Urinary biomonitoring of fuel ether oxygenates using a needle trap device packed with a novel molecularly imprinted polymer surface modified Zeolite Y.

This study introduces an innovative needle trap device (NTD) featuring a molecularly imprinted polymer (MIP) surface-modified Zeolite Y. The developed NTD was integrated with gas chromatography-flame ionization detector (GC-FID) and employed for analysis of fuel ether oxygenates (methyl tert­butyl ether, MTBE, ethyl tert­butyl ether, ETBE, and tert­butyl formate, TBF) in urine samples. To optimize the key experimental variables including extraction temperature, extraction time, salt concentration, and stirring speed, a central composite design-response surface methodology (CCD-RSM) was employed. The optimal values for extraction in the study were found to be 51.2 °C extraction temperature, 46.2 min extraction time, 27 % salt concentration, and 620 rpm stirring speed. Under the optimized conditions, the calibration curves demonstrated excellent linearity within the range of 0.1-100 µg L-1, with correlation coefficients (R2) exceeding 0.99. The limits of detection (LODs) for MTBE, ETBE, and TBF were obtained 0.06, 0.08, and 0.09 µg L-1, respectively. Moreover, the limits of quantification (LOQs) for MTBE, ETBE, and TBF were obtained 0.18, 0.24, and 0.27 µg L-1, respectively. The enrichment factor was also found to be in the range of 98-129.The NTD-GC-FID procedure demonstrated a high extraction efficiency, making it a promising tool for urinary biomonitoring of fuel ether oxygenates with improved sensitivity and selectivity compared to current methods.

A straightforward method for determination of the sevoflurane metabolite hexafluoroisopropanol in urinary occupational medical samples by headspace-gas chromatography mass spectrometry.

Biological monitoring of the unmodified sevoflurane and its metabolite hexafluoroisopropanol (HFIP) in urine samples was proposed to determine the individual exposure levels of the medical staff. In this study, a method for simultaneous determination of both compounds in urine using static headspace-gas chromatography-mass spectrometry (HS-GC-MS) was developed. The method is linear over a broad concentration range from 1 to 1000 µg/L (r2 > 0.999) and shows high precision. Limits of quantification (LOQ) are 0.6 µg/L for sevoflurane and 3 µg/L for HFIP, representing an excellent sensitivity without the necessity of analyte enrichment. The method was successfully applied in a German pilot-study to monitor both compounds in samples from medical personnel working in operating theatres. Urinary concentrations of HFIP ranged between < LOQ and 145 µg/L, while sevoflurane was below the LOD in all samples.

The urinary metabolic profile of diethylene glycol methyl ether and triethylene glycol methyl ether in Sprague-Dawley rats and the role of the metabolite methoxyacetic acid in their toxicity.

Ethylene glycol ethers are a well-known series of solvents and hydraulic fluids derived from the reaction of ethylene oxide and monoalcohols. Use of methanol as the alcohol results in a series of mono, di and triethylene glycol methyl ethers. The first in the series, monoethylene glycol methyl ether (EGME or 2-methoxyethanol) is well characterised and metabolises in vivo to methoxyacetic acid (MAA), a known reproductive toxicant. Metabolism data is not available for the di and triethylene glycol ethers (DEGME and TEGME respectively). This study evaluated the metabolism of these two substances in male rats following single oral gavage doses of 500, 1000 and 2000 mg/kg for DEGME and 1000 mg/kg for TEGME. As for EGME, the dominant metabolite of each was the acid metabolite derived by oxidation of the terminal hydroxyl group. Elimination of these metabolites was rapid, with half-lives <4 h for each one. Both substances were also found to produce small amounts of MAA (~0.5% for TEGME and ~1.1% for DEGME at doses of 1000 mg/kg) through cleavage of the ether groups in the molecules. These small amounts of MAA produced can explain the effects seen at high doses in reproductive studies using DEGME and TEGME.

Epigenetic and Transcriptional Modifications in Repetitive Elements in Petrol Station Workers Exposed to Benzene and MTBE.

