(PCB) 1 ng/l (µg/kg, wet) (µg/kg) 10 (0.01) 1 (0.001) 1 (0.001) 10 (0.01) 1 (0.001) 1 (0.001) 10 (0.01) 1 (0.001) 1 (0.001) 10 (0.01) 1 (0.001) 1 (0.001) 10 (0.01) 1 (0.001) 1 (0.001) 10 (0.01) 1 (0.001) 1 (0.001) 10 (0.01) 1 (0.001) 1 (0.001) 10 (0.01) 1 (0.001) 1 (0.001) 10 (0.01) 1 (0.001) 1 (0.001) 10 (0.01) 1 (0.001) 1 (0.001) MS GC/MS-SIM 1M KOH GC/MS-SIM Wellington Laboratories BP-WD Wellington Laboratories BP-MS KC-300 KC-400 KC-500, KC-600 100mg/L 400mg/L I-1
Wellington Laboratories BP-WD PCB PCB Congener IUPAC No. 2- Chlorobiphenyl 1 4-Chlorobiphenyl 3 2,6-Dichlorobiphenyl 10 4,4'-Dichlorobiphenyl 15 2,2',6-Trichlorobiphenyl 19 3,4,4'- Trichlorobiphenyl 37 2,2',6,6'-Tetrachlorobiphenyl 54 3,3',4,4'- Tetrachlorobiphenyl 77 2,2',4,6,6'-Pentachlorobiphenyl 104 3,3',4,4',5- Pentachlorobiphenyl 126 2,2',4,4',6,6'-Hexachlorobiphenyl 155 3,3',4,4',5,5'- Hexachlorobiphenyl 169 2,2',3,4',5,6,6'-Heptachlorobiphenyl 188 2,2',3,4,4',5,5'- Heptachlorobiphenyl 189 2,2',3,3',4,4',5,5'-Octachlorobiphenyl 202 2,3,3',4,4',5,5',6-Octachlorobipheny 205 2,2',3,3',4,4',5,5',6-Nonachlorobiphenyl 206 2,2',3,3',4,5,5',6,6'- Nonachlorobiphenyl 208 2,2',3,3',4,4',5,5',6,6'-Decachlorobiphenyl 209 Wellington Laboratories BP-MS PCB PCB Congener IUPAC No. Monochlorobiphenyl 1, 3 Dichlorobiphenyl 4, 8, 10, 15 Trichlorobiphenyl 18, 19, 22, 28, 33, 37 Tetrachlorobiphenyl 44, 49, 52, 54, 70, 74,77, 81 Pentachlorobiphenyl 87, 95, 99, 101, 104, 105, 110, 114, 118, 119, 123, 126 Hexachlorobiphenyl 128, 138, 149, 151, 153, 155, 156, 157, 158, 167, 168, 169 Heptachlorobiphenyl 170, 171, 177, 178, 180, 183, 187, 188, 189, 191 Octachlorobiphenyl 194, 199, 201, 202, 205 Nonachlorobiphenyl 206, 208 Decachlorobiphenyl 209 Wellington Laboratories MBP-CG I-2
Wellington Laboratories MBP-CG 13 C PCB PCB Congener IUPAC No. 4-Chloro[13C12]biphenyl 3 4,4'- Dichloro[13C12]biphenyl 15 2,4',5- Trichloro[13C12]biphenyl 31 2,2',5,5'- Tetrachloro[13C12]biphenyl 52 2,3',4,4',5- Pentachloro[13C12]biphenyl 118 2,2',4,4',5,5'- Hexachloro[13C12]biphenyl 153 2,2',3,4,4',5,5'- Heptachloro[13C12]biphenyl 180 2,2',3,3',4,4',5,5'- Octachloro[13C12]biphenyl 194 2,2',3,3',4,4',5,5',6- Nonachloro[13C12]biphenyl 206 2,2',3,3',4,4',5,5',6,6'- Decachloro[13C12]biphenyl 209 d12 1000 m 700 2 ODS Sep-Pak Plus Silica Cartridge (690 mg) ( aters ) 10ml 60 80 96% 1M KOH 1M 5% C-200 130 15 95g 300ml 5ml 30 15 I-3
30cm 10mm 5g 2cm 40ml GC/MS MS MS 1L 2L 10ml 30g 10ng 100ng 100ml 10 50ml 200ml 200ml 30 1ml 20g 200ml 10ng 100ng 1M KOH 50ml 80 50ml (GF/A) 20ml 30ml I-4
300ml 50ml 10 20ml 300ml 50ml 300ml 50ml 300ml 50ml 200ml 200ml 30 3ml 10ml 10ml 1ml 100ng 50ml 30 3ml 1ml 100ng 10mg I-5
100ml 100 g/ml 20 HT8 30 0.25 m 5% DB-5MS Ultra2 SGE 70 2 30 170 5 300 10 1.5 0.25 250 40cm/sec He 70 I-6
4-Chloro[13C12]biphenyl 4,4'- Dichloro[13C12]biphenyl 2,4',5- Trichloro[13C12]biphenyl 2,2',5,5'- Tetrachloro[13C12]biphenyl 2,3',4,4',5- Pentachloro[13C12]biphenyl 2,2',4,4',5,5'- Hexachloro[13C12]biphenyl 2,2',3,4,4',5,5'- Heptachloro[13C12]biphenyl 2,2',3,3',4,4',5,5'- Octachloro[13C12]biphenyl 2,2',3,3',4,4',5,5',6- Nonachloro[13C12]biphenyl 2,2',3,3',4,4',5,5',6,6'- Decachloro[13C12]biphenyl d 12 264.2 5% 70 (1.9min)--8 /min--300 (15min) I-7
4-Chloro[13C12]biphenyl 4,4'- Dichloro[13C12]biphenyl 2,4',5- Trichloro[13C12]biphenyl 2,2',5,5'- Tetrachloro[13C12]biphenyl 2,3',4,4',5- Pentachloro[13C12]biphenyl 2,2',4,4',5,5'- Hexachloro[13C12]biphenyl 2,2',3,4,4',5,5'- Heptachloro[13C12]biphenyl 2,2',3,3',4,4',5,5'- Octachloro[13C12]biphenyl 2,2',3,3',4,4',5,5',6- Nonachloro[13C12]biphenyl 2,2',3,3',4,4',5,5',6,6'- Decachloro[13C12]biphenyl d 12 264.169 GC/MS GC/MS I-8
p,p'-ddt 1mg/L 1 L GC/MS DDT DDD DDE 20% DDT 20% cm SIM (RF) RF RF 15% RF 15% RF 15% RF RF=(As Cis)/(Ais Cs) As Ais Cis (ng) Cs (ng) KC-300 KC-600 (Cs ng) (ng) = (ng) 0.01 100mg/L KC-300 KC-600 1 BZ#1 BZ#1 (ng) = 100ng 0.1856 0.01 = 0.1856ng GC/MS SIM RF 8 RF RF 15% GC/MS RF I-9
