Application of the urinary S-phenylmercapturic acid test as a biomarker for low levels of exposure to benzene in industry.

Sittert, N. J. Van; Boogaard, Pieter J van den; Beulink, G. D. J.

doi:10.1136/oem.50.5.460

Cited by 57 publications

(65 citation statements)

References 12 publications

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“…In order to estimate benzene uptake, S-phenylmercapturic acid (SPMA), a urinary benzene metabolite, was measured according to a method described by Van Sittert et al (1993). The LOD was 10 nmol SPMA/l urine.…”

Section: Methodsmentioning

confidence: 99%

Dermal exposure assessment to benzene and toluene using charcoal cloth pads

Joode

Tielemans²,

Vermeulen

et al. 2004

J Expo Sci Environ Epidemiol

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Charcoal cloth pads have been used to assess volatile chemicals on the skin in a laboratory setting; however, they have not yet been applied to measure dermal exposure in occupational settings. This study aimed at evaluating whether charcoal pads can be used to assess dermal exposure to benzene and toluene in workers of a petrochemical plant. Inhalation and dermal exposure levels to benzene and toluene were assessed for workers of a petrochemical plant performing different jobs. Benzene uptake was assessed by determining S-phenylmercapturic acid in workers' urine samples. Dermal exposure levels on the charcoal pads were adjusted for ambient air levels of benzene and toluene by subtracting the amount of benzene or toluene measured in personal air from the amount of benzene or toluene measured on the charcoal pad. In general, measured external and internal exposure levels were low. The estimated contribution of the dermal route to internal benzene exposure levels was less than 0.06% for all jobs. Toluene personal air concentrations and benzene and toluene dermal exposure levels differed statistically significantly between job titles. For benzene, differences between jobs were larger for adjusted dermal exposures (maximum 17-fold, P ¼ 0.02) than for inhalation exposures (maximum two-fold, P ¼ 0.08). Also for toluene, although less clear, differences between jobs were larger for adjusted dermal exposures (maximum 23-fold, P ¼ 0.01) as compared to inhalation exposures (maximum 10-fold, P ¼ 0.01). Charcoal pads appeared to measure dermal exposures to benzene and toluene in addition to ambient air levels. Future studies applying charcoal cloth pads for the dermal exposure assessment at workplaces with higher dermal exposure to organic solvents may provide more insight into the biological relevance of dermal exposure levels measured by charcoal cloth pads. In addition, the design of the dermal sampler might be improved by configuring a dermal sampler, where part of the sampler is protected against direct contact and splashes, but still permeable for the gas phase. This design would most likely result in a better ability to correct for airborne concentrations at a given body location.

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Section: Methodsmentioning

confidence: 99%

Dermal exposure assessment to benzene and toluene using charcoal cloth pads

Joode

Tielemans²,

Vermeulen

et al. 2004

J Expo Sci Environ Epidemiol

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“…The samples were transported to the Shell Biomedical Laboratory, Rotterdam, for determination of urinary S-PMA, tt-MA and creatinine. Urinary creatinine was previously shown to provide a good adjustment for the variations in concentration of spot urine samples due to differences in fluid intake among workers (6,10). For many workers with potential exposure to benzene, personal air sampling of benzene in the breathing zone was performed by local staff using 3M gas diffusion badges or charcoal tubes.…”

Section: Study Populations and Collections Ofurinary And Airborne Sammentioning

confidence: 99%

“…AUCs were calculated using the linear trapezoidal rule in the absorption phases and the logarithmic trapezoidal rule in the elimination phases as described previously (6,10). Apparent urinary elimination rate constants (ke) for S-PMA and tt-MA were calculated from workers who had provided urine samples at the beginning and end of a shift on at least two consecutive days.…”

Section: Caculations and Statisticsmentioning

confidence: 99%

“…An aliquot of 1.00 ml of alkaline urine was applied to a SAX column, which was subsequently washed with 3 ml 1% (v/v) aqueous acetic acid. The tt-MA was then eluted Creatinine was determined as described previously (6).…”

Section: Determination Ofurinary Metabolitesmentioning

confidence: 99%

“…Since only S-PMA seemed to enable detection of exposure to benzene at levels below 1 ppm, the method of Stommel and co-workers (5) for determination of urinary S-PMA was modified in our laboratory to be applicable for routine biological monitoring. This S-PMA test was validated in 12 separate studies in various chemical manufacturing plants, oil refineries, and natural gas production installations and proved a reliable and sensitive biomarker capable of measuring 8-hr TWA benzene exposures of 0.3 ppm and higher (6). In the past few years, the method by Inoue and coworkers for assessment of tt-MA has also been modified by several investigators, and a sensitivity as low as 1 ppm (8-hr TWA) has been reported (7)(8)(9).…”