Benzene, a known human carcinogen, and methyl tert-butyl ether (MTBE), not classifiable as to its carcinogenicity, are fuel-related pollutants. This study investigated the effect of these chemicals on epigenetic and transcriptional alterations in DNA repetitive elements. In 89 petrol station workers and 90 non-occupationally exposed subjects the transcriptional activity of retrotransposons (LINE-1, Alu), the methylation on repeated-element DNA, and of H3K9 histone, were investigated in peripheral blood lymphocytes. Median work shift exposure to benzene and MTBE was 59 and 408 µg/m³ in petrol station workers, and 4 and 3.5 µg/m³, in controls. Urinary benzene (BEN-U), S-phenylmercapturic acid, and MTBE were significantly higher in workers than in controls, while trans,trans-muconic acid (tt-MA) was comparable between the two groups. Increased BEN-U was associated with increased Alu-Y and Alu-J expression; moreover, increased tt-MA was associated with increased Alu-Y and Alu-J and LINE-1 (L1)-5'UTR expression. Among repetitive element methylation, only L1-Pa5 was hypomethylated in petrol station workers compared to controls. While L1-Ta and Alu-YD6 methylation was not associated with benzene exposure, a negative association with urinary MTBE was observed. The methylation status of histone H3K9 was not associated with either benzene or MTBE exposure. Overall, these findings only partially support previous observations linking benzene exposure with global DNA hypomethylation.

Environmental and biological measurements of isoflurane and sevoflurane in operating room personnel.

PURPOSE: The present study aimed to compare the concentration of isoflurane and sevoflurane in the individual's breathing zone and ambient air of operating rooms (ORs), to investigate the correlation between breathing zone levels and urinary concentrations, and to evaluate the ORs pollution in the different working hours and weeks. METHODS: Environmental and biological concentrations of isoflurane and sevoflurane were evaluated at 9ORs. Air samples were collected by active sampling method and urine samples were collected from each subject at the end of the work shift. All samples were analyzed using gas chromatography. RESULTS: The geometric mean ± GSD concentration of isoflurane and sevoflurane in breathing zone air were 1.41 ± 2.27 and 0.005 ± 1.74 ppm, respectively, while in post-shift urine were 2.42 ± 2.86 and 0.006 ± 3.83 µg/lurine, respectively. A significant positive correlation was found between the urinary and environmental concentration of isoflurane (r 2 = 0.724, P < 0.0001). The geometric mean ± GSD values of isoflurane and sevoflurane in ambient air were 2.30 ± 2.43 and 0.004 ± 1.56 ppm, respectively. The isoflurane concentration was different for three studied weeks and significantly increased over time in the ambient air of ORs. CONCLUSIONS: The occupational exposure of OR personnel to isoflurane and sevoflurane was lower than national recommended exposure limits. The urinary isoflurane could be a good internal dose biomarker for monitoring of occupational isoflurane exposure. Considering the accumulation of anesthetic waste gases in the studied ORs, real-time air monitoring is better to be done at the end of the work shift.

Determination and pharmacokinetics of chinensinaphthol methyl ether in rat urine by a sensitive and specific UFLC-ESI-MS/MS method.

A rapid, stable, and sensitive method based on ultra-fast liquid chromatography combined with electrospray ionization tandem mass spectrometry (UFLC-ESI-MS/MS) was established and optimized for quantification and pharmacokinetics analysis of chinensinaphthol methyl ether (CME) in rat urine. Samples were prepared by liquid phase extraction with ethyl acetate, and chromatographic separation was performed on an ACQUITY UPLC(®) BEH Phenyl column (2.1×50mm, 1.7µm). For gradient elution, we used a mobile phase consisting of water containing 0.1% formic acid and 5mmol/L ammonium formate and methanol with 0.1% formic acid. The quantification was executed under multiple reaction monitoring (MRM) in positive mode. The precursor/product transition (m/z) in the positive ion mode was [M+H](+)m/z=395.1→346.1. This method was validated by evaluating specificity, linearity, matrix effects, recovery, accuracy, precision, and stability, which were all shown to be reasonable and reliable. The lower limit of quantification (LOQ) was 0.5ng/mL, and the linear range was 0.5-100ng/mL. The method was successfully applied to quantify and analyze the pharmacokinetics of CME in rat urine. After oral administration of a single dose of CME (5.0mg/kg), the accumulated amount of CME excreted in urine was 162.3±54.1ng, and the terminal elimination half-life was 53.4±5.3h, indicating low CME excretion in urine and significant CME metabolism in vivo.