PCB PCB window (5% phenyl methyl siloxane) PCB IUPAC #1, #3, #10, #15, #19, #37, #54, #77, #104, #126, #155, #169, #188, #189, #202, #205, #206, #208, #209 GC 5% phenyl methyl siloxane 4 4 2,2,6,6 - (IUPAC : #54) PCB 3,3,4,4 - (IUPAC : #77) GC PCB PCB 5 20% PCB SGE HT8 PCB PCB PCB (M-70) 5 20% PCB PCB PCB RF PCB Wellington Laboratories BP-MS BP-MS RF KC-300 KC-600 PCB PCB KC-300 KC-600 I-10
RF (ng) (ng)=(as Cis)/(Ais RF) As Ais Cis (ng) 10 50% 120% 80% 120% (CRM) (x) (s) (DL) DL = x + 1 943 s I-11
2 5 2 5 (s) (DL) DL = 1 943 s MS PCB ODS 1M KOH 50ml 1M KOH 100ml I-12
HPLC µbondapak NH 2, 9mm i.d. 30cm, Waters (LC-NH 2 ) PCB 5% 400 5 10g MS HPLC PCB GC PCB KC300 KC600 M+70 PCB 5 10 JIS Z8402 1974 PCB CRM NIST SRM 1939 Wellington Laboratories CARP-1 20g WindowsPCB19 100ng -d 10 I-13
20g 100ng IUPAC PCB 1 2-93.4 96 94.7 3 4-101.9 108.1 105.0 10 2,6-72.3 95.8 84.1 19 2,2',6-54.2 68.5 61.4 15 4,4'- 96.6 101.4 99.0 54 2,2',6,6'- 42.2 46.3 44.3 104 2,2',4,6,6'- 64.4 68 66.2 37 3,4,4'- 162.5 114.1 138.3 155 2,2',4,4',6,6'- 77.3 78.6 78.0 77 3,3',4,4'- 103.3 126.1 114.7 188 2,2',3,4',5,6,6'- 75.4 79 77.2 126 3,3',4,4',5-42.9 51.4 47.2 202 2,2',3,3',5,5',6,6-77.3 102.4 89.9 169 3,3',4,4',5,5'- 59.9 51.6 55.8 189 2,3,3',4,4',5,5'- 156.6 175.2 111.1 208 2,2',3,3',4,5,5',6,6'- 60 80.4 70.2 205 2,3,3',4,4',5,5',6-145.5 93.7 119.6 206 2,2,',3,3',4,4',5,5,6-78.7 86.6 82.7 209 2,2',3,3',4,4',5,5,6,6'- 45.9 82.2 64.1 20g 100ng IUPAC PCB 1 2-69 69.2 69.1 3 4-76 93.2 84.6 10 2,6-83.8 82.2 83.0 19 2,2',6-96.3 90.2 93.3 15 4,4'- 83.2 87.1 85.2 54 2,2',6,6'- 90.1 84.4 87.3 104 2,2',4,6,6'- 56.7 60.5 58.6 37 3,4,4'- 100 83.1 91.6 155 2,2',4,4',6,6'- 77.1 74.6 75.9 77 3,3',4,4'- 77.3 82.1 79.7 188 2,2',3,4',5,6,6'- 78 75.2 76.6 126 3,3',4,4',5-91.3 93.1 92.2 202 2,2',3,3',5,5',6,6-58.4 57 57.7 169 3,3',4,4',5,5'- 64.6 65.7 65.2 189 2,3,3',4,4',5,5'- 53.7 59.2 56.5 208 2,2',3,3',4,5,5',6,6'- 64.8 69.8 67.3 205 2,3,3',4,4',5,5',6-79.7 74 76.9 206 2,2,',3,3',4,4',5,5,6-67.2 65.3 66.3 209 2,2',3,3',4,4',5,5,6,6'- 74.2 73.9 74.1 I-14
1997 4,4'- 1997 JIS Z8402 1974 WHO 1994 Analytical Chemistry of PCBs, M. D. Erickson, Butterworth Publishers, 1986. Polychlorinated biphenyls in the environment, V. Lang, J. Chromatogr., 595, 1-43, 1992. Mass Spectrometric Determination of Polychlorinated Biphenyls as Isomer Groups, J. E. Gebhart, T. L. Hayes, A. L. Alford-Stevens and W. L. Budde, Anal. Chem., 57, 2458-2463, 1985. Determination of Byproduct Polychlorobiphenyls in Commercial Products and Waters by High-Resolution Gas Chromatography/Electron Impact Mass Spectrometry, M. D. Erickson, J. S. Stanley, J. K. Turman, J. E. Going, D. P. Redford and D. T. Heggem, Environ. Sci. Technol, 22, 71-76, 1988. 9 Comparison of methods for the gas-chromatographic determination of PCB congeners and chlorinated pesticides in marine reference materials, M. M. Schantz, R. M. Parris, J. Kurz, K. Ballschmiter and S. A. Wise, Fresenius J. Anal. Chem., 346, 766-778, 1993. I-15
- 16
p,p -DDT p,p -DDE p,p -DDD trans- cis- trans- cis- (PBB) (BaP) 25ng/L 5µg/kg GC/MS-SIM GC/MS-SIM GC/MS-SIM GC/MS-SIM (2-, 3-, 4- ) (4,4'- ) p,p'-ddt- 13 C 12 HCB- 13 C 6 BaP-d 12 -d10 -d 10 p- -d 14 1000 II-1
m ODS 96% II-2 700 2 60/100 130 16 2 5% C- 200 130 15 95g 300ml 5ml 30 15 (Atlas Powder Co. )100g 2L 1L 30 1L 130 2.5% 25g 75g 30 Sep-Pak Plus Silica Cartridge (690 mg) (Waters ) 10ml 60 80
30ml (KD) 30cm 15mm 10g 2cm 100ml 30cm 10mm 5g 2cm 40ml 30cm 10mm 2.5% 10g 30% 2cm 30% GC/MS 1L 2L 30g 10ng 100ng 50ml 10 KD 5ml 1ml 20g 100ml 10ng 100ng 50ml 10 10 3000rpm 10 5 II-3
500ml 1 50ml 5 KD 5ml BaP 40g 20ng 200ng 40ml 80ml 3000rpm 10 2 500ml 200ml KD 50ml 50ml 25ml 25ml 100ml 50ml 50ml 5ml 5 500ml 1L 50ml 300ml 100ml KD 5ml 25ml 50ml 10ml 50ml KD 5ml 2% II-4
ml KD 100ng 1000ng 1ml (Fr 1) 4 100ml(Fr 2) 15 150ml(Fr 3) 5ml Fr 1 5 10g 10g 10mm 300mm KD ml 100ng 1000ng 1ml (Fr 1) 4 100ml(Fr 2) 15 150ml(Fr 3) 5ml KD ml 100ng 1000ng 1ml 5ml KD ml 1ml 10mg 100mg/L p,p'-ddt- 13 C 12 HCB- 13 C 6 BaP-d 12 -d 10 -d 10 p- -d 14 II-5