Section: Introductionmentioning

confidence: 99%

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Suitability of S-Phenyl Mercapturic Acid and trans-trans-Muconic Acid as Biomarkers for Exposure to Low Concentrations of Benzene

Boogaard¹,

Sittert²

1996

Environmental Health Perspectives

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Phenol is not reliable as a biomarker for exposure to benzene at concentrations below 5 ppm (8-hr time-weighted average [TWAI). S-Phenylmercapturic acid (S-PMA) and trans-trans-muconic acid (tt-MA), two minor urinary metabolites of benzene, have been proposed as biomarkers for low-level exposures. The aim of this study was to compare their suitability as biomarkers. S-PMA and tt-MA were determined in 434 urine samples collected from 188 workers in various settings in the petrochemical industry and from 52 control workers with no occupational exposure to benzene. Benzene concentrations in the breathing zone of the potentially exposed workers were assessed by personal air monitoring. Strong correlations were found between S-PMA and tt-MA concentrations in end-of-shift samples and between either of these parameters and airborne benzene concentrations. Exposure to 1 ppm benzene (8-hr TWA) leads to an average concentration in end-of-shift samples of 21 mol S-PMA and 1.5 mmol tt-MA per mol creatinine. Of an inhaled dose of benzene, on average 0.1 1 % (range 0.05-0.26%) was excreted as S-PMA with an apparent elimination half-life of 9.1 (standard error [SE] 0.7) hr and 3.9% (range 1.9-7.3%) as tt-MA with a half-life of 5.0 (SE 0.5) hr. Due to its longer elimination half-life, S-PMA proved a more reliable biomarker than tt-MA for benzene exposures during 12-hr shifts. Specificity of S-PMA, but not tt-MA, was sufficient to discriminate between the 14 moderate smokers and the 38 nonsmokers from the control group. The mean urinary S-PMA was 1.71 (SE 0.27) in smokers and 0.94 (SE 0.15) mol/mol creatinine in nonsmokers (p=0.013). The mean urinary tt-MA was 0.046 (SE 0.010) in smokers and 0.029 (SE 0.013) mmol/mol creatinine in nonsmokers (p= 0.436). The inferior specificity of tt-MA was due to relatively high background values of up to 0.56 mmol/mol creatinine, which may be found in nonexposed individuals and limits the use of tt-MA to concentrations of benzene over 1 ppm (8-hr TWA). We conclude that S-PMA is superior to tt-MA as a biomarker for low-level benzene exposures because it is more specific, enabling reliable determination of benzene exposures down to 0.3 ppm (8-hr TWA), and because its longer half-life makes it more suited for biological monitoring of operators working in shifts longer than 8 hr.

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Validation of biomarkers in humans exposed to benzene: Urine metabolites

Melikian

et al. 2000

Am. J. Ind. Med.

112

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Background The present study was conducted among Chinese workers employed in glue‐ and shoe‐making factories who had an average daily personal benzene exposure of 31±26 ppm (mean±SD). The metabolites monitored were S‐phenylmercapturic acid (S‐PMA), trans, trans‐muconic acid (t,t‐MA), hydroquinone (HQ), catechol (CAT), 1,2,4‐trihydroxybenzene (benzene triol, BT), and phenol. Methods S‐PMA, t,t‐MA, HQ, CAT, and BT were quantified by HPLC‐tandem mass spectrometry. Phenol was measured by GC‐MS. Results Levels of benzene metabolites (except BT) measured in urine samples collected from exposed workers at the end of workshift were significantly higher than those measured in unexposed subjects (P < 0.0001). The large increases in urinary metabolites from before to after work strongly correlated with benzene exposure. Concentrations of these metabolites in urine samples collected from exposed workers before work were also significantly higher than those from unexposed subjects. The half‐lives of S‐PMA, t,t‐MA, HQ, CAT, and phenol were estimated from a time course study to be 12.8, 13.7, 12.7, 15.0, and 16.3 h, respectively. Conclusions All metabolites, except BT, are good markers for benzene exposure at the observed levels; however, due to their high background, HQ, CAT, and phenol may not distinguish unexposed subjects from workers exposed to benzene at low ambient levels. S‐PMA and t,t‐MA are the most sensitive markers for low level benzene exposure. Am. J. Ind. Med. 37:522–531, 2000. © 2000 Wiley‐Liss, Inc.

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Application of the urinary S-phenylmercapturic acid test as a biomarker for low levels of exposure to benzene in industry.

Cited by 57 publications

References 12 publications

Dermal exposure assessment to benzene and toluene using charcoal cloth pads

Dermal exposure assessment to benzene and toluene using charcoal cloth pads

Suitability of S-Phenyl Mercapturic Acid and trans-trans-Muconic Acid as Biomarkers for Exposure to Low Concentrations of Benzene

Validation of biomarkers in humans exposed to benzene: Urine metabolites

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