Exposure to BTEX and Ethers in Petrol Station Attendants and Proposal of Biological Exposure Equivalents for Urinary Benzene and MTBE.

OBJECTIVE: To assess exposure to benzene (BEN) and other aromatic compounds (toluene, ethylbenzene, m+p-xylene, o-xylene) (BTEX), methyl tert-butyl ether (MTBE), and ethyl tert-butyl ether (ETBE) in petrol station workers using air sampling and biological monitoring and to propose biological equivalents to occupational limit values. METHODS: Eighty-nine petrol station workers and 90 control subjects were investigated. Personal exposure to airborne BTEX and ethers was assessed during a mid-week shift; urine samples were collected at the beginning of the work week, prior to and at the end of air sampling. RESULTS: Petrol station workers had median airborne exposures to benzene and MTBE of 59 and 408 µg m(-3), respectively, with urinary benzene (BEN-U) and MTBE (MTBE-U) of 339 and 780 ng l(-1), respectively. Concentrations in petrol station workers were higher than in control subjects. There were significant positive correlations between airborne exposure and the corresponding biological marker, with Pearson's correlation coefficient (r) values of 0.437 and 0.865 for benzene and MTBE, respectively. There was also a strong correlation between airborne benzene and urinary MTBE (r = 0.835). Multiple linear regression analysis showed that the urinary levels of benzene were influenced by personal airborne exposure, urinary creatinine, and tobacco smoking [determination coefficient (R(2)) 0.572], while MTBE-U was influenced only by personal exposure (R(2) = 0.741). CONCLUSIONS: BEN-U and MTBE-U are sensitive and specific biomarkers of low occupational exposures. We propose using BEN-U as biomarker of exposure to benzene in nonsmokers and suggest 1457 ng l(-1) in end shift urine samples as biological exposure equivalent to the EU occupational limit value of 1 p.p.m.; for both smokers and nonsmokers, MTBE-U may be proposed as a surrogate biomarker of benzene exposure, with a biological exposure equivalent of 22 µg l(-1) in end shift samples. For MTBE exposure, we suggest the use of MTBE-U with a biological exposure equivalent of 22 µg l(-1) corresponding to the occupational limit value of 50 p.p.m.

Urinary biomarkers of exposure and of oxidative damage in children exposed to low airborne concentrations of benzene.

The aim of this work was to evaluate the oxidative damage to nucleic acids in children (5-11 years) associated with exposure to environmental pollutants and tobacco smoke (ETS). For each subject, urinary sampling was done twice (evening and next morning) to measure by tandem LC-MS-MS such oxidated products of nucleic acids as 8-oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo), 8-oxo-7,8-dihydroguanosine (8-oxoGuo), and 8-oxo-7,8-dihydroguanine (8-oxoGua). Methyl tert-butyl ether (U-MTBE), benzene (U-Benz), and its metabolites (t,t-muconic and S-phenylmercapturic acids, t,t-MA and S-PMA, respectively) were determined as biomarkers of exposure to air pollution, and cotinine as a biomarker of exposure to ETS. Biomarkers of exposure (S-PMA and U-MTBE) and of DNA oxidation (8-oxodGuo) were dependent on the urbanization and industrialization levels and increased in the evening sample as compared to next morning (p<0.05). In both evening and next morning samples, 8-oxodGuo and 8-oxoGuo correlated with each other (r=0.596 and r=0.537, respectively, p<0.01) and with biomarkers of benzene exposure, particularly S-PMA (r=0.59 and r=0.45 for 8-oxodGuo and r=0.411 and r=0.383 for 8-oxoGuo, p<0.01). No such correlations were observed for U-MTBE and cotinine. Multiple linear regression analyses showed that 8-oxodGuo was positively associated with S-PMA at both sampling times (ß=0.18 and ß=0.14 for evening and next morning sampling, respectively; p<0.02) and weakly with U-MTBE (ß=0.07, p=0.020) only in the evening urines. These results suggest that the selected biomarkers of exposure to benzene, particularly S-PMA, are good tracers of exposure to complex mixtures of oxidative pollutants and that the associated oxidative damage to nucleic acids is detectable even at very low levels of exposure.