20 GC/MS 30m 0.25mmi.d. 0.25 m 0.25mmi.d. 40cm 250 300 40cm 250 280 5% 50 (1 ) 10 1 1 L 280 15m 0.25mmi.d. 0.10 m 15m 50 (1 ) 10 1 1 L 280 70eV EI SIM 1 2 II-6
(PTRI, Programmed Temperature Retention Index) PTRI No CAS RN * 319-84-6 1700 180.9 218.9 182.9 319-85-7 1748 180.9 218.9 182.9 58-89-9 1767 180.9 218.9 182.9 319-86-8 1822 180.9 218.9 182.9 p,p -DDT 50-29-3 2361 235.0 237.0 165.1 p,p -DDE 72-55-9 2185 246.0 317.9 316.9 p,p -DDD 72-54-8 2275 235.0 237.0 165.1 72-43-5 2487 227.1 228.1 115-32-2 2473 139.0 250.0 111.0 309-00-2 1983 262.9 264.9 66.0 60-57-1 2200 79.0 262.9 276.8 72-20-8 2245 262.9 81.0 264.9 959-98-8 2142 195.0 240.9 338.9 33213-65-9 2270 195.0 240.9 338.9 76-44-8 1910 271.8 100.0 273.8 1024-57-3 2064 352.8 354.8 81.0 trans- 5103-74-2 2113 374.8 372.8 236.8 cis- 5103-71-9 2140 374.8 372.8 236.8 27304-13-8 115.0 386.8 236.8 trans- 39765-80-5 2146 408.8 406.8 410.8 cis- 5103-73-1 2302 408.8 406.8 410.8 (HCB) 118-74-1 1705 283.8 285.8 248.8 29082-74-4 379.7 377.7 381.7 50-32-8 2920 252.1 * PTRI n- 5% 234.0 152.1 232.0 311.9 309.9 313.9 389.8 391.8 230.0 469.7 467.7 471.7 547.6 549.6 387.8 627.5 625.5 629.5 623.5 621.5 625.5 II-7
No p,p'-ddt- 13 C 12 247.0 249.0 177.1 HCB- 13 C 6 289.8 291.8 283.8 -d 12 264.2 -d 10 188.1 -d 10 212.1 p- -d 14 244.2 GC/MS GC/MS p,p'-ddt (DFTPP) 1mg/L 1 L GC/MS DDT DDD DDE 20% DDT 20% cm MS DFTPP 3 DFTPP SIM II-8
(RF) (RF) RF RF 15% RF 15% RF 15% RF RF=(As Cis)/(Ais Cs) As Ais Cis (ng) Cs (ng) 1 GC/MS SIM RF p,p'-ddt- 13 C 12 DDD DDE 20% 20% 8 RF RF 15% GC/MS RF 5 20% II-9
RF RF (ng) (ng)=(as Cis)/(Ais RF) As Ais Cis (ng) 10 80% 120% 80% 120% NIST EU BCR CRM (CRM) CRM II-10
(x) (s) (DL) DL = x + 1 943 s 2 5 2 5 (s) (DL) DL = 1 943 s (5ml) 2 g 5ml 20ml GC/MS p,p'-dde p,p'-ddt p,p'-dde 4% 100ml p,p'-ddt 15% 150ml BaP ODS II-11
15 30 GC/MS 30% Fr.3 Fr.3 5% 10ml 5% (5g) : 10ml Hexane 5% Acetone-Hexane 30% Acetone-Hexane Fr.1-1 Fr.1-2 Fr.1-3 Total Fr.2-1 Fr.2-2 Fr.2-3 Total Fr.3-1 Fr.3-2 Fr.3-3 Total 74 25 1 99 1 0 0 1 0 0 0 0 BaP 0 0 1 1 86 12 0 99 0 0 0 0 α-hch 0 0 0 0 2 71 27 100 0 0 0 0 β-hch 0 0 0 0 0 0 99 99 1 0 0 1 γ-hch 0 0 0 0 0 0 100 100 0 0 0 0 δ-hch 0 0 0 0 0 0 98 98 2 0 0 2 0 97 2 99 1 0 0 1 0 0 0 0 0 99 1 99 1 0 0 1 0 0 0 0 0 0 0 0 0 0 100 100 0 0 0 0 0 0 3 3 82 14 0 97 0 0 0 0 0 0 33 33 65 2 0 67 0 0 0 0 0 0 0 0 0 1 99 100 0 0 0 0 0 1 91 92 7 0 0 8 0 0 0 0 0 98 1 99 1 0 0 1 0 0 0 0 0 0 0 0 0 0 100 100 0 0 0 0 0 0 0 0 0 0 100 100 0 0 0 0 0 0 0 0 0 0 87 87 13 0 0 13 0 0 1 1 29 59 11 99 0 0 0 0 0 19 79 98 2 0 0 2 0 0 0 0 0 0 0 0 0 0 100 100 0 0 0 0 (Fr 1) II-12
15 150ml 209 RF %RSD 15% DDT HCB 13 C BaP 80% 120% 5 10 JIS Z8402 1974 CRM ( NIST SRM 1588) (EU BCR CRM 187, CRM 188) (EU BCR CRM 430) CRM 20g II-13
Compound µ µ Hexachlorobenzene 96 6.2 0.019 * alpha-hch 83.0 6.0 0.019 48 0.57 1.9 beta-hch 85.6 6.9 0.022 55 0.87 2.9 gamma-hch 85.4 7.2 0.022 delta-hch 84.1 6.5 0.021 Heptachlor 91.1 6.6 0.021 Aldrin 83.6 6.1 0.019 Heptachlor 92.9 6.8 0.021 epoxide Oxychlordene 91.9 9.2 0.029 trans-chlordane 93.6 6.9 0.022 60 0.1 0.34 cis-chlordane 94.4 5.4 0.017 152 0.15 0.49 Endosulfan I 84.3 7.1 0.022 trans-nonachlor 92.4 6.9 0.022 139 0.2 0.7 4,4'-DDE 86.4 5.7 0.018 58 0.6 2 Dieldrin 92.9 7.4 0.023 74 1.4 4.8 Endrin 97.6 5.9 0.019 4,4'-DDD 75.7 6.7 0.021 * cis-nonachlor 84.9 5.8 0.018 Endosulfan sulfate 77.6 6.3 0.020 4,4'-DDT 81.0 5.2 0.016 * Endrin ketone 71.7 6.9 0.022 Methoxychlor 82.1 5.4 0.017 Benzo(a)pyrene 98.4 8.3 0.026 * 1991 1991 1987 Standard Methods 19th ed. American Public Health Association, 1995. EPA Method 8270B, US EPA, 1994. Official Methods of Analysis of The Association of Official Analytical Chemists 15th ed. Vol. 1, Association of Official Analytical Chemists, Inc., 1990. II-14
4,4'- 1997 1989 1996 1996 JIS Z8402 1974 J.R. Chapman, Wiley 1995 WHO 152 1995 II-15
