J Expo Sci Environ Epidemiol

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Owing to its carcinogenic properties, benzene is one of the most important environmental air pollutants. We have applied a simple pharmacokinetic model to estimate the individual daily exposure of persons of the general population to benzene using their urinary excretion of S-phenylmercapturic acid as biomarker of exposure. On the basis of a non-representative convenience sample of the general population, spontaneous urine samples of 43 non-smoking persons, 13 persons with exposure to environmental tobacco smoke (ETS) (as determined by urinary cotinine) and 72 smokers were analyzed for S-phenylmercapturic acid, and benzene exposure was back calculated on the basis of the results. The pharmacokinetic model was based either on estimated daily urinary volume or creatinine excretion. Median daily exposure of non-smokers was calculated to be 47 mg/day (volume-based model) and 63 mg benzene/day (creatinine-based model). ETS-exposed persons had a slightly higher median daily exposure of 65 mg/day (volume-based model) and 72 mg benzene/day (creatinine-based model). The daily exposure of smokers was significantly higher with median values of 491 mg benzene/day (volumebased model) and 693 mg benzene/day (creatinine-based model). Our biomarker-based model gave plausible results for daily benzene exposure that were in good agreement with exposure estimations published earlier. As it is purely based on the determination of individual internal dose, our model provides a powerful tool for the risk assessment of environmental benzene.

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“…Uma metodologia automatizada para a determinação de AFM e outros quatro ácidos mercaptúricos em urina utilizando uma pré-coluna de extração on-line ao sistema LC-MS/MS foi descrita e validada por Zhang et al, apresentando adequada eficiência analítica 67 . Outros estudos utilizando a mesma técnica foram realizados por Liao et al 75 , Lin et al 76 e Schettgen et al 77 . As desvantagens de extração on-line envolvem a necessidade de aparatos instrumentais específicos que, em geral, devem ser adquiridos à parte da configuração padrão do cromatógrafo e também o custo mais elevado da pré-coluna de extração, quando comparado ao custo dos tradicionais cartuchos de SPE.…”

Section: Pré-tratamento E Procedimentos De Extraçãounclassified

Estratégias analíticas com cromatografia e espectrometria de massas para biomonitorização da exposição ao benzeno pela determinação do ácido S-fenilmercaptúrico urinário

Gonçalves

Borges

Carvalho

et al. 2017

Rev. bras. saúde ocup.

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Resumo Introdução: o benzeno é uma substância de reconhecida toxicidade e sua biomonitorização torna-se fundamental para a prevenção de danos à saúde humana, principalmente em situações de exposição ocupacional. Dentre os biomarcadores de exposição, o ácido S-fenilmercaptúrico é considerado o único específico, mas, devido a suas baixas concentrações na urina, é requerido o uso de técnicas analíticas sensíveis capazes de quantificar traços. Objetivo: revisar metodologias baseadas na cromatografia e na espectrometria de massas para a determinação do ácido S-fenilmercaptúrico. Método: revisão da literatura sobre a determinação do ácido S-fenilmercaptúrico urinário por técnicas de cromatografia e espectrometria de massas, nas principais bases de dados científicas, considerando o período entre 1951 e 2015. Resultados: 120 documentos serviram como base teórica para a construção desta revisão. A técnica analítica mais empregada foi o acoplamento da cromatografia a líquido com a espectrometria de massas. Contudo, os métodos diferem quanto ao preparo das amostras. Conclusão: o alto custo de aquisição e a manutenção de equipamentos são fatores limitantes para a difusão dos sistemas de cromatografia e espectrometria de massas. No entanto, sua elevada sensibilidade e seletividade faz com que essas técnicas, acopladas, possibilitem elucidar situações de exposição ocupacional e ambiental a poluentes, como o benzeno.

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Fast determination of urinary S-phenylmercapturic acid (S-PMA) and S-benzylmercapturic acid (S-BMA) by column-switching liquid chromatography–tandem mass spectrometry

Cited by 72 publications

References 37 publications

Analysis of 18 urinary mercapturic acids by two high-throughput multiplex-LC-MS/MS methods

Analysis of 18 urinary mercapturic acids by two high-throughput multiplex-LC-MS/MS methods

A biomarker approach to estimate the daily intake of benzene in non-smoking and smoking individuals in Germany

Estratégias analíticas com cromatografia e espectrometria de massas para biomonitorização da exposição ao benzeno pela determinação do ácido S-fenilmercaptúrico urinário

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