Biomonitoring occupational sevoflurane exposure at low levels by urinary sevoflurane and hexafluoroisopropanol.

This study aimed to correlate environmental sevoflurane levels with urinary concentrations of sevoflurane (Sev-U) or its metabolite hexafluoroisopropanol (HFIP) in order to assess and discuss the main issues relating to which biomarker of sevoflurane exposure is best, and possibly suggest the corresponding biological equivalent exposure limit values. Individual sevoflurane exposure was measured in 100 healthcare operators at five hospitals in north-east Italy using the passive air sampling device Radiello(®), and assaying Sev-U and HFIP concentrations in their urine collected at the end of the operating room session. All analyses were performed by gas chromatography-mass spectrometry. Environmental sevoflurane levels in the operating rooms were also monitored continuously using an infrared photoacoustic analyzer. Our results showed very low individual sevoflurane exposure levels, generally below 0.5 ppm (mean 0.116 ppm; range 0.007-0.940 ppm). Sev-U and HFIP concentrations were in the range of 0.1-17.28 µg/L and 5-550 µg/L, respectively. Both biomarkers showed a statistically significant correlation with the environmental exposure levels (Sev-U, r=0.49; HFIP, r=0.52), albeit showing fairly scattered values. Sev-U values seem to be influenced by peaks of exposure, especially at the end of the operating-room session, whereas HFIP levels by exposure on the previous day, the data being consistent with the biomarkers' very different half-lives (2.8 and 19 h, respectively). According to our results, both Sev-U and HFIP are appropriate biomarkers for assessing sevoflurane exposure at low levels, although with some differences in times/patterns of exposure. More work is needed to identify the best biomarker of sevoflurane exposure and the corresponding biological equivalent exposure limit values.

Methyl tert-butyl ether (MTBE) detected in abnormally high concentrations in postmortem blood and urine from two persons found dead inside a car containing a gasoline spill.

Two deep frozen persons, a female and a male, were found dead in a car. There had been an explosive fire inside the car which had extinguished itself. On the floor inside the car were large pools of liquid which smelled of gasoline. The autopsy findings and routine toxicological analyses could not explain the cause of death. Carboxyhemoglobin levels in the blood samples were <10%. Analysis with a headspace gas chromatography revealed methyl tert-butyl ether (MTBE) concentrations of 185 mg/L (female victim) and 115 mg/L (male victim) in peripheral blood. The urine MTBE concentrations were 150 mg/L and 256 mg/L, respectively. MTBE is a synthetic chemical which is added to gasoline as a fuel oxygenate. Gasoline poisoning is likely to be the cause of the death in these two cases, and MTBE can be a suitable marker of gasoline exposure, when other volatile components have vaporized.

Biomarkers of exposure to aromatic hydrocarbons and methyl tert-butyl ether in petrol station workers.

This cross-sectional study was aimed at reconstructing the exposure to gasoline in 102 petrol station attendants by environmental and biological monitoring of benzene, toluene, ethylbenzene and xylene (BTEX) and biomonitoring of methyl tert-butyl ether (MTBE). Airborne BTEX were higher for manual refuelers than self-service assistants and were highly correlated with each other. Significant relationships were found between airborne BTX and the corresponding urinary solvents (U-BTX) and beween airborne B and urinary MTBE (U-MTBE). Smokers eliminated higher values of U-B, trans,trans-muconic (t,t-MA) and S-phenylmercapturic (S-PMA) acids but not U-MTBE. All these biomarkers were, however, significantly raised during the shift, independently from smoking. Linear regression confirmed that occupational exposure was a main predictor of U-MTBE, U-B and S-PMA values, both the latter confounded by smoking habits. The study supports the usefulness of biomonitoring even at low exposure levels.

Development and validation of a direct headspace GC-FID method for the determination of sevoflurane, desflurane and other volatile compounds of forensic interest in biological fluids: application on clinical and post-mortem samples.