-16
4-t- 4-n- 4-n- 4-4-t- 4-n- 100ng/L 50ng/g 10ng/L 5ng/g SS SS GC/MS-SIM GC/MS-SIM GC/MS-SIM GC/MS-SIM -d 8 -d 10 700 8 III-1
2cm 20cm 5 15g 2cm GC/MSGC MS L 1M ph 3 30g SS JIS-K0102 SS SS 5mL 50mL 10 0.5mL 1M ph3.5 L 5mL 10mL 0.3mL 0.2 0.3mL III-2
20g 5ml 100ml 50ml 10 10 3000rpm 10 5 500ml L 50ml 10 2 0.5ml 20g 100ml 10 3000rpm 20 300ml 3 5ml 30ml 300ml 30ml 5 500ml L 1mL 50ml 10 0.5ml 0.5mL 100ml 100ml 1ml -d 8 -d 10 1µg/ml 1ml 1ml -d 8 -d 10 g/ml ml 1mL -d 8 -d 10 g/ml ml III-3
3g 20g g 100mg 1000mg/L -d 8 -d 10 20 GC/MS GC 30m 0.25mmI.D. d f =0.25 m 60 10 280 5 280 L He 40cm 280 MS EI 70eV 250 III-4
SIM PTRI= Programmed Temperature Retention Index CAS Registry Number PTRI 4-t- 98-54-4 1306 135 107 4-n- 14938-35-3 1461 107 164 4-n- 2446-69-7 1522 107 178 4-1987-50-4 1668 107 192 4-t- 140-66-9 1614 135 107 4-n- 1806-26-4 1770 107 206 104-40-5 1669 1801 135 107 -d 8 <1200 136 -d 10 1794 188 PTRI n- L GC L GC 15 GC/MS 20 III-5
µg/ml ng ml GC L ml µg/g ng ml GC L g 100 L 130 15 95 5mL 30 15 SS Sep-Pack SP- 2 Oasis TM HLB SDB-RPS 15 30ml III-6
6 (1996) 363-373. 30-31 (1998). 74-75 (1998). III-7
2,4-10ng/L 5ng/g SS SS GC/MS-SIM GC/MS-SIM GC/MS-SIM GC/MS-SIM -d 10 N,O-bis(trimethylsilyl)trifluoroacetamide 700 8 2cm 20cm 5 III-8
15g 2cm GC/MSGC MS L 1M ph 3 30g -d 16 SS JIS-K0102 SS SS 5mL 50mL 10 0.5mL 1M ph3.5 L 9mL 10mL 0.5mL III-9
20g 5ml µg100ml 50ml 10 10 3000rpm 10 5 500ml L 50ml 10 2 0.5ml 20g µg 100ml 10 3000rpm 20 300ml 3 5ml 30ml 300ml 30ml 5 500ml L 1mL 50ml 10 0.5ml 100ml 100ml ml 15ml 1ml -d 8 -d 10 1µg/ml 1ml 0.5ml -d 10 g/ml ml 0.5mL III-10
N,O-bis(trimethylsilyl)trifluoroacetamide 200 L 0.2 0.3mL 1mL 1000mL 20g g 100mg 1000mg/L -d 10 20 GC/MS GC 30m 0.25mmI.D. d f =0.25 m 60 10 280 5 280 L He 40cm 280 MS EI 70eV 250 III-11
SIM TMS PTRI=Programmed Temperature Retention Index PTRI TMS 2230 357 372 2,4- TMS 1372 219 234 TMS 1883 323 338 TMS 371 386 -d 10 2140 212 PTRI n- ml 0.5mL L GC L GC 15 GC/MS 20 III-12
µg/ml ng ml GC L ml µg/g ng ml GC L g 100 L 16 6 8 130 15 95 5mL 30 15 SS Sep-Pack SP- 2 Oasis TM HLB SDB-RPS 15 30ml III-13
2,4- TMS TMS N,O-bis(trimethylsilyl)trifluoroacetamide -d 16 6 8 III-14
1.0mL No ph GC/MS L (30g) 1.0mL ph =3 3.5 Yes 50mL A No ph GC/MS L (30g) 0.5mL BSTFA ph =3 3.5 Yes 0.2mL 50mL
20g 20g GC/MS A 20g 20g GC/MS BSTFA
4-t- 4-n- 4-n- 4-n- 4-t- 4-n- 0.01 g/l 0.1 g/l 1.0 g/kg 10 S/N=3 g/l g/kg 4-t- 0.005 0.5 4-n- 0.01 1.0 4-n- 0.01 1.0 4-t- 0.003 0.3 4-n- 0.01 1.0 4-n- 0.01 1.0 0.03 3.0 -A 0.002 0.2 10 KOH GC/MS-SIM GC/MS-SIM 17
10 10 n- Sep-Pak Plus PS-2 Sep-Pak R Cartridges Florisil R 10ml 4ml 10ml 18
5ml 10ml 3ml 10g 100ml 30ml 10 3000rpm 10 100ml 20ml 5% 200ml 50ml 50ml 50ml 10g 100ml 30ml 10 3000rpm 10 100ml 1N-KOH 0.5ml 0.2ml 10 1N-KOH 5ml 70 8ml 0.5 g/ml 1.0ml 10ml 0.7ml 3ml 4% 1ml 4% 10ml 19
4% 8ml 0.5ml 10g g 10 g 100 g/ml 1000 g/ml 1.0 g/ml 10 g/ml a 25m 0.32mmI.D.,d=0.52 f m 5% 60 15 280 250 1.5 l He 7.5psi 250 b 70e 250 300 SIM c 20
4-t- 163 178 4-n- 192 135 4-n- 206 135 4-t- 163 135 4-n- 135 220 4-n- 234 135 177 163 -A 269 284 10 10 10 164 188 212 4-t- 4-n- 4-n- 4-t- 10 4-n- 10 10 1.0 g/ml 10 g/ml 1.0ml 10ml 1N-KOH 0.5ml 0.2ml 10 1N-KOH 5ml 8ml 0.5 g/ml 1.0ml 0.7ml l GC/MS 15% 21
15% GC/MS 20% g/l ng ml g/g ng 1000 JEOL DX-303 1/10 0.05 g/ml 3ml 2.7ml 0.1ml 1/10 2,4-22
10ml 10ml 20ml/min 0.3ml 1N KOH 23
1/10 24
10
1 ( 1) -n- * * -2- * ( 2) 2 -n- -2-0.5 g/l 0.2 g/l -n- -2-25 g/kg 10 g/kg -n- -2-10 3 GC/MS-SIM ( ) GC/MS-SIM 5 GC/MS-SIM ( ) / SIM / 5 GC/MS-SIM -1
4 4.1 ( 3) 200 2 1L ( 4) ( ) 4.2-10 4.2 5 ( 5) 5.1 1000 ( 6) -d -d -n- -d -n- -d -2- -d -d -d 4- -d -d -d -d -d -d -d PCB ( 7) 500 700 ( 8) ( 9) ( 10) 5 5 (W/V) (60/100 ) 130 16 100g -2
5.7mL 4 5 ( 99.999 ) 5.2 30cm 1cm 2g 1cm, 2 ( 11) SPC 200 2 ( 11) 200 2 ( 11) 40000 ( GPC) 8 20mm 300mm ( 12) HPLC GPC GC/MS 6 6.1 (1) ( 13) 95ml SPC 100ml( 14) ( 15) 15g( 16) 2.5ml( 17) ( 18) 1 4 ( 19) 1ml( 20) -3
