Browse > Article
http://dx.doi.org/10.15269/JKSOEH.2016.26.2.178

Biological Monitoring of Workers Exposed to Diisocyanates using Urinary Diamines  

Lee, Jong Seong (Occupational Lung Diseases Research Institute, Korea Workers' Compensation & Welfare Service)
Kim, Boowook (Occupational Lung Diseases Research Institute, Korea Workers' Compensation & Welfare Service)
Shin, Jungah (Occupational Lung Diseases Research Institute, Korea Workers' Compensation & Welfare Service)
Baek, JinEe (Occupational Lung Diseases Research Institute, Korea Workers' Compensation & Welfare Service)
Shin, Jae Hoon (Occupational Lung Diseases Research Institute, Korea Workers' Compensation & Welfare Service)
Kim, Ji-hye (Occupational Lung Diseases Research Institute, Korea Workers' Compensation & Welfare Service)
Publication Information
Journal of Korean Society of Occupational and Environmental Hygiene / v.26, no.2, 2016 , pp. 178-187 More about this Journal
Abstract
Objectives: Diisocyanates are a potent inducer of diseases of the airways, especially asthma. In this study, toluenediamine(TDA) and methylenedianiline(MDA) in urine were evaluated as biomarkers of exposure to tolunenediisocyanate(TDI) and methylenediphenyl diisocyanate(MDI), respectively. Methods: Workers exposed to TDI and MDI, as well as non-occupationally exposed subjects, were studied and pre- and post-shift urine samples were collected from 8 control subjects and 8 workers from a factory which manufactures polyurethane products for reducing noise and vibration in automobiles. Airborne TDI and MDI(n=8) were sampled on solvent-free glass filters impregnated with n-butylamine and detected by liquid chromatography atmospheric pressure ionization tandem mass spectrometry. Urinary TDA and MDA were detected as pentafluoropropionic acid anhydride(PFPA) derivatives by liquid chromatography electrospray ionization tandem mass spectrometry. Results: The median levels of urinary 2,6-TDA(p<0.001), 2,4-TDA(p=0.001), and MDA(p<0.001) of workers in post-shift samples were significantly higher than those of controls. The median levels of urinary 2,6-0TDA($0.63{\mu}g/g$ creatinine vs $0.34{\mu}g/g$ creatinine, p=0.017) and MDA($4.21{\mu}g/g$ creatinine vs $3.18{\mu}g/g$ creatinine, p=0.017) of workers in post-shift samples were significantly higher than those of the pre-shift samples. There were significant correlations between the urinary 2,6-TDA, 2,4-TDA, and MDA of workers in post-shift samples and the airborne 2,6-TDI(rho=0.952, p<0.001), 2,4-TDI(rho=0.833, p=0.001), and MDI(rho=0.952, p<0.001). Conclusions: These urinary diamines, metabolites of diisocyanates, in post-shift samples were useful biomarkers to assess occupational exposure to diisocyanates.
Keywords
biological monitoring; methylenedianiline(MDA); methylenediphenyl diisocyanate(MDI); toluenediamine(TDA); tolunediisocyanate(TDI);
Citations & Related Records
Times Cited By KSCI : 1  (Citation Analysis)
연도 인용수 순위
1 Brown WE & Burkert AL. Biomarkers of toluene diisocyanate exposure. Appl Occup Environ Hyg 2002;17(12):840-845   DOI
2 Carino M, Aliani M, Licitra C, Sarno N, Ioli F. Death due to asthma at workplace in a diphenylmethane diisocyanate-sensitized subject. Respiration 1997;64(1):111-113   DOI
3 Creely KS, Hughson GW, Cocker J, Jones K. Assessing isocyanate exposures in polyurethane industry sectors using biological and air monitoring methods. Ann Occup Hyg 2006;50(6):609-621   DOI
4 Dahlin J. Aerosols of isocyanates, amines and anhydrides. 2007 Universitetsservice, US-AB. Stockholm(ISBN 978-91-7155-415-4)
5 Donnelly R, Buick JB, Macmahon J. Occupational asthma after exposure to plaster casts containing methylene diphenyl diisocyanate. Occup Med(Lond) 2004;54(6):432-434   DOI
6 Fent KW, Jayaraj K, Ball LM, Nylander-French LA. Quantitative monitoring of dermal and inhalation exposure to 1,6-hexamethylene diisocyanate monomer and oligomers. J Environ Monit 2008;10(4):500-507   DOI
7 Glindmeyer HW, Lefante JJ Jr, Rando RJ, Freyder L, Hnizdo E et al. RN. Spray-painting and chronic airways obstruction. Am J Ind Med 2004;46(2):104-111   DOI
8 Health and Safety Executive(HSE).(2005) EH40/2005 Workplace exposure limit. Sudbury Suffolk, UK: HSE books
9 HSE.(2009) Safety in motor vehicle repair: working with isocyanates paints. INDG 388(rev1). Available at http://www.hse.gov.uk/pubns/indg388.pdf. Accessed 16 Jan 2014
10 IARC monographs volumes 1-109(14 January 2014). http://monographs.iarc.fr/ENG/Classification/ClassificationsAlphaOrder.pdf
11 International Organization for Standardization(ISO) 17734-1:2013(E) Determination of organonitrogen compounds in air using liquid chromatography and mass spectrometry - Part I: Isocyanates using dibutylamine derivatives. 2nd edition(2013.12.01.)
