6 - A bs tract- Chromium in Erythrocytes as a Biological Marker of Worker Expos ed to Hexavalent Chromium Ui- Seoung Yoon, Kw ang- Jong Kim Departm en

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1 6 - A bs tract- Chromium in Erythrocytes as a Biological Marker of Worker Expos ed to Hexavalent Chromium Ui- Seoung Yoon, Kw ang- Jong Kim Departm ent of Preventive M edicine & Institute for Occupational and E nvironm ental H ealth, Colleg e of M edicine, K orea U niversity Objective - T o evaluate the usefulness of chromium in erythrocytes as a biological marker of exposure to hexavalent chromium in chromate producers and chrome platers Methods - Blood and urine samples were ramdomly obtained from chromate prodecers (n=34) and chrome platers (n=35), and non- exposed workers (n=75). chromium level in erythrocytes and plasma, and urine were measured. Different chromium exposure workers were assessed through measurements of airborne hexavalent chromium concentrations using a personal air sampler. Linear associations between variables were evaluated with correlation analysis. Results - T he chromate producers had mean chromium levels in erythrocytes five fold as higher than the chrome platers, and fifteen fold higher than non- exposed group. Among the chromium exposed workers, airborne hexavalent chromium was positively and strongly correlated with in erythrocytes (r= p< 0.01), and erythrocytes chromium was inversely correlated with hematocrit (r= , p< 0.01), hemoglobin (r= , p< 0.01) and the number of red blood cells (r=- 0.28, p< 0.05). Conclusions - In conclusion, this study suggests that chromium in erythrocytes is a good indicator of the chromium body burden caused by exposure to hexava.lent chromium. Key Word : chromeplater, biological marker, erythrocytes, hexavalent chromium , : T el) , Fax) , E- mail) kkjo@mail.korea.ac.kr

2 1..,,,,,, (Ladou, 1997)., ,, (WHO, 1988; Langard, 1990) (Wetterhan, 1989; Ryberg Alexander, 1990; Capellmann Bolt, 1992). (1998) (American Conference of Governmental Industrial Hygienists, ACGIH, 1999) /, ACGIH A1". (National Institute for Occupational Safety and Health, NIOSH) / (NIOSH, 1994) (Lukanova, 1996 ; Miksche Lewalter, 1997 ; Harzdorf Lewalter, 1997) (Wiegand, 1985; Alexander Aaseth, 1995). (WHO, 1988 ; Miksche Lewalter, 1997; Harzdorf Lewalter, 1997) ,, ) 9

3 ,, 1,,,,, ) (2) isotonic saline solution 1,200rpm isotonic saline ml ultra water. (1) 6 6 NIOSH Manual of Analytical Methods No.7600 (NIOSH, 1994). PVC (pore size 5.0, 37mm) (Gilian, USA) 1.5 /min 8. 6 Wang (1997, 1999) ultrasonication and strong anion- exchange solid phase extraction method., M(NH4)2SO4/0.05M NH4 OH(pH8) 10 (< 40 ) strong anion- exchange /min 0.5M(NH4)2SO4/0.1M NH4OH(pH8) % HCl mM diphenylcarbazide nm (Ceil 3000, England). 1.25%(NH4)2HPO4 1% T riton X % HNO (GF- AAS, Hitachi Z- 8100, Japan). GF- AAS 3 [1 : (40 ), 2 : (10 ), 3 : (30 )], 3 [1 : (40 ), 2 : 600 (10 ), 3 : 700 (5 )}, 2,900 (5 ) 357.9nm. 1000ppm 1% HNO3 0.5, 1.0, 1.5 / /, /.. (3) 30

4 4 2 microwave oven % 200 1% T riton X ,. 1000ppm 1% HNO3 4, 8, 16, 24 /. /, /g creatinine. (UCT - 1, Japan), (Olympus AU 400, Japan) Jaffe method /. (4),, 2 (Nion Kohden, MEK- 6108K, Japan),,. (5) SPSS 8.0.,. t- test, ANOVA.,,,,,,,,, ,,, T able , 4.1, 1.2, ,,,. 6 T able 2. T able 1. General characteristics of exposed and non- exposed group. Exposed (n=69) Non- exposed (n=75) mean(sd) p- value* Age(year) 34.3( 8.1) 32.3(8.9) 0.16 Work duration(year) 4.1( 3.4) 4.2(3.3) 0.87 Alcohol consumption(bottle /week) 1.2( 1.4) 1.4(1.6) 0.54 Smoking amount(cigarettes/day) 17.6(10.7) 19.3(8.6) 0.20 SD: Standard Deviation * : t- test : 24% alcohol, 360 volume