GC/MS ( 21) ( 22) GPC GC/MS (2) ( )20g 100ml ( 15) ( 23)30ml 5 10 3000rpm 10 2 1/4 15ml SPC 1 5ml( 24 25) GPC ( 26) SPC 1ml ( 25) GC/MS ( 21 27) 1/4 15ml 5 100ml 300ml 25ml 40 ( 28) 10ml 1ml / 50ml( 29) (0.5 100)100ml( 30) 1ml / 40 ( 28) 10ml 1ml( 20) GC/MS ( 21 27) GC/MS (3) 20g 200ml ( 15) ( 23)30ml 2 5 3000rpm 10 1/4 15ml SPC 1 5ml( 24 25) GPC ( 26) SPC 1ml ( 25) GC/MS ( 21 27) 1/4 15ml -4
5ml 5 20ml 5 100ml 300ml 25ml 40 ( 28) 10ml (10 300mm 2g 1cm ) 1ml / 50ml( 29) (0.5 100)100ml( 30) 1ml / 40 ( 28) 10ml 1ml( 20) GC/MS ( 21 27) GC/MS 6.2 GPC ( 31) GPC ( 12) ( 32) ( 8mm Shodex AsahipakGF-310HQ 0.5 0.6ml/min) 30 6.3 6.4 ( 33) 1000mg/L GPC 100mg/L ( 0.1mg/L) 1000mg/L ( 1 10mg/L) -5-5
6.5 GC/MS (1) ( 34) 30m 0.25mmi.d. 0.25 m 5% 50 (2 ) 10 270 10 210 250 1 1 l 40cm ( ) 270 (2) EI 70V 220 280 200 ( 35) (3) (m/ ) 149 (m/ ) 177 -n- 209 209 -n- 223 237 -n- 251-2- 167 167 206 (m/ ) 153 (m/ ) 4- -d 130 -d 136 -d 164 -d 188 -d 212 -d 240 -d 264 6.6 GC 1 5 1 GC 5 6.7 ( 36) -6
1 GC 1 GC GC g/ml g/g (ng) (ml)/ ( l) 1/ (ml g) 20g 1/4 1 GC 70 130 7 10 1 1 1 10 60 8 -n- DBP DEHP 1000 PCB 1000 PCB HPLC DBP DEHP PCB DBP DEHP 1 3-7
500 700 8 10 11 500 2 Giam 320 10 500 SPC 12 Shodex AsahipakGF-310HQ 13 EPA method506 PID EPA method525.2 GC/MS 6 8 SPME 14 SPC 15 DBP DEHP (1 2 ) 16 10 15 17 Speed98' Speed98' 0.1 0.5ml 18 19 20 21-8
22 23 24 GPC 8mm GPC 1 500 8mm GPC 1 2ml 25 SPC 60 26 GPC THF 27 28 29 1 30 31 32 33 34 GC GC 35 SIM 36-9
1. 7 2. 59 3. 58 4. 56 5. 50 6.( ) ) 7. EPA:Method 8270B, US EPA 8. EPA:Method 525.2,USEPA 9. EPA:Method 506, USEPA -10
1-2- (DEHA) 2 0.01 g/l 10 g/ 3 GC/MS-SIM 5 GC/MS-SIM ( 1) / 5 GC/MS-SIM ( 1) -2- ( 2) 4 4.1 ( 3) 1L ( 4) ( ) 4.2-1
-10 4.3 5 5.1 PCB 1000 ( 5) DEHA DEHA-d8 -d10 PCB ( 6) 500 700 8 ( 7) 5 5 (w/v) 5 5 (w/v) (60/100 ) 130 16 100g 5.7ml 4 5 5.2 30cm 1cm 2g 1cm SPC SPC GC/MS -2
6 6.1 (1) ( 8) 1000ml 2L ( 9) ( 10) ( 11)50g 100ml 5 100mL 30 ( 12) 10ml 1ml( 13 14) (2) ( )20g 100ml ( 10) ( 15)50ml 5 10 3000rpm 10 2 5 500ml( 16) 1000ml 100ml 30 10ml 5ml (3) 20g 100ml ( 10) ( 15)50ml 2 5 3000rpm 10 10ml 5 20ml 5 500ml( 16) 1000ml 100ml 10 30 10ml 5ml 6.2 (1) GC/MS ( 17) GC/MS -3
(2) (10 300mm 5g 1cm ) 1ml / 50ml( 18) (1 100)100ml( 19) 1ml / 30 10ml 1ml( 14) GC/MS ( 17) ( 20) ( 21) GC/MS 6.3 6.4 ( 22) DEHA 1000mg/L (DEHA-d) 8 DEHA 100mg/L ( 0.1mg/L) ( -d 10) DEHA 1000mg/L ( 1 10mg/L) -5 6.5 GC/MS ( 23) 30m 0.25mmi.d. 0.25 m 5% 50 (2 ) 10 260 10 250 1 1 l 40cm ( ) 270 EI -4
70V 220 280 200 ( 24) (m/ ) DEHA 129(147) (m/ ) DEHA-d8 137 (m/ ) -d10 212 6.6 DEHA 1 GC DEHA 5 DEHA -d10 1 GC DEHA -d10 5 DEHA DEHA-d8 6.7 ( 25) 1 GC DEHA 1 GC DEHA -d10 GC DEHA DEHA g/ml g/g (ng) (ml)/ ( l) 1/ (ml g) 1 GC DEHA DEHA-d8 DEHA-d 8 DEHA (DEHA-d 8) ( -d 10) (DEHA-d) 8 70 130-5
7 10 1 1 1 10 60 8, -2- GPC DEHA DEHP DEHP 300 GC/MS -2-1000 500 700 8 DEHA EPA method506 PID EPA method525.2 GC/MS 1 5ml DEHA 10 11 PCB 12 K.D. 5ml 13 14 DEHA 0.25ml 15 16 68.8 81.6 5 17-6
18 1 19 DEHA 20 (10 300mm 5g 2cm ) 50ml (5 95)50ml 130 15 95g 5g 30 15 21 (10 300mm 5g 5, ) 50ml (2 98)50ml 5g 5 95g 30 G 100g 2L 1L 30 1L 1L 130 130 22 DEHA DEHA-d 8 -d10 DEHA 23 GC 270 1 24 SIM 25-7
1. 2. 55 3. 53 4. EPA:Method 8270B, US EPA 5. EPA:Method 525.2,USEPA 6. EPA:Method 506, USEPA -8
[a] (BaP) 4-0.01 g/l 1 g/kg GC/MS-SIM ( 1 3) BaP GC/MS-SIM 4- ( ) ( 4) GC/MS-SIM GC/MS-SIM GC/MS-SIM ( 5) 1 L Na 2 SO 4 100 ml 2 1 ml GC/MS 0.3 ml BaP 4- Na2SO4 GC/MS
Na2SO4 GC/MS Na2SO4 GC/MS Na2SO4 GC/MS (1) ( 6) ( 7) BaP ( 8) 4- ( 9) 1,3- (DPP) cis-1,2- (cis-dpcb) trans-1,2- (trans-dpcb) 2,4- -1- (DPB) ( 10) 2,4,6- -1- (TPH) 1- -4-(1'- ) (PPET; 4 ) 1,3,5- (TPCH) BaP-d12 -d10 -d10 1,2- -d14 d12( 11) 100 mg 100 ml BaP 100 ml 1000 g/ml 10 ml 100 ml 100 ml 1 ml 100 g ( 12) 100 mg 100 ml BaP-d12 100 ml 1000 g/ml
10 ml 100 ml 100 ml 1 ml 100 g ( 13) ( 1 cm 30 cm) 5 % ( 14) 5 g 2 cm 10 ml ( 7 mm) ( 60 80 ) 2cm ( 15) 5% NaCl 5%(W/V) 1 M 28.1 g 500 ml (2) ( 1L ) ( 1L) ( 100 300 ml) ) ( 100 300 ml) ) ( ) KD GC/MS GC MS ( 16) (1) ( ) (4 ) ( ) (2) ( ) 1 L 2 L ( 17) 50 g 100 ml 5