12 Jeong JY. Assessment of Worker's Diisocyanates Skin Exposure at Polyurethane Foam manufacturing Companies. J Korean Soc Occup Environ Hyg 2013;23(2):57-64
13 Kaaria K, Hirvonen A, Norppa H, Piirila P, Vainio H. Exposure to 4,4'-methylenediphenyl diisocyanate (MDI) during moulding of rigid polyurethane foam: determination of airborne MDI and urinary 4,4'-methylenedianiline(MDA). Analyst 2001;126(4):476-479   DOI
14 Kang HK & Kim H. Assessment of total is ocyanates by OSHA and NIOSH analytical methods : accuracy and precision and airborne concentrations by process. Korean Ind Hyg Assoc J 1999;9(2):1-18
15 Lee SI, Cho BM, Hwang IK, Lee CH, Park JR. A study on comparison of the metabolites related with working methods and immunity of the toluene diisocyanateexposed workers. Korean J Occup Med, 1998:10(3);320-332
16 Liljelind I, Norberg C, Egelrud L, Westberg H, Eriksson K et al. Dermal and inhalation exposure to methylene bisphenyl isocyanate(MDI) in iron foundry workers. Ann Occup Hyg 2010;54(1):31-40   DOI
17 Liu Q & Wisnewski AV. Recent developments in diisocyanate asthma. Ann Allergy Asthma Immunol 2003;90(5 Suppl 2):35-41   DOI
18 Marand A, Karlsson D, Dalene M, Skarping G. Determination of amines as pentafluoropropionic acid anhydride derivatives in biological samples using liquid chromatography and tandem mass spectrometry. Analyst 2004;129(6):522-528   DOI
19 Marand A, Karlsson D, Dalene M, Skarping G. Solvent-free sampling with di-n-butylamine for monitoring of isocyanates in air. J Environ Monit 2005;7(4):335-43   DOI
20 Ott MG. Occupational asthma, lung function decrement, and toluene diisocyanate(TDI) exposure: a critical review of exposure-response relationships. Appl Occup Environ Hyg 2002;17(12):891-901   DOI
21 Petsonk EL, Wang ML, Lewis DM, Siegel PD, Husberg BJ. Asthma-like symptoms in wood product plant workers exposed to methylene diphenyl diisocyanate. Chest. 2000;118(4):1183-1193   DOI
22 Piirila PL, Nordman H, Keskinen HM, Luukkonen R, Salo SP et al. Long-term follow-up of hexamethylene diisocyanate-, diphenylmethane diisocyanate-, and toluene diisocyanate-induced asthma. Am J Respir Crit Care Med 2000;162(2 Pt 1):516-522   DOI
23 Pronk A, Yu F, Vlaanderen J, Tielemans E, Preller L et al. Dermal, inhalation, and internal exposure to 1,6-HDI and its oligomers in car body repair shop workers and industrial spray painters. Occup Environ Med 2006;63(9):624-631   DOI
24 Rattery NJ, Botham PA, Hext PM, Woodcock DR, Fielding I et al. Induction of respiratory hypersensitivity to diphenylmethan-4,4'diisocyanate (MDI) in guiea pigs. Influence of rout of exposure. Toxicol 1994;88:15-30   DOI
25 Redlich CA & Karol MH. Diisocyanate asthma: clinical aspects and immunopathogenesis. Int Immuno-pharmacol 2002;2(2-3):213-224   DOI
26 Redlich CA & Herrick CA. Lung/skin connections in occupational lung disease. Curr Opin Allergy Clin Immunol 2008;8(2):115-119   DOI
27 Rosenberg C & Savolainen H. Determination of occupational exposure to toluene diisocyanate by biological monitoring. J Chromatogr 1986;367(2) :385-392   DOI
28 Sabbioni G, Dongari N, Kumar A. Determination of a new biomarker in subjects exposed to 4,4'-methylene diphenyl diisocyanate. Biomarkers 2010;15(6) :508-515   DOI
29 Sari-Minodier I, Charpin D, Signouret M, Poyen D, Vervloet D. Prevalence of self-reported respiratory symptoms in workers exposed to isocyanates. J Occup Environ Med 1999;41(7):582-588   DOI
30 Sennbro CJ, Lindh CH, Ostin A, Welinder H, Jonsson BA et al. A survey of airborne isocyanate exposure in 13 Swedish polyurethane industries. Ann Occup Hyg 2004a;48(5):405-414   DOI
31 Sennbro CJ, Lindh CH, Tinnerberg H, Welinder H, Littorin M. Biological monitoring of exposure to toluene diisocyanate. Scand J Work, Environ Health 2004b;30(5):371-378   DOI
32 Tinnerberg H, Dalene M, Skarping G. Air and Biological Monitoring of Toluene Diisocyanate in a Flexible Foam Plant. Am Ind Hyg J 1997;58(3): 229-235   DOI
33 Usui Y, Aida H, Kimula Y, Miura H, Takayama S et al. Hypersensitivity pneumonitis induced by hexamethylene diisocyanate. Intern Med 1992 ;31(7):912-916   DOI
34 Woellner RC, Hall S, Greaves I, Schoenwetter WF. Epidemic of asthma in a wood products plant using methylene diphenyl diisocyanate. Am J Ind Med 1997;31(1):56-63   DOI
35 American Conference of Governmental Industrial Hygienists(ACGIH). 2013 TLVs and BELs based on the documentation of the threshold limit values for chemical substance and physical agents and biological exposure indices. Cincinnati, OH, ACGIH, 2013
36 Anh YS, Roh JH, Kim CN, Park YJ, Jung SH. Biological monitoring of workers exosed to toluene diisocyanate. The Kor J Occup Med 1995;7(2):354-361
37 Boutin M & Dufresne A. Determination of Airborne Isocyanates Generated During the Thermal Degradation of Car Paint in Body Repair Shops. Ann Occup Hyg 2006;50(4):385-393   DOI