4. Desorbed amount of formaldehyde diffusive sampler was increased by high relative humidity. 5. Wheth diffusive samplers were stored at room temperat

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1 9 1 K o r e a n In d. H y g. A s s oc. J V o l. 9, N o. 1. M a y, A bs tract- T he Dev elopment of New Diffus ive Sampler for F ormaldehyde in Air. Mee- heon Choe, Kw ang- Mook Lee, and Young- Man Roh Departm ent of Occupational H ygiene, Graduate School of Occupational H ealth, T he Catholic U niversity of K orea, Seoul, K orea T o utilize diffuse sampling of formaldehyde in air, a new sampler was designed. A glass fiber filter was impegnated with 2,4- dinitrophenylhydrazine(dnp) and phosphoric acid and mounted 37 cassette. T he formaldehyde vapor was sampled in the dynamic chamber and measured by high performance liquid chromatograph and compared with solid sorbent tube. T he results were as follows ; 1. T he desorption efficiencies of diffusive sampler between 97.0% and 100%. 2. The sampling rate is constant as in /min when sampling times are between 120 and 360 min. 3. T here was a significant relationship between concentrations of diffusive samples and active samples with the coefficient of determination(r2) of

2 4. Desorbed amount of formaldehyde diffusive sampler was increased by high relative humidity. 5. Wheth diffusive samplers were stored at room temperature or at refrigerator there was no statistically significant difference in the accuracy of result. 6. When the diffusive samplers, which collected formaldehyde vapor, were exposed to clean air for three hours, there was no significant loss of formaldehyde due to reverse diffusion. In conclusion, this study suggest that developed diffusive samplers will be a reasonable substitute for the solid sorbent tube for sampling formaldehyde and practical comparitive study of developed diffusive sampler should be performed at workplaces of manufacturing industry..,,,,,,,,,,,,,,.,,,,,,,, ( ),,. (, 1996)... (, 1996). (International Agency for Research on Cancer : IARC) (, 1995). bis- chloromethyl ether(bmce) (Frankel et al, 1979). (National Institute for Occupational Safety and Health, NIOSH) (potential occupational carcinogen). 37% 50% (, 1995). NIOSH 3500 ( ), 2541 (, NIOSH No. 2541). (Levin et al, 1985 ;, 1993), (NIOSH, 1994 ;, 1995)

3 ,, (Feigley, 1982).,. (Feigley, 1982).., NIOSH Fick 1 (Lautenberger et al, 1980 : Rose & Perkins, 1982 : Palmes et al, 1986 ). W = - DA dc dx...(1) W = (mass transfer rate, ng/sec) D = (diffusion coefficient, /sec) A = (cross sectional area of diffusion path, ) dc/dx = {the instantaneous rate of change in concentration over diffusion path, (ng/ )/ } (1) (L) ( C 1 -. C 0 ) (2) W = D A L ( C 1- C 0 )...(2) L C 1 C 0 =, =, ng/ =, ng/ C 0 0 (2) C 0 = 0 (t) (3). M = D A L ( C 1) t...(3) M =, ng t =, sec (3) DA/L /sec. (sampling rate, SR)

4 . (3) (4). C 1 = ML DA t...(4). L A, M, t. D

5 (dynamic system) (Permeater PD- 1B, Gastec, Japan) (Yao & Krueger, 1993 ;, 1993).,

6 ., (Alnor System, Model 360). (Gilian, M- odel LFS113D, USA) 0.1 /min. (Junsei chemical Co, Japan) 24 (Junsei c- hemical Co, Japan) (Aldrich chemical, USA) 1 60 GC. (formaldehyde oxazolidine, SUPELCO, U- SA). GC Table 1. acetonitrile(em Science, USA) pore size Millex- SR Filter 10 HPLC. formaldehyde- 2,4- DN- PH(SUPELCO, USA). HPLC T able 2. Table 1. Analysis condition of gas chromatography Variance System Gas chromatograph Detector Column Operating conditions Carrier gas Flow rate Injection volume Injection temperature Detection temperature Oven temperature Condition HP Flame Ionization Detector(FID) HP- FFAP 25m He 30 /min , isothermal Table 2. Varia nce HPLC Column Pum p Mobile phase Flow rate Detecter Analysis condition of High Performance Liquid Chromatograph conditions Injection volum e 3. 1) T LV, 1.0 T LV, 1.5 T LV, 2.0 T LV HPLC. 2) 2 3. Fick , 0.5, Condition W aters Nova- Pak C * 150 M odel 600E DW : Methanol(40 : 60, V /V ) 0.8 / m in is ocratic UV,

7 0.5 20% 80%. 3) ( ) (4 6 ) 1, 3, 7. 4) , 2, 4 3. Table 3. Desorption efficiency of formaldehyde from 2,4- DNP- coated filters(n=6) Amount spiked ( ) ) Value measured Mean( ) SD * Des orption E fficiency ( % ) = 7 V alue meas ured ( ) 100 A mount s piked ( ) Desorption efficiency (%) T able Fick 68 /min /min, /min. 4. SAS. t- test,. 25%.. 1. T able %. F ig. 3. Effect of s am pling tim e on sampling rate of diffusive sampler