A simple and reliable headspace GC-flame ionization detection (HS-GC-FID) method has been developed and validated for the simultaneous determination of seven volatile compounds of forensic interest: sevoflurane, desflurane, ethanol, methanol, 1-propanol, acetone and acetaldehyde. All seven compounds including acetonitrile (internal standard) eluted within 10 min and were well resolved with no endogenous interference. Good linearity was observed in the range of 1-12 mg/dL for both anesthetics and 2.5-40 mg/dL for the other five analytes. The method showed good precision, sensitivity and repeatability. Most of the analytes remained stable during the storage of samples at 4°C. Desflurane and acetone degraded (>10%), when the samples remained on the autosampler for more than 2 and 3 h, respectively. The method was finally applied on clinical and post-mortem blood and urine samples. The clinical samples were collected both from patients who underwent surgery, as well as from the occupationally exposed medical and nursing staff of the university hospital, working in the operating rooms. The hospital staff samples were found negative for all compounds, while the patients' samples were found positive for the anesthetic administered to the patient. The post-mortem blood samples were found positive for ethanol and acetaldehyde.

Urinary methyl tert-butyl ether and benzene as biomarkers of exposure to urban traffic.

Methyl tert-butyl ether (MTBE) and benzene are added to gasoline to improve the combustion process and are found in the urban environment as a consequence of vehicular traffic. Herein we evaluate urinary MTBE (MTBE-U) and benzene (BEN-U) as biomarkers of exposure to urban traffic. Milan urban policemen (130 total) were investigated in May, July, October, and December for a total of 171 work shifts. Personal exposure to airborne benzene and carbon monoxide (CO), and atmospheric data, were measured during the work shift, while personal characteristics were collected by a questionnaire. A time/activity diary was completed by each subject during the work shift. Spot urine samples were obtained for the determination of MTBE-U and BEN-U. Median personal exposure to CO and airborne benzene were 3.3 mg/m(3) and 9.6 µg/m(3), respectively; median urinary levels in end-of-shift (ES) samples were 147 ng/L (MTBE-U) and 207 ng/L (BEN-U). The time spent on traffic duty at crossing was about 40% of work time. Multiple linear regression models, taking into account within-subject correlations, were applied to investigate the role of urban pollution, atmospheric conditions, job variables and personal characteristics on the level of biomarkers. MTBE-U was influenced by the month of sampling and positively correlated to the time spent in traffic guarding, CO exposure and atmospheric pressure, while negatively correlated to wind speed (R(2) for total model 0.63, P<0.001). BEN-U was influenced by the month and smoking habit, and positively correlated to urinary creatinine; moreover, an interaction between CO and smoking was found (R(2)=0.62, P<0.001). These results suggest that MTBE-U is a reliable marker for assessing urban traffic exposure, while BEN-U is determined mainly by personal characteristics.

Urinary BTEX, MTBE and naphthalene as biomarkers to gain environmental exposure profiles of the general population.

The aim of this work was to evaluate urinary benzene, toluene, ethylbenzene, m+p-xylene, o-xylene (BTEX), methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and naphthalene (NAP) as biomarkers of exposure to environmental pollutants. Personal air and urine samples from 108 subjects belonging to the Italian general population were compared. Urinary profiles were obtained by headspace gas chromatography-mass spectrometry. BTEX, MTBE, ETBE and NAP median airborne exposures during a 5-h sampling were 4.0, 25.3, 3.8, 9.3, 3.4, 3.4, <0.8, and 3.4 microg/m(3), respectively. Meanwhile, median urinary levels, as geometric means of three determinations were: 122, 397, 74, 127, 43, 49, <15, and 46 ng/L, respectively. Urinary benzene and toluene concentrations were 4.6- and 1.2-fold higher in smokers than in non-smokers. For most chemicals, significant positive correlations between airborne exposure (log-transformed) and the corresponding biological marker (log-transformed) were found, with Pearson's r values for correlation, ranging from 0.228 to 0.396. Multiple linear regression analysis showed that the urinary level of these chemicals was influenced by personal airborne exposure, urinary creatinine, and urinary cotinine, with R(2) 0.733 for benzene. Urinary chemicals are useful biomarkers of environmental exposure. Given the ease of rapidly obtaining urine samples, they represent a non-invasive alternative to blood chemical analysis. The possibility of obtaining urinary exposure profiles makes this method an appealing tool for environmental epidemiology.

