本研究運用 HPLC-Flu.分析 PAHs 能夠達到比 GC/MS 更高的感度
，並且能快速的完成分析，能夠達到有效減少廢液的產生。
透過以毒性當量的方法所建立出來的毒性當量表，所評估出來的健 康風險值，能了解到學校週遭民眾的健康風險情形，雖然評估的結果都在 一般民眾所能接受 10-6 以下，且近幾年的結果中健康風險值也有降低的趨 勢，雖然如此仍需要密切的對大氣環境進行監測調查，才能了解空氣品質 的變化並且適時的對大眾提出警訊。
5-2 研究限制
本研究限制為:
健康風險評估的結果計算，並未包含全部的PAHs。
5-3 應用與建議
本研究團隊從1990 年開始一直到現在，秉持著對環境的重視，每年固 定在冬季，都會進行大氣中PAHs 的採樣，透過研究的過程、研發更方便、
更快速的分析技術，另一方面也找出對環境衝突最小的方法，希望透過本 研究的歷程，建立出一套簡便、快速的分析方法。
大氣環境的變化，與民眾的健康息息相關，建議政府部門能訂立一套 毒性當量表，並增加環境中 PAHs 的公告系統，以方便民眾了解該地區的 PAHs 的情形。
Table 1 Proposed toxic equivalency factors (TEFs) for individual PAHs
Compound Clement
（1986）
Chu and Chen(1984)
EPA (1984)
Nisbet and LaGoy(1992）
Malcolm and Dobson（1994）
Kalberlah et al.（1995）
McClure and Schoeny（1995）
Table 2 The nomenclatures and the acronyms of 21 PAHs
nomenclatures acronyms
Naphthalene Nap
Acenaphthylene AcPy
Acenaphthene AcP Fluorene Flu Phenanthere PA Anthracene Ant Fluoranthene FL
Pyrene Pyr Cyclopentata(c,d)pyrene CYC
Benzo(a)anthracene BaA
Chrysene CHR Benzo(b)fluoranthene BbF
Benzo(k)fluoranthene BkF Benzo(e)pyrene BeP Benzo(a)pyrene BaP
Perylene PER Indeno(1,2,3-cd)pyrene IND
Dibenzo(a,h)anthracene DBA Benzo(b)chrycene BbC Benzo(ghi)perylene BghiP
Coronene COR
Table 3 Basic characters of selected PAHs
acronym Vapour pressure
（㎜ Hg） CAS No. molecular weight
chemical formula
chemical structure formula
fusion point
（℃）
boiling point
（℃）
IARC classification
Pyr 2.5×10-6 129-00-0 202 C16H10 156 406 Group 3
BkF 9.6×10-11 207-08-9 252 C20H12 217 481 Group 2B
BaP 5.6×10-9 50-32-8 252 C20H12 177 496 Group 2A
B(ghi)P 1.0×10-10 191-24-2 276 C22H12 278 542 Group 3
DB(a,e)P _ 92-65-4 302 C24H14 _ _ Group 2B
- : Not available
Table 4 Evaluations classified by group of IARC
Group 1: The agent (mixture) is carcinogenic to humans. The exposure circumstance entails exposures that are carcinogenic to humans.
Group 2A: The agent (mixture) is probably carcinogenic to humans. The exposure circumstance entails exposures that are probably carcinogenic to humans.
Group 2B: The agent (mixture) is possibly carcinogenic to humans. The exposure circumstance entails exposures that are possibly carcinogenic to humans.
Group 3: The agent (mixture, or exposure circumstance) is not classifiable as to carcinogenicity in humans.
Group 4: The agent (mixture, exposure circumstance) is probably not carcinogenic to humans.