100 ml 5% NaCl 50 ml 5 KD 5 ml ( 18) 1 ml ( 19) ( ) (a) BaP (b) 4-20 g 1 L ( 20) ( 2) 200 ml 10 g 20 ml 10 ( 21) 20 ml 10 ( 22) KD 5 ml 1 ml (c) ( 23) 20 g ( ) 200 ml ( 2) 1 M 100 ml 1 100 ml 3000 rpm 10 5 % 400 ml 1 L 100 ml 5 100 ml 5 % 50 ml 2 KD ( 18) 5 ml 1 ml ( ) (a) BaP (b) 4-20 g 100ml ( 2) 50 ml 5 3000 rpm 10 50 ml 1 L 300 ml ( 21, 24) 10 g 20 ml 10 20 ml 10 ( 22) ( 25) KD 5 ml 1 ml ( 23)
( ) ( 5) 20 ml - (5:95 V/V) 100 ml ( 26 27) KD 5 ml 0.3 ml 10 l 1 L GC/MS ( 28) (3) (4) 0.1 5 g/ml (5) ( ) GC/MS ( 29) (a) GC 50% ( 0.2 0.75 mm 15 30 m 0.1 3.0 ) ( 30 32) 50 ( ) 20 / 300 (30 ) 250 ( 40 cm ) (1 ) (b) MS :EI 70eV 300 A 230 (c) ( 33 34) BaP 252 (250) 105 (182) 4-137 (91) DPP 92(196) cis-dpcb trans-dpcb 104 (208) DPB 91 (208) TPH 91 (207) PPET 129 (207) TPCH 104 (208) BaP-d 12 264 -d10 188 -d10 192 -d 5 128 1,2- -d14 196 -d12 240 ( ) (6) 0.3 ml 10 l 1 l GC/MS
( 26 34) (7) ( g/l) (ng) (ml) ( l) (L) 1) GC/MS [a] [e] 2-3- GC/MS SIM 2) GC/MS BaP BaP-d12 -d10 4- -d5 1,2- -d14 3) (ODS) ( 1 m 450 ) 3000 rpm 10 4) 5) PR (60 100 ) 130 15 ( ) ( FL LC- Florigil 5 10 g ) ( 1 cm
30 cm) 7 g 2 cm ( ) 6) 7) 250 450 8 8) BaP 9) 10) 11) -d8 -d10 -d10 p- -d14-13 C6 (HCB- 13 C6) 12) 13) SI (5 g) LC-Si (5 g) ( ) 14) 5 % C-200 ( ) 130 15 95 g 5 ml 30 15 15) 16) BaP 17) ( ) 3000 rpm 10 18) 30 19) 0.3 ml 10 l 20) 30 ml 21) 22) 20 g 500 ml ( 1b) 5 g 5 10 ml 90 23) BaP 24) 100 ml 300 ml 25) 26) -
(5:95 V/V) 27) GC/MS 28) 29) GC 270 30) DB-17 TC-17 HP-50+ SPB-50 ( ) 31) PET DB-WAX ( ) 32) PET DB-1 HP-1 DB-5 HP-5 ( ) 33) 11 -d 8 136 -d10 176 -d10 188 p- 14 244 HCB- 13 C6 290 34) BaP BaP-d12 -d10 4- -d5 1,2- -d14 d10 d 12 1) 1 (1995). 2 (1991). 3 63 (1989). 4 55 (1981). 5 EPA: Method 8270B, US EPA. 6 EPA: Method 525, US EPA. 7 39, 110-119 (1998). 8.
1,2- -3- (DBCP) n- 0.01 g/l 1 g/kg GC/MS-SIM ( 1 3) GC/MS NaCl GC/MS NaCl (1) 105 3 ( 4) DBCP n- ( 5) 30 50 ml 100 ml DBCP n- 100 mg 100 ml ( 6) 50 90 ml 100 ml 4-100 mg 100 ml ( 7) 50 80 ml 100 ml 10 ml 100 ml (2) 50 250 ml 50 250 ml 105 3 50 ml 105 3
(10 100 ml) 10 30 ( 8) ( 9) 105 3 ( 10 11) GC/MS GC MS (1) ( ) (4 ) ( ) (4 ) ( 12) (2) ( ) ( 13) 10 100 ml 1 l ( ) 20 g 3000 rpm 20 10 ml 10 3000 rpm 10 10 ml 10 3000 rpm 10 (25 50 ml) ( 13) 9.4 ml 0.6 ml 9.4 94 ml 0.6 6 ml ( 14) 1 l ( ) 20 70 30 120 GC/MS ( 15) (3)
(4) 10 ml 1 10 ml (100 g/ml) 1 50 g/ml (5) ( ) ( 16) 10 psi 140 150 0.01 0.05 0.1 ( ) GC-MS (a) GC ( 0.2 0.75 mm 25 120 m 0.1 3.0 m ) ( 17) 35 (3 ) 10 / 230 (7 ) 200 ( 40 cm/ ) (1 ) (b) MS EI 70eV 300 A 230 (c) DBCP 75 (157) 104 (78) n- 134 (91) 4-174 ( ) (6) 0.02 50 g/l ( 18) 1 l GC/MS (7) ( g/l) (ng) (ml)
1) GC/MS ( ) ( ) 1,2-1,1,1-1,1,2-1,1- cis-1,2- trans-1,2-1,2-1,3- -1-1,4-2) SIM 3) 11 55 % 4) 1 3 L 1/3 5) (1 mg/ml) 6) 7) 8) 9) 10) 11) 0.5 5 ml 20 60 0.5 12) 13) 30 % 14) 90% 9.4 ml 0.6 ml 10 100 ml 15) GC/MS 16) 17) VOCOL Aquatic DB-624 DB-WAX DB-1301 ( ) 18)
1) 1 (1993). 2 (1994). 3 JIS K0125 (1990). 4, 7, 69-79 (1997).
1,2- -3- (DBCP) n- 0.01 g/l 1 g/kg GC/MS-SIM ( 1 3) GC/MS GC/MS GC/MS (1) ( 4) DBCP n- 50 80 ml 100 ml 1 ml 100 ml (2) 5 25 ml ( 5) 105 3 ( 6) GC/MS GC MS
(1) ( ) ( ) (2) ( ) 5 25 ml 1 l ( ) 9.8 ml 0.2 ml 4.9 24.5 0.1 0.5 ml ( 7) 1 l ( ) 20 g 3000 rpm 20 10 ml 3 3000 rpm 10 10 ml 10 3000 rpm 10 (25 50 ml) 9.8 ml 0.2 ml 4.9 24.5 0.1 0.5 ml ( 7) 1 l ( ) GC/MS ( 8 10 (3) (4) (5) ( ) ( 8 10) 10 4-150 2 220
3 220 20 260 ( GC-MS (a) GC ( 0.2 0.75 mm 25 120 m 0.1 3.0 m ( 11) 40 (5 ) 7 / 230 (5 ) 180 ( 40cm/ ) (b) MS EI 70eV 300 A 230 (c) DBCP 75 (157) 104 (78) n- 134 (91) 4-174 ( ) (6) 0.25 250 ng ( 12) 1 l GC/MS (7) ( g/l) (ng) (ml) 1) GC/MS 2) SIM 3) GC/MS ( ) ( ) 1,2-1,1,1-1,1,2-1,1- cis-1,2- trans-1,2-1,2-1,3- -1-1,4-4)
5) 6) 7) 90% 9.8 ml 0.2 ml 5 25 ml 8) 9) GC/MS 10) 11) VOCOL Aquatic DB-624 DB-WAX DB-1301 ( 1) 12) 1) 1 61 (1987). 2 (1993). 3 (1994). 4 JIS K0125 (1990). 5 EPA: Method 624, US EPA.