Single-walled carbon nanotubes as an effective adsorbent in solid-phase microextraction of low level methyl tert-butyl ether, ethyl tert-butyl ether and methyl tert-amyl ether from human urine.

Carbon nanotubes (CNTs) are a kind of new carbon-based nano-materials which have drawn great attention in many application fields. The potential single-walled carbon nanotubes (SWCNTs) as solid-phase microextraction (SPME) adsorbents for the preconcentration of environmental pollutants have been investigated in recent years. The goal of this work was to investigate the feasibility of SWCNTs used as adsorbents for solid-phase microextraction of methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE) and tert-amyl methyl ether (TAME) in human urine. SWCNTs were attached onto a stainless steel wire through organic binder. Potential factors affecting the extraction efficiency were optimized, including extraction time, extraction temperature, desorption time, desorption temperature, and salinity. The developed method showed good performance according to the ICH performance criteria for bioanalytical methods. The calibration curves of the ethers were linear (r(2)>or=0.992) in the range from 10 to 5000 ng L(-1). The limits of detection at a signal-to-noise (S/N) ratio of 3 were 10 ng L(-1) for all the analytes. In addition, compared with the commercial carboxen/polydimethylsiloxane (CAR/PDMS) fiber, the SWCNT fiber showed better thermal stability (over 350 degrees C) and longer life span (over 150 times). The developed method was applied successfully to determine trace level of the ethers in urine of 10 healthy male volunteers.

Toxicokinetics of methyl tert-butyl ether (MTBE) and tert-amyl methyl ether (TAME) in humans, and implications to their biological monitoring.

Healthy male volunteers were exposed via inhalation to gasoline oxygenates methyl tert-butyl ether (MTBE) or tert-amyl methyl ether (TAME). The 4-hr exposures were carried out in a dynamic chamber at 25 and 75 ppm for MTBE and at 15 and 50 ppm for TAME. The overall mean pulmonary retention of MTBE was 43 +/- 2.6%; the corresponding mean for TAME was 51 +/- 3.9%. Approximately 52% of the absorbed dose of MTBE was exhaled within 44 hr following the exposure; for TAME, the corresponding figure was 30%. MTBE and TAME in blood and exhaled air reached their highest concentrations at the end of exposure, whereas the concentrations of the metabolites tert-butanol (TBA) and tert-amyl alcohol (TAA) concentrations were highest 0.5-1 hr after the exposure and then declined slowly. Two consecutive half-times were observed for the disappearance of MTBE and TAME from blood and exhaled air. The half-times for MTBE in blood were about 1.7 and 3.8 hr and those for TAME 1.2 and 4.9 hr. For TAA, a single half-time of about 6 hr best described the disappearance from blood and exhaled air; for TBA, the disappearance was slow and seemed to follow zero-order kinetics for 24 hr. In urine, maximal concentrations of MTBE and TAME were observed toward the end of exposure or slightly (< or = 1 hr) after the exposure and showed half-times of about 4 hr and 8 hr, respectively. Urinary concentrations of TAA followed first-order kinetics with a half-time of about 8 hr, whereas the disappearance of TBA was slower and showed zero-order kinetics at concentrations above approx. 10 micro mol/L. Approximately 0.2% of the inhaled dose of MTBE and 0.1% of the dose of TAME was excreted unchanged in urine, whereas the urinary excretion of free TBA and TAA was 1.2% and 0.3% within 48 hr. The blood/air and oil/blood partition coefficients, determined in vitro, were 20 and 14 for MTBE and 20 and 37 for TAME. By intrapolation from the two experimental exposure concentrations, biomonitoring action limits corresponding to an 8-hr time-weighted average (TWA) exposure of 50 ppm was estimated to be 20 micro mol/L for post-shift urinary MTBE, 1 mu mol/L for exhaled air MTBE in a post-shift sample, and 30 micro mol/L for urinary TBA in a next-morning specimen. For TAME and TAA, concentrations corresponding to an 8-hr TWA exposure at 20 ppm were estimated to be 6 micro mol/L (TAME in post-shift urine), 0.2 micro mol/L (TAME in post-shift exhaled air), and 3 micro mol/L (TAA in next morning urine).