(data from:http://monographs.iarc.fr/monoeval/grlist.html)
Table 5 Wavelengths for fluorometric detection of PAHs
Excitation: EX Emission: EM narometer: nm
Compound EX(nm) EM(nm)
Pyr 331 390
B(k)F 370 406
B(a)P 370 406
B(ghi)P 367 410
DB(a,e)P 306 398
Table 6 Apparatus and operating condition for PAHs analysis
HPLC Shimadzu system Pump：LC-9A
System controller：SCL-10A auto injector：SIL-10A
Detector Fluorescence RF-10AXL
Column Kaseisorb LC ODS SUPER 2.0mm×150mm Inject vol. 10µl
Mobile phase Acetonitrile/H2O(75/25, v/v) Flow rate 0.6ml/min
Column temp. 30℃
Analysis time 13min
Table 7 Individual calibration and R2 of PAHs
Compound Conc.(ng/ml) Equation R2
Pyr 0.02~1.30 Y=1976246x+41444 0.9991 B(k)F 0.03~2.67 Y=152932x+101255 0.9995 B(a)P 0.06~4.83 Y=466755x+98520 0.9993 B(ghi)P 0.03~2.39 Y=97401X+137909 0.9956 DB(a,e)P 0.01~0.71 Y=129034X+165664 0.9996
Table 8 Reproducibility of retention time, peak area and peak height of PAHs by HPLC
Pyr B(K)F B(a)P B(ghi)P DB(a,e)P Retention
time
（CV％） 0.9 0.8 0.5 0.2 0.2
Peak area
（CV％） 5.7 2.4 8.6 9.1 5.8
Peak height
（CV％） 5.2 10 9.2 7.3 3.1
CV％: coefficient of variation n=7
Table 9 The detection limit of PAHs
standard deviation：S.D CV％: Coefficient of variation L.O.D: limit of detection n=7
Compound Conc.
(pg/ml) Peak area S.D CV％ L.O.D (pg) Pyr 16.03 33482.43 1933.67 5.78 0.03 B(k)F 32.92 45771.86 1104.12 2.41 0.02 B(a)P 14.82 107915.60 9353.77 8.67 0.04 B(ghi)P 29.32 120322.00 11018.57 7.33 0.08 DB(a,e)P 8.78 361598.14 21184.85 5.86 0.01
Table 10 Reproducibility of QC of PAHs by HPLC
Pyr B(K)F B(a)P B(ghi)P DB(a,e)P Retention
time
（CV％） 0.2 0.2 0.8 0.2 0.2
Peak area
（CV％） 1.9 3.0 3.2 6.4 16.6
Peak height
（CV％） 2.2 4.5 2.5 5.4 14.5
QC : Quality Control
CV％: Coefficient of variation n=5
Table 11 Geometric mean concentrations and ratio assessments of individual PAHs
Year Pyr B(k)F B(a)P B(ghi)P DB(a,e)P B(a)P B(ghi)P
1990 1.23 2.15 3.36 5.92 0.82 0.57 1991 1.05 1.73 2.65 5.04 0.77 0.53 1992 1.15 1.38 2.45 4.68 0.58 0.52 1993 0.20 0.27 0.91 1.78 - 0.51 1994 0.59 1.29 3.05 8.00 0.71 0.38 1995 0.16 0.64 0.55 1.36 0.55 0.40 1998 0.76 1.24 1.08 3.65 0.31 0.30 1999 0.45 0.87 0.95 1.73 0.39 0.55 2000 0.28 0.88 0.97 2.24 0.30 0.43 2001 0.94 1.40 0.14 3.28 N.D 0.04 2002 1.43 0.28 0.19 0.60 N.D 0.32 2003 0.96 0.26 0.18 0.61 N.D 0.30 2004 0.18 0.33 0.45 1.54 0.06 0.29
＊ concentration unit:ng/m3,air
＊ ND: non-detected
＊ _: no data
Table 12 PAHs concentrations and cancer risk assessment based on B(a)P,1990-2004
＊ concentration unit:ng/m3,air
Year Pyr B(k)F B(a)P B(ghi)P DB(a,e)P RISK ASSESSMENT 1.25(hours)
1990 1.23 2.15 3.36 5.92 0.82 4.69E-09 1991 1.05 1.73 2.65 5.04 0.77 3.70E-09 1992 1.15 1.38 2.45 4.68 0.58 3.42E-09 1993 0.20 0.27 0.91 1.78 - 1.27E-09 1994 0.59 1.29 3.05 8.00 0.71 4.26E-09 1995 0.16 0.64 0.55 1.36 0.55 7.67E-10 1998 0.76 1.24 1.08 3.65 0.31 1.51E-09 1999 0.45 0.87 0.95 1.73 0.39 1.33E-09 2000 0.28 0.88 0.97 2.24 0.30 1.35E-09 2001 0.94 1.40 0.14 3.28 - 1.95E-10 2002 1.43 0.28 0.19 0.60 - 2.65E-10 2003 0.96 0.26 0.18 0.61 - 2.51E-10 2004 0.18 0.33 0.45 1.54 0.06 6.28E-10 average 0.72 0.98 1.30 3.11 0.50 1.82E-09
