Akito Takeuchi

Unmetabolized VOCs in Urine as Biomarkers of Low Level Exposure in Indoor Environments

Unmetabolized VOCs in Urine as Biomarkers of Low Level Exposure in Indoor Environments: Bing‐Ling Wang, et al. Department of Public Health, Okayama University Graduate School of Medicine, Dentistry and Pharmaceutical Sciences—This study aimed to test the possible use of unmetabolized volatile organic compounds (VOCs) in urine as biomarkers of low‐level indoor environmental exposure. Twenty‐four subjects in 13 dwellings in a prefecture of Japan participated in this study. Air samples of the breathing zone were collected in the living room and bedroom, along with spot urine samples (before bedtime and first morning voids). Toluene, ethylbenzene, xylene isomers, styrene and p‐dichlorobenzene in the air and urine samples were measured by gas chromatography/mass spectrometry. For the 21 subjects without solvent exposure at work, there were significant correlations between the timeweighted average air concentrations in the bedroom and morning urinary concentrations for toluene, oxylene, total xylene and p‐dichlorobenzene (correlation coefficients of 0.54, 0.61, 0.56 and 0.84, respectively). Multiple linear regression analysis showed only air VOCs in the bedroom influenced the morning urinary VOC concentrations. We concluded that unmetabolized VOCs in the urine can provide a reliable biological indicator for air VOC exposures in non‐occupational environments.

Biological monitoring of occupational exposure to 1-bromopropane by means of urinalysis for 1-bromopropane and bromide ion

The purposes of the present study are (1) to develop a sensitive analytical method to measure 1-bromopropane (1-BP) in urine, (2) to examine if 1-BP or bromide ion (Br) in urine is a useful biomarker of exposure to 1-BP, and (3) to identify the lowest 1-BP exposure concentration the method thus established can biomonitor. A factory survey was carried out on Friday, and 33 workers (all men) in cleaning and painting workshops participated; each worker was equipped with a diffusive sampler (carbon cloth KF-1500 as an adsorbent) to monitor 1-BP vapour for an 8-h shift, and offered a urine sample at the end of the shift for measurement of 1-BP and Br in urine. In addition, 10 non-exposed men offered urine samples as controls. The performance of the carbon cloth diffusive sampler was examined to confirm that the sampler is suitable for monitoring time-weighted average 1-BP vapour exposure. A head-space GC technique was employed for analysis of 1-BP in urine, whereas Br in urine was analysed by ECD-GC after derivatization to methyl bromide. The workers were exposed to vapours of seven other solvents (i.e. toluene, xylenes, ethylbenzene, acetone, etc.) in addition to 1-BP vapour; the 1-BP vapour concentration was 1.4 ppm as GM and 28 ppm as the maximum. Multiple regression analysis however showed that 1-BP was the only variable that influenced urinary 1-BP significantly. There was a close correlation between 1-BP in urine and 1-BP in air; the correlation coefficient (r) was >0.9 with a narrow variation range, and the regression line passed very close to the origin so that 2 ppm 1-BP exposure can be readily biomonitored. The correlation of Br in urine with 1-BP in air was also significant, but the r (about 0.7) was smaller than that for 1-BP, and the background Br level was also substantial (about 8 mg l-1). Thus, it was concluded that 1-BP in end-of-shift urine is a reliable biomarker of occupational exposure to 1-BP vapour, and that Br in urine is less reliable.

Sequential extraction of inorganic arsenic compounds and methyl arsenate in human urine using mixed‐mode monolithic silica spin column coupled with gas chromatography‐mass spectrometry

A sequential analytical method was developed for the detection of arsenite, arsenate, and methylarsenate in human urine by gas chromatography-mass spectrometry (GC-MS). The combination of a derivatization of trivalent arsenic compounds by 2,3-dithio-1-propanol (British antilewisite; BAL) and a reduction of pentavalent arsenic compounds (arsenate and methylarsenate) were accomplished to carry out the analysis of arsenic compounds in urine. The arsenic derivatives obtained using BAL were extracted in a stepwise manner using a monolithic spin column and analyzed by GC-MS. A linear curve was observed for concentrations of arsenic compounds of 2.0 to 200 ng/mL, where the correlation coefficients of calibration curves were greater than 0.996 (for a signal-to-noise (S/N) ratio >10). The detection limits were 1 ng/mL (S/N > 3). Recoveries of the targets in urine were in the range 91.9-106.5%, and RSDs of the intra- and interday assay for urine samples containing 5, 50, and 150 ng/mL of arsenic compounds varied between 2.95 and 13.4%. The results from real samples obtained from a patient suspected of having ingested As containing medications using this proposed method were in good agreement with those obtained using high-performance liquid chromatography with inductively coupled plasma mass spectrometry.