Determination of low level methyl tert-butyl ether, ethyl tert-butyl ether and methyl tert-amyl ether in human urine by HS-SPME gas chromatography/mass spectrometry.

Methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE) and tert-amyl methyl ether (TAME) are oxygenated compounds added to gasoline to enhance octane rating and to improve combustion. They may be found as pollutants of living and working environments. In this work a robotized method for the quantification of low level MTBE, ETBE and TAME in human urine was developed and validated. The analytes were sampled in the headspace of urine by SPME in the presence of MTBE-d12 as internal standard. Different fibers were compared for their linearity and extraction efficiency: carboxen/polydimethylsiloxane, polydimethylsiloxane/divinylbenzene, and polydimethylsiloxane. The first, although highly efficient, was discarded due to deviation of linearity for competitive displacement, and the polydimethylsiloxane/divinylbenzene fiber was chosen instead. The analysis was performed by GC/MS operating in the electron impact mode. The method is very specific, with range of linearity 30-4600 ng L(-1), within- and between-run precision, as coefficient of variation, <22 and <16%, accuracy within 20% the theoretical level, and limit of detection of 6 ng L(-1) for all the analytes. The influence of the matrix on the quantification of these ethers was evaluated analysing the specimens of seven traffic policemen exposed to autovehicular emissions: using the calibration curve and the method of standard additions comparable levels of MTBE (68-528 ng L(-1)), ETBE (<6 ng L(-1)), and TAME (<6 ng L(-1)) were obtained.

Exposure to MTBE, TAME and aromatic hydrocarbons during gasoline pump maintenance, repair and inspection.

The exposure of gasoline pump repairers and inspectors to gasoline was studied at service stations and repair shops in Finland in April-June 2004. The average air temperature ranged from 7 degrees C to 16 degrees C and wind speed from 2.5 to 7 m/s. The gasoline blends contained mixtures of methyl tert-butyl ether (MTBE) and tert-amyl methyl ether (TAME), the total content of oxygenates being 11-12%. The content of benzene was <1%. Breathing zone air was collected during the work task using passive monitors. The mean sampling period was 4.5 h. The mean TWA-8 h concentrations for MTBE, TAME, hexane, benzene, toluene, ethylbenzene and xylene were 4.5, 1.3, 0.55, 0.23, 2.2, 0.26 and 1.1 mg/m3, respectively. None of the individual benzene concentrations exceeded the binding limit value for benzene (3.25 mg/m3). The sum concentration of MTBE and TAME in urine was between 8.9 and 530 nmol/l in individual post-shift samples. The individual sum concentrations of the metabolites tert-butyl alcohol and tert-amyl alcohol collected the following morning after the exposure ranged from 81 to 916 nmol/l. All individual results were below corresponding biological action levels. Exposure to aromatic hydrocarbons was estimated from post-shift urine samples, with benzene showing the highest concentration (range 4.4 and 35 nmol/l in non-smokers). The exposure levels were similar to those measured in previous studies during unloading of tanker lorries and railway wagons. The results indicated a slightly higher exposure for inspectors, who calibrated fuel pump gauges at the service stations, than for pump repairers. No significant skin exposure occurred during the study.

[Urinary MTBE as biological marker of exposure to traffic exhaust fumes]. / Valutazione di MTBE urinario come indicatore biologico di esposizione a traffico autoveicolare.

Methyl tert-butyl ether (MTBE) is an oxygenated compound added to Italian fuel in quantity of about 3% v/v. In the present study the excretion of urinary MTBE (U-MTBE) was evaluated as biomarker of exposure to traffic exhaust fumes. With this aim 127 Milan urban policemen, working as traffic wardens, were investigated. Spot urine samples were obtained prior to and at the end of the work shift, in different seasons. Median U-MTBE varied from 74 to 164 ng/L (range 60-657 ng/L). Comparing the pre-shift and end-shift samples an increase of about 14% in the U-MTBE level during the workshift was observed. An influence of the different seasons was observed, with lower values in spring and higher values in winter. Smoking did not affect the excretion of U-MTBE. The results of this study suggest that U-MTBE is a sensitive and specific marker for the assessment of exposure to traffic exhaust fumes.