Table 13 PAHs concentrations and cancer risk assessment based on B(a)Peq, 1990-2004
Year Pyr B(k)F B(a)P B(ghi)P DB(a,e)P B(a)P(eq) RISK ASSESSMENT 1.25(hours)
1990 1.23 2.15 3.36 5.92 0.82 4.46 6.22E-09 1991 1.05 1.73 2.65 5.04 0.77 3.64 5.08E-09 1992 1.15 1.38 2.45 4.68 0.58 3.22 4.49E-09
1993 0.20 0.27 0.91 1.78 _ 0.96 1.33E-09
1994 0.59 1.29 3.05 8.00 0.71 3.97 5.54E-09 1995 0.16 0.64 0.55 1.36 0.55 1.18 1.64E-09 1998 0.76 1.24 1.08 3.65 0.31 1.55 2.16E-09 1999 0.45 0.87 0.95 1.73 0.39 1.44 2.02E-09 2000 0.28 0.88 0.97 2.24 0.30 1.38 1.93E-09
2001 0.94 1.40 0.14 3.28 _ 0.31 4.38E-10
2002 1.43 0.28 0.19 0.60 _ 0.23 3.14E-10
2003 0.96 0.26 0.18 0.61 _ 0.21 2.97E-10
2004 0.18 0.33 0.45 1.54 0.06 0.56 7.79E-10 average 0.72 0.98 1.30 3.11 0.50 1.93 2.69E-09
＊ concentration unit:ng/m3,air
Table 14 Monitoring station of
PSI>100
statistics in 2004
data from:（http://www.tcepb.gov.tw/）
m : month
Station Pollutant indx 1m. 2m. 3m. 4m. 5m. 6m. 7m. 8m. 9m. 10m. 11m. 12m. sum O3 0 0 0 0 0 0 0 0 0 0 2 0 2 PM10 0 6 0 0 0 1 0 0 0 0 3 3 13 Jhongming
station
Subtotal 0 6 0 0 0 1 0 0 0 0 5 3 15 O3 0 1 0 3 1 0 0 1 0 0 2 0 8 PM10 0 4 0 0 0 1 1 0 0 0 5 3 14 Situn
station
Subtotal 0 5 0 3 1 1 1 1 0 0 7 3 22
Sum 0 11 0 3 1 2 1 1 0 0 12 6 37
Table 15 Concentrations of airborne particless PAHs in individual environment and risk assessment
location Pry B(k)F B(a)P B(ghi)P DB(a,e)P Risk assessment (Thomas et al., 1996)
Carbon anode production 2.27 100.35 1154.60 8.41 - 8.15E-02 Graphite production 0.33 7.37 83.37 0.98 - 5.89E-03
Silicon carbide
production 0.06 1.54 35.57 0.41 - 2.50E-03 Bitumen paving work 0.15 4.50 14.28 0.76 - 1.03E-03 Metal recycling process 0.43 0.77 9.80 0.06 - 6.94E-04 (Yang et al., 2002)
Steel and iron industries
- Coke 10000.00 530.00 280.00 1890.00 - 9.46E-02 Steel and iron industries
- Heavy oil 6420.00 120.00 550.00 310.00 - 8.45E-02 Steel and iron industries
- Electricity 14400.00 290.00 300.00 1340.00 - 1.25E-01 (Pleil et. al, 2004)
Top floor in the school 0.09 0.14 0.09 0.19 - 6.27E-07
＊ concentration unit:ng/m3,air
(Tsai et al., 2004) -
highway toll station workers
- dayshift 134.00 124.00 121.00 59.90 26.90 1.22E-02 highway toll station workers
- nightshift 96.90 56.40 118.00 35.60 24.90 1.11E-02 highway toll station workers
- late-nighshift 67.50 61.40 105.00 16.00 16.80 8.97E-03 (Fang et al., 2004)
Taichung Industrial park 119.50 10.90 8.70 3.00 - 6.96E-04 Background(Tungghai
University) 34.60 4.00 4.60 2.70 - 3.54E-04 (This study, 2004)
roadside dormitory in top
floor 0.18 0.33 0.45 1.54 0.06 7.79E-10
0
Fig. 1 Main cancer mortality rate tendency of men in Taiwan (data from :http://www.doh.gov.tw/statistic/)
1983 1994 2003 year 1983 1994 2003 year
0
Fig. 2 Main cancer mortality rate tendency of women in Taiwan (data from :http://www.doh.gov.tw/statistic/)