5 T able 2. Airborne hexavalent chromium concentrations in exposed group Industry No. of workers Hexavalent chromium( / ) GM GSD Range p- value* Chromate producing Chrome plating T otal GM(GSD): Geometric Mean(Geometric Standard Deviation) * : t- test / ( / ) 7.2 / ( / ) / (, 1998 ). T able / ( / ) 4.81 / ( / ), 1.64 / ( / ) 5, /1012cells ( /1012cells) 0.48 /1012cells ( /1012cells), 0.15 /1012cells ( /1012cells), 4, /ghb ( /g T able 3. Mean chromium concentrations in erythrocytes among exposed and non- exposed group. Variable Erythrocytes( /, corrected for Hct) Chromate producers Chrome platers Non- exposed N 34 GM (GSD) (1.04) Range N GM (GSD) (0.67) Range N 75 GM (GSD) 1.64 (1.33) Range p- value* Erythrocytes ( /1012 cells) (0.88) (0.87) (1.33) Erythrocytes ( /ghb) (0.90) (0.70) (1.33) GM(GSD): Geometric Mean(Geometric Standard Deviation) * : ANOVA test : Variable is corrected with hematocrit, number of red blood cells, and hemoglobin.

6 Hb) 1.31 /ghb ( /ghb), 0.47 /ghb ( /ghb) 5, 14. T able / ( / ) 2.13 / ( / ), 0.65 / ( / ), (P< 0.001) /g creatinine ( /g creatinine) /g creatinine ( /g creatinine), /g creatinine ( /g creatinine) (P< 0.001). 6,, T able 5. 6, (A- cr), (U- cr), (P- cr) (E- cr),,, T able 4. Mean chromium concentrations in plasma and in urine among exposed and non- exposed group Group Exposed group chromate producers chrome platers Non- exposed group No. of Workers Chromium in plasma( / ) Chromium in urine ( /g creatinine) GM(GSD) Range GM(GSD) Range 5.70(1.38) 2.13(1.36) 0.65(1.52) (0.87) 38.05(0.91) 13.14(0.70) p- value=0.000* p- value=0.000* GM(GSD) : Geometric Mean(Geometric Standard Deviation) * : ANOVA test T able 5. Chromium concentrations in erythrocytes, plasma, and urine by hexavalent chromium exposure level Hexavalent chromium level in air( / ) No. of Workers Cr in erythrocytes ( / ) Cr in plasma ( / ) Cr in Urine ( /g crea.) GM(GSD) GM(GSD) GM(GSD) 6.24(0.96) 12.03( 0.32) 39.33(0.62) 2.20(1.38) 5.09(1.35) 9.55(1.13) 35.37(0.86) 47.66(0.93) 60.81(0.87) p- value=0.000* p- value=0.001* p- value=0.109* GM(GSD): Geometric Mean(Geometric Standard Deviation) * : ANOVA test

7 T able 6. T he correlation coefficients matrix of selected study variables Age Age Work duration work duration 0.482** Smoking amount smoking amount Log P- cr Log P- cr Log U- cr Log U- cr ** * ** Log U- cr/ crea. Log U- cr/crea ** Log A- cr ** 0.279* 0.219* Log A- cr Log E- cr Log E- cr ** 0.423** 0.259* 0.689** Log P- cr: Log plasma chromium Log U- cr: Log urinary chromium corrected specific gravity Log U- cr/crea.: Log urinary chromium corrected for creatinine Log A- cr: Log airborne hexavalent chromium Log E- cr : Log erythrocyte chromium * : p< 0.05, ** : p< 0.01 T able 6. 6 (r=0.689, p< 0.01) 6, (p< 0.01), (0< 0.05)., (p< 0.01), (p< 0.01) 0.346(p< 0.01) (0< 0.05). (r= , P< 0.05). 6,,, T able 7. 6 (r= , p< 0.01) (r= , p< 0.01). T able 7. Correlation coefficients between hexavalent chromium in air, chromium in erythrocytes and hemoglobin, hematocrit, and the number of red blood cells Hemoglobin Hematocrit RBCs * : p< 0.05, ** : p< 0.01 Log hexavalent chromium in air correlation coefficient(r) ** ** Log chromium in erythrocytes correlation coefficient(r) ** ** *

8 Fig. 1. Scatterplot between Cr in air and in erythrocytes Fig. 2. Scatterplot between Cr in urine and in erythrocytes

9 (r= , P 0.01) (r= , P 0.01), (r= , P 0.05). 6, 1, 2. 6 Log Y= Log X (r2=0.475, p=0.000). Log Y= Log X (r2=0.179, p=0.000). 4., (Yoshikawa Hara, 1980), 6 3 (Nomiyama, 1980) transferrin. 6 (WHO, 1988) (real risk) (Gao, 1993; Finley, 1996; Lukanova, 1996) /, 5, 15, /, 1.64 /, Lukanova (1996) /, / / 2.13 /, 0.65 /, Gao (1994) / / /g creatinine (1995) / 25.4 /g creatinine, 38.5 /g creatinine Lai (1998) /g creatinine.,,,. 6, 10.7 / ( ) 7.2