N- 1) 2) 1) GC/MS HPLC GC/MS 2) 0.01~0.05µg/l 0.5~50µg/kg GC/MS SIM GC/MS SIM GC/MS SIM a) b) -d 10 -d 10 -d 12 -d 12 c) d) 600 C 4 e) 1 99.999% f) a) b) - IX-1 -
c) (ODS) 200-1,000mg 5ml 5ml 5ml d) e) 3ml 1g f) 3ml 0.2 0.3g g) KD h) i) j) 1µm k) / (GC/MS) a) SS 50µg/ml 1µm 5% l 50g 50ml 10 3 300ml 100ml 4 KD 2ml 3) 200ml 4) b) 1µm 5-10ml 500ml 10ml 10ml 10 3ml 20% / 10ml 2ml 5ml 2ml - IX-2 -
- IX-3-10~25g 25ml 10 10 3,000rpm 10 3 5% 400ml 1l 50ml 10 500ml 100ml 10 30g 50ml KD 2ml KD 10ml 250ml 5% 5~10ml/min 10ml 10 3ml 20% / 10ml 2ml 5ml 2ml 5) 10~25g 50ml 10 10 3,000rpm 15 50ml 1l 30ml 5 30ml 5 5ml 5% 500ml 50ml 10 50ml 40 C 10ml 10ml 2ml 5) 5% 5.2
10ml 5~10ml 1ml 2 10ml 20% 10ml 2ml Envi-Carb 3ml 0.25g 20% 10ml 50% 5ml 2ml 130 C 10g 1.0 ~1.5 30cm 2g 10ml 2ml 100ml 20% 2ml 0.5ml GC/MS 100µg/ml 1.0µg/ml 6) 0-1.0ml 0.5ml 0.5ml -d 10 -d 10 -d 12 -d 12 0.5µg/ml 6) - IX-4 -
a) GC/MS (GC) 0.25mm 30m 0.25µm 50 C 1min -20 C/min-200 C -5 C/min-280 C(5min) 250 1.0min 40-50cm/sec (MS) 280 C 270 C 70eV 300µA (EI) MS DFTPP (decafluorotriphenylphosphin) PFTBA(Perfluorotributylamine) PFK Perfluorokerosene MS 500 1 1 (M/Z) IS-1 -d 10 188 188 - IS-2 -d 10 212 212 - IS-3 -d 12 240 240 - IS-4 -d 12 264 264-215 200 (215) IS-1 269 160 (188) IS-1 201 201 (186) IS-1 291 109 (291) IS-2 201 144 (115) IS-2 330 173 (127) IS-2 283 283 (202) IS-3 335 306 (335) IS-1 214 198 (144) IS-1 4 415 163 (181) IS-4 - IX-5 -
419 125 (167) IS-4 (2 ) 419 125 (167) IS-4 (2 ) 390 183 (163) IS-4 285 198 (212) IS-1 b) 2µl GC/MS c) 2µl GC/MS d) C µg/l S abs ng V conc ml V inj GC/MS µl V spl ml GC/MS 5 (s) 3s (µg/l kg) 10s (µg/l kg) C( µ g / l) = S ( ng) Vconc( ml) 1,000 abs V ( µ l) V 10 1 ±20% 2 10% 2 30% inj spl ( ml) - IX-6 -
2,4,5-2 4-D 2,4-2,4,5-T 0.05µg/l 5~10µg/kg ph2 GC/MS SIM 1N - 1:9 ph2 20% / GC/MS a) 2,4- (2,4-D) b) 2,4,5- (2,4,5-T) c) -d 10 d) 2,4- e) f) g) 600 C 4 h) N- -N - -N- i) j) k) l) a) b) c) d) e) f) g) h) 3ml 0.5 1g : i) / (GC/MS) - IX-7 -
- IX-8-5.1 1) 1l 25g 20% ph2 100ml 10 100ml 25 C 2) 10ml 1N 10ml 10ml 70 C 15 3) 100ml 30ml 5 4) 20% ph2 30ml 10 30ml 25 C 1) 2) 3) 2,4-D 2,4,5-T 4) 10~25g 50ml 2,4-20µg/ml 0.1ml 1N - 1:9 20ml 10 10 3,000rpm 10 1N - 1:9 20ml 2 25 C + 5ml 1N 10ml 70 C 15 100ml 30ml 5 20% ph2 20% 50ml 10 20% 50ml 3 20% 25 C 10~25g 2,4-20µg/ml 0.1ml 1N - 1:9 30ml 10 10 3,000rpm 10 3 20%
0.5ml / 1ml 5) 1 0.5 -d 10 0.5µg/ml 10µl 5) N- -N - -N- 10% / 5ml 20% 5ml 0.5ml 5.1 5.3 2,4-D 2,4,5-T 100mg 100ml 1,000µg/ml 10µg/ml -d 0.5µg/ml a) GC/MS (GC) 0.25mm 30m 0.25µm 50 C 1min -20 C/min-200 C -5 C/min-280 C(5min) 250 1.0min 40-50cm/sec (MS) 280 C 270 C 70eV 300µA (EI) m/z188 -d 10 - IX-9 -
m/z199 234 2,4-D-Me m/z233 263 2,4,5-T-Me b) 0-1.0µg/ml 5 0.5ml / 1ml 1 0.5ml -d 10 0.5µg/ml 10µl 2µl GC/MS c) 2µl GC/MS d) C µg/l S abs ng V conc ml V inj GC/MS µl V spl ml GC/MS 5 (s) 3s (µg/l kg) 10s (µg/l kg) C( µ g / l) = S ( ng) Vconc( ml) 1,000 abs V ( µ l) V 10 1 ±20% 2 10% 2 30% inj spl ( ml) - IX-10 -
2- MBC: Methylbenzinidazol-2-yl carbamate MBC 0.1µg/l 2µg/kg 20µg/kg MBC 1.52 /MBC GC/MS 0.1N ph2 GC/MS 0.1N a) 98% b) -d 10 c) d) e) 600 C 4 f) N- -N - -N- g) h) PCB i) j) a) b) c) d) e) KD f) g) / (GC/MS) - IX-11 -
- IX-12-5.1 1l 50g 50ml 10 300ml 1) 2 10-20ml 100ml 0.1N 50ml 5 5N 0.2N ph 6.4 200ml 50ml 5 50ml 50ml KD 3-5ml 1) 200ml 2) N- -N - -N- 10% / / 10 25g 50ml 15 15 3,000rpm 10 50ml 40 C 0. 1N 30ml 50ml 200ml 5 50ml 40 C 50ml 100ml 0.1N 30ml 5 0.1N 20ml 5 5N 0.2N ph6.4 50ml 5 30ml 5 5.1.3 10 25g 50ml 15 15 3,000rpm 10 50ml 30ml 2 40 C 0.1
0.1N 30ml 50ml 0.5ml / 1ml 2) 1 -d 10 0.5µg/ml 0.2ml 5.1 5.3 100mg 100ml 1,000µg/ml 1ml 0.2N 50ml 100ml 5 5N 0.2N ph6.5 2.5g 20ml MBC 100ml 2 100ml 10µg/ml MBC 10 0-1.0ml 0.5ml / 1ml 1 -d 10 0.5µg/ml 0.2ml MBC 1.52 a) GC/MS (GC) 5% 0.25mm 30m 0.25µm 50 C 1min -20 C/min-200 C -5 C/min-280 C(5min) 250 1.0min 40-50cm/sec (MS) 280 C 270 C 70eV 300µA (EI) m/z188 -d 10 m/z146 205 MBC-Me - IX-13 -