1983 1994 2003 year 1983 1994 2003 year
174 183
219 204
248 231
0 50 100 150 200 250 300
1998 1999 2000 2001 2002 2003
year
number
Fig. 3 Lung cancer statistics in Taichung city（data from : http://www.doh.gov.tw/statistic）
Fig. 4 Extraction procedure of PAHs in airborne
particlessFilter 13.5 ㎜ φ × 2
CH3CN 3ml
Ultrasonic ext. 20'
Centrifuge 3000 rpm 10'
HPLC
mv
minute
0 5 10 15
0 50 100 150 200 250 300 350 400 450 500
Pyrene
BkF BaP
BghiP
DB(a,e)P
Fig. 5 HPLC chromatograms of airborne particless extracts
pyrene y = 197624.6049 x + 41444.5217
b(ghi)p y = 97401x + 137909
R2 = 0.9956
db(ae)p y = 129034x + 165664
R2 = 0.9996
Fig. 6 Individual calibration curve of PAHs
0 0.5 1
1990 1991 1992 1993 1994 1995 1996 1999 2000 2001 2002 2003 2004
year
R atio
Fig. 7 The trend of B(a)P to B(ghi)P ratio in airborne particless of winter sample,1990-2004, Taichung.
B(a)P
0 1 2 3 4
1990 1991 1992 1993 1994 1995 1998 1999 2000 2001 2002 2003 2004 year
conc .( ng/ m
3,a ir )
Fig. 8 B(a)P concentrations in airborne particless of winter sample, 1990-2004, Taichung.
pyr
0 0.2 0.4 0.6 0.8 1 1.2 1.4
1990 1991 1992 1993 1994 1995 1998 1999 2000 2001 2002 2003 2004 year
conc .( ng/ m
3,a ir )
Fig. 9 Pyrene concentrations in airborne particless of winter sample, 1990-2004, Taichung.
B(k)F
0 0.5 1 1.5 2 2.5
1990 1991 1992 1993 1994 1995 1998 1999 2000 2001 2002 2003 2004 year co nc .( n g/ m
3,a ir )
Fig.10 B(k)F concentrations in airborne particless of winter sample, 1990-2004, Taichung.
B(ghi)P
0 2 4 6 8 10
1990 1991 1992 1993 1994 1995 1998 1999 2000 2001 2002 2003 2004 year
co nc .( ng/ m
3,a ir )
Fig. 11 B(ghi)P concentrations in airborne particless of winter sample, 1990-2004, Taichung.
DB(a,e)P
0 0.2 0.4 0.6 0.8 1
1990 1991 1992 1994 1998 1998 1999 2000 2001 2002 2003 2004
year
conc .( ng/ m
3,a ir )
Fig. 12 DB(a,e)P concentrations in airborne particless of winter sample, 1990-2004, Taichung.
0 2 4 6 8 10
1990 1991 1992 1993 1994 1995 1998 1999 2000 2001 2002 2003 2004
year
Conc.(ng/m3 ,air)
pyrene B(k)F B(a)P B(ghi)P DB(a,e)P
Fig. 13 PAHs concentrations in airborne particless of winter sample, 1990-2004, Taichung.
B(a)P
0 1 2 3 4
1990 1991 1992 1993 1994 1995 1998 1999 2000 2001 2002 2003 2004 year
conc .( n g /m
3,ai r)
Fig. 14 Annual cancer risk for resident, based on B(a)P concentration in 1990-2004, Taichung
B(a)Peq
0.00E+00 1.00E-09 2.00E-09 3.00E-09 4.00E-09 5.00E-09 6.00E-09 7.00E-09
1990 1991 1992 1993 1994 1995 1998 1999 2000 2001 2002 2003 2004
year
ri sk
Fig. 15 Annual cancer risk for resident, based on B(a)Peq concentration in 1990-2004, Taichung
0.00E+00 1.00E-09 2.00E-09 3.00E-09 4.00E-09 5.00E-09 6.00E-09 7.00E-09
1990 1991 1992 1993 1994 1995 1998 1999 2000 2001 2002 2003 2004
year
ri sk
B(a)Peq B(a)P
Fig.16 Annual comparison in cancer risk between B(a)P and B(a)Peq,1990-2004,Taichung
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