10 / ( / ) 1.5, 50.0 /. 6, 6,,. 6 (Boeniger, 1993). 6,... 6 (subclinical anemia),, 6,. Lukanova (1996) / (r=- 0.66, p< 0.01) (r=- 0.62, P< 0.02), (r=- 0.55, P< 0.04) (, 1997) , 75 6,,. 1) / ( / ) 7.2 /. 2) / ( / ) 5, 15. 3) 5.70 / ( / ), /g creatinine ( /g creatinine)

11 . 6. 4) (r=0.689, p< 0.01),,. 5) 6 (r= , p< 0.01) (r= , p< 0.01).,,. chemical exposure with emphasis on creatinine adjustment : A review. Am Ind Hyg Assoc. J. 1993; 54: Capellmann M, Bolt HM. Chromium( ) reducing capacity of ascorbic acid and of human plasma in vitro. Arch T oxicol 1992;66:45-50 Finley BL, Scot Pk, Norton RL, Gargas ML, Paustenbach DJ. Urinary chromium col,(i) ntj TD Tc (u) Tj5.43(D RE FE RE NCE S.., ( ). ;1998,,,,,,,,. 8- hydroxydeoxyguanosine. 1995;28: Alexander J, Aaseth J. Uptake of chromium in human red blood cells and isolated rat liver cells: T he role of the anion carrier. Analyst 1995; 120: American Conference of Governmental Industrial Hygienists(ACGIH): T hreshold Limit Values for chemical substances and physical agents and biological exposure indices, OH:NIOSH;1999 Boeniger MF, Lowry LK, Rosenberg J. Interpretation of urine results used to assess

12 Panev T, Popov T, T aioli E, Costa M. Occupational exposure to Cr( ) : Comparison with between chromium levels in lymphocytes, erythrocytes, and urine. Int Arch Occup Environ Health 1996;69:39-44 Miksche LW, Lewalter J. Health surveillance and biological effect monitoring for chromium exposed workers. Regul T oxicol and Pharmaco 1997; 26:94-99 NIOSH. NIOSH Manual of analytical Methods, 6th Editions, DHHS(NIOSH) Publication. Cincinnati, Ohio: NIOSH;1994 Nomiyama H, Yotoriyama M, Nomiyama. K. Normal Chromium levels in urine and blood Japanese subjects determined by the direct flameless atomic absorption spectrophotometer and chemical forms of chromium in urine after exposure to hexavalent chromium. Am lnd Hyg Assoc 1980;41:98 Ryberg D Alexander J. Mechanisms of chromium toxicity in mitochondria. Chem Biol Interact 1990;75: Wang J, Ashley K, Marlow D. Field method for the determination of hexavalent chromium by ultrasonication and strong anion- exchange solidphase extraction. Anal Chem 1999;71: Wang J, Ashley K, Kennedy ER, Neumsister C. Determination of hexavalent chromium in industrial hygiene samples using ultrasonic extraction and flow injection analysis. Analyst 1997;122; Wetterhan KE, Halmiton JW, Alyar J, Borges KM, Floyd R. Mechanism of chromium( ) carcinogenesis, reactive intermediates and effect on gene expression. Biol T race Element Res 1989;21: World Health organization. Environmental health Criteria 61. Chromium. Geneva:WHO;1988 Wiegand HJ. Fast uptake kinetics in vitro of chromium- 51( ) by red blood cells of man and rat. Arch T oxicol 1985;57:31-34 Yoshikawa H, Hara N. Distribution of Chromium in organ of mice injected subcutaneously daily with trivalent and hexavalent chromium. Jap J Ind Health 1980;22:126

17 1 ( ) J Korean Soc Occup Environ Hyg 2007;17(1):31-42 Assessment of Indoor Air Quality in Commercial Office Buildings Jee Yeon Jeong 1 Byung

17 1 ( ) J Korean Soc Occup Environ Hyg 2007;17(1):31-42 Assessment of Indoor Air Quality in Commercial Office Buildings Jee Yeon Jeong 1 Byung 17 1 (2007 ) J Korean Soc Occup Environ Hyg 2007;17(1):1-42 Assessment of door Air Quality in Commercial Office Buildings Jee Yeon Jeong 1 Byung Kyoo Lee 1 Young Gyu Phee 1 Department of Occupational Environment