Determination of dimethyl sulfoxide and dimethyl sulfone in urine by gas chromatography-mass spectrometry after preparation using 2,2-dimethoxypropane.

A method for routinely determination of dimethyl sulfoxide (DMSO) and dimethyl sulfone (DMSO(2)) in human urine was developed using gas chromatography-mass spectrometry. The urine sample was treated with 2,2-dimethoxypropane (DMP) and hydrochloric acid for efficient removal of water, which causes degradation of the vacuum level in mass spectrometer and shortens the life-time of the column. Experimental DMP reaction parameters, such as hydrochloric acid concentration, DMP-urine ratio, reaction temperature and reaction time, were optimized for urine. Hexadeuterated DMSO was used as an internal standard. The recoveries of DMSO and DMSO(2) from urine were 97-104 and 98-116%, respectively. The calibration curves showed linearity in the range of 0.15-54.45 mg/L for DMSO and 0.19-50.10 mg/L for DMSO(2). The limits of detection of DMSO and DMSO(2) were 0.04 and 0.06 mg/L, respectively. The relative standard deviations of intra-day and inter-day were 0.2-3.4% for DMSO and 0.4-2.4% for DMSO(2). The proposed method may be useful for the biological monitoring of workers exposed to DMSO in their occupational environment.

A Guillain-Barré Syndrome-like Neuropathy Associated with Arsenic Exposure

A Guillain‐Barré Syndrome‐like Neuropathy Associated with Arsenic Exposure: Sunyoung KIM, et al. Department of Neurology, Ulsan University Hospital, University of Ulsan College of Medicine, Republic of Korea—

Direct determination of N-methyl-2-pyrrolidone metabolites in urine by HPLC-electrospray ionization-MS/MS using deuterium-labeled compounds as internal standard

N-methyl-2-pyrrolidone (NMP) has been used in many industries and biological monitoring of NMP exposure is preferred to atmospheric monitoring in occupational health. We developed an analytical method that did not include solid phase extraction (SPE) but utilized deuterium-labeled compounds as internal standard for high-performance liquid chromatography-electrospray ionization-mass spectrometry using a C30 column. Urinary concentrations of NMP and its known metabolites 5-hydoxy-N-methyl-2-pyrrolidone (5-HNMP), N-methyl-succinimide (MSI), and 2-hydroxy-N-methylsuccinimide (2-HMSI) were determined in a single run. The method provided baseline separation of these compounds. Their limits of detection in 10-fold diluted urine were 0.0001, 0.006, 0.008, and 0.03 mg/L, respectively. Linear calibration covered a biological exposure index (BEI) for urinary concentration. The within-run and total precisions (CV, %) were 5.6% and 9.2% for NMP, 3.4% and 4.2% for 5-HNMP, 3.7% and 6.0% for MSI, and 6.5% and 6.9% for 2-HMSI. The method was evaluated using international external quality assessment samples, and urine samples from workers exposed to NMP in an occupational area.

Development of an Analytical Method for the Determination of Arsenic in Urine by Gas Chromatography-mass Spectrometry for Biological Monitoring of Exposure to Inorganic Arsenic

Development of an Analytical Method for the Determination of Arsenic in Urine by Gas Chromatography‐mass Spectrometry for Biological Monitoring of Exposure to Inorganic Arsenic: Akito TAKEUCHI, et al. Osaka Occupational Health Service Center, Japan Industrial Safety and Health Association—

Determination Method for Mono- and Diethanolamine in Workplace Air by High-performance Liquid Chromatography

Determination Method for Mono‐ and Diethanolamine in Workplace Air by High‐performance Liquid Chromatography: Akito TAKEUCHI, et al. Osaka Occupational Health Service Center, Japan Industrial Safety and Health Association—

Determination Method for Nitromethane in Workplace Air

Determination Method for Nitromethane in Workplace Air: Akito Takeuchi, et al. Osaka Occupational Health Service Center, Japan Industrial Safety and Health Association

Comparison of the exposure-excretion relationship between men and women exposed to organic solvents

Comparison of the exposure‐excretion relationship between men and women exposed to organic solvents: Toshio Kawai, et al. Osaka Occupational Health Service Center