8 Table 4. Effect of formaldehyde concentration on sampling rate of diffusive sampler ( Mean SD) HCHO level Sampling time. min (t) Amount measured by sampler. (Q) / Concentration meas ured by NIOSH method / (C) Calculated SR* / min 1.0 T LV ** T LV ** T LV * SR = Sampling Rate= ** P< 0.01 Q ( C )( t ) 1, 000 2) T able 4 1.0, 0.5, /min /min , 0.5 (P< 0.01). Fig. 4. Y = 1.84X (R =0.92). (R=0.96). 3) T able % 20%. T able 5 20% 15 80% (P< 0.01) , (P< 0.01). 3. T able %, 1%, 1 7 (P> 0.05). 8% 24% NIOSH 25%. 4. T able 7 30, 2,

9 3 (P> 0.05) % 28%. Fig. 4. Correlation of concentration of formaldehyde betw een diffus ive and active samples..,,,, (Environmental Protection Agency : EPA) 0.1ppm 0.5ppm 1.0ppm 3.0ppm (Ness, 1991).,.. NIOSH 3 75% %. NIOSH /min. Levin 60.9 /min 3.7 /min(levin et al, 1986),,. Kring 68 /min, Fick 0.16 /sec (Kring et al, 1982). (1996) GC HPLC 3, 2.5 HPLC GC. GC HPLC. SKC (, 1996) /min, /min 8% 62%. Feigly 27% 61% (Feigly & Lee, 1987) /min

10 T able 5. Effect of relative humidity on sampling rate of diffusive sampler and active sampler RH % S a m p l i n g time min (t) Amount measured by sampler (Q) / Concentration measured by NIOSH method / (C) Calculated SR* /min ** ** ** ** ** 38.4** ** RH : Relative humidity * SR = Sampling Rate= ** P< 0.01 Q ( C )( t ) 1000 T able 6. Effect of storage stability in diffus sampler (n=3) Item (unit) 1 day (A)** 3 days 7 days Room temp Mean( ) * SD RSD Bias*** < Accuracy****(%) Refrigeration Mean * SD RSD Bias < Accuracy 8 15 * P> 0.05 * Data on day 1 w ere used as reference value( A ) *** Bias = ( V alue meas ured on each time) - A A **** A ccuracy(% ) = Bias + 2(RSD) (Short term exposure limits : ST EL) 30 (Cassinelli et al, 1987). 0.1 /min /min. (1996) n- hexane

11 T able 7. Reverse diffusion of formaldehyde in diffusive sampler (N=3) Sampling time (min) Item (unit) A (A) B 30 Mean( ) * SD RSD Bias < 0.01 Accuracy(%) Mean * SD RSD Bias 0.01 Accuracy(%) Mean * SD RSD Bias 0.01 Accuracy(%) 9 A : Without expos ure, formaldehyde vapors w ere collected for 30 minutes and for tw o and four hours and immediately analyzed. B : With exposure, formaldehyde vapors w ere collected for 30 minutes and for tw o and four hours and the samplers were expos ed to clean air for three hours to evaluate revers e diffusion. * P> 0.05 ** Data on immediately w ere used as reference value( A ) *** Bias = ( V alue measured on each time) - A A **** A ccuracy(% ) = Bias + 2( RSD) 100 /min 2. (R) , Levin (1986) , 0.5, 0.11ppm, 0.27ppm, 0.29ppm(, 1996).. (P< 0.01), 2 (P< 0.01)

12 . Smith 0.85ppm 0.52ppm, 1.16ppm 1.02ppm (Smith et al, 1983) 7 2.5%, 1% (P> 0.05). 3M %. SKC 100 5%, Gilian % (, 1996).,, (Cassinelli et al, 1987). T able 7 30, 2, %.. 2, 2.,.,... DNP 37.,,,,,, % 100% /min 61.8 /min. 3. (R2) , (2 ),, NIOSH

13 . REFERENCES. 1996;93 :45 46.,, ,,,..

14 (NMAM), 4th ed, Method No Ohio : NIOSH, Ness S A. Air Monitoring for T oxic Exposures : Palmes E D, Burton R M, Ravishankar K, Solomon J J. A sampler mathematical model for diffusional sampler operation. Am. Ind. Assoc. J ; 47 : Rose V E and Perkins J L. Passive dosimetry state of the art review. Am. Ind. Assoc. J ; 43 : Smith D L, Michele Bolyard, E R Kennedy. Instability of formaldehyde air samples collected on a solid sorbent. Am. Ind. Assoc. J. 1983;44: T ompkins F C and R L Goldsmith. A new personal dosimeter for monitoring of industrial pollutants. Am. Ind. Assoc. J ; 38 : Yao C, Krueger D. A multipurpose industrial hygiene controlled atmosphere testing chamber. Am. Ind. Assoc. J ; 54 :

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