b) 2µl GC/MS c) 2µl GC/MS d) C( µ g / l) = S ( ng) Vconc( ml) 1,000 abs V ( µ l) V ( ml) C µg/l S abs ng V conc ml V inj GC/MS µl V spl ml GC/MS 5 (s) 3s (µg/l kg) 10s (µg/l kg) 10 1 ±20% 2 10% 2 30% inj spl 3- -1,2,4- - IX-14 -
1µg/l 1µg/kg ph4.0 ODS HPLC- 2% o- HPLC 40% HPLC a) (amitrol) 3- -1,2-,4-98% b) (fluorescamine) (fluram) c) 0.1M (ph9.5)50ml o- 5ml(5ml 270mg o- ) 2-0.2ml 2-50µl d) 60g 16.4g 600ml ph3.8-4.0 e) f) 700 C 4 g) h) No.5C 5 C i) ODS j) k) AG50W-X8 l) IRC-50 a) b) c) d) e) f) g) - IX-15 -
5 C 20ml 50ml 2ml (ph4.0) 1) 0.2% - 4ml 2) 2 20 C 50ml 17g 1N 1ml 5-10ml ODS 2ml 2ml 3, 4) 1) ph3.8-4.0 2) 0.2% - 4ml 15-30% 0.2% - 3) o- o- 1 R-NH 2 - o- 4) - 2 2 4 10 25g 50ml 2% 10ml 10 3,000rpm 5 No.5C 2 100ml 0.1M ph9.0 10ml 20ml 50ml o- 1ml 10 O- 10ml 5 2 50ml 10 25g 20ml 5 5 3,000rpm 10 40% 20ml 50ml 20ml 5 / 100ml 10ml 1ml 75 C 30 10ml 5) 10ml 2.8% 12ml n- 30ml 45 5ml 6) 5ml 50ml 2.8% 35ml n- 100ml 0.1M 2ml 1ml 0.2% / 0.1ml 1 0.1M 0.5ml HPLC - IX-16 -
6) 10mm 300mm 0.063 0.156µm 1ml 5ml 7) 0.33 0.50µm 5ml 1N 2.8% 1N 5.1 100mg 100ml 1,000µg/ml 5µg/ml 5 a) HPLC- ODS 5mm 15cm 5µm 40 C 9% - 10:9 2ml/min 395nm 480nm b) 10ml 1ml 1ml ph4.0 0.2ml 0.2% - 0.4ml 2 20 C 10ml 0.5µg/ml 20µl HPLC -20 C 1 o- c) 20µl HPLC d) C( µ g / l) = S ( ng) Vconc( ml) 1,000 abs V ( µ l) V ( ml) C µg/l S abs ng inj spl - IX-17 -
V conc ml V inj HPLC µl V spl ml HPLC 5 (s) 3s (µg/l kg) 10s (µg/l kg) 10 1 ±20% 2 10% 2 30% N- 0.03µg/l 2µg/kg 1µg/kg N- CH 3 NH 2 o- OPA OPA 10% 10% HPLC - IX-18 -
a) 99% b) c) d) e) o- 2- f) g) 650C 24 h) i) j) k) l) 99.99% a) b) c) d) KD e) f) g) HPLC 5.1.1 l l 100g 70g 50 ml 10 1 300ml 100ml 2, 3, 30 C 4) 1µg/ml / 1:9 1ml 5) 1) 200ml 2) 30 C 3) KD 4) 50ml 5% - IX-19 -
- IX-20-1g 10ml 10% 20ml 5) HPLC 10 25g 100ml 50ml 10 10 3,000rpm 10 50ml 10% 500ml l 50ml 5 l 50ml 50ml 5 50ml 2 10ml 30 C 10~12mm 300mm 5% 1g 2cm 10ml 50ml 10% / 20ml 1ml 1µg/ml : 1:9 1ml 5.1 100mg 100ml 1000µg/ml 1:9 0-1.0µg/ml µg/ml 10 a) HPLC ODS (1:9)
1ml/min 40 C 1 50mM 100 C 0.4ml/min 2 o- / 50 C 0.4ml/min 345nm 450nm b) 20µl HPLC c) 20µl HPLC d) C µg/l S abs ng V conc ml V inj HPLC µl V spl ml HPLC 5 (s) 3s (µg/l kg) 10s (µg/l kg) C( µ g / l) = S ( ng) Vconc( ml) 1,000 abs V ( µ l) V 10 1 ±20% inj spl ( ml) - IX-21 -
2 10% 2 30% 1) (1993).. 2) (1983) 1- (NAC). 57, pp207-213, ( 58 5 ) 3) (1988) (BPMC MTMC PHC MIPC X MC NAC methyl 2-benzimidazol carbamate). 62, pp83-99, ( 63 6 ) 4) (1992). 3, pp35-54, ( 4 6 ) 5) (1993) P (MEP) (MPP) (EDDP) EPN (PMP) α- (α-cvp) β- (β-cvp). 4, pp65-94, ( 5 6 ) 6) (1994). 5, pp35-55, ( 6 6 ) 7) (1996) 2,4- p-t-. 7, pp109-126, ( 8 6 ) 8) (1984) 3- -1,2,4-. 58, pp269-276, ( 59 5 ) 9) (1992). 3, pp55-68, ( 4 6 ) 10) (1994) N-. 35, 470-478. 11) (1977). 2, 27-27. GC/MS LC/MS GC/MS/MS - IX-22 -
, 150g, 50ml 1.0l 0.5 1l 0.5l SS:50mg/l 10, 2 GC/MS IS: phenanthrene-d 10, fluoranthene-d 10 chrysene-d 12, perylene-d 12, 25ml 3, 10 25g, 3,000rpm, 10 10 5%, 400ml, 50ml 2, 10, 10ml, 250ml 10ml 20% / 10ml, 50ml 2 50% / 10ml,, 10~25g 10 3,000rpm, 10 5%, 500ml, 50ml 2, 30ml 3, 10 100ml 20% / 100ml 1 - IX-23 -
,, 25g 100ml 2, 10ml 1N, 10ml, 10ml 1l, 30ml ph, 20%, 10 20%, 30ml 2, 25 70, 15, 5 ph 2, 10, 0.5ml /, 1ml GC/MS, 1, 5ml 20% /, 5ml IS: 2,4-1N / 1:9, 20ml 2 IS: -d10 10 25g, 10 3,000rpm, 10, 10ml 1N, 10ml 20% /,, 10ml 20% 5ml 2 ph 2 70, 15, 0.5ml /, 1ml, 10 IS: 2,4-1N / 1:9, 20ml 2 10 25g, 10 2 - IX-24 -
NaCl, 150g, 50ml, 10 20ml, 1, 10, 50ml 3 0.1N, 50ml 5N 0.5N, 10 20ml, 50ml 2, 5 ph (6.5),50ml 2 GC/MS, 1 IS: phenantherene-d 10, 0.5mg/ml, 0.2ml 10 25g, 15 3000rpm, 10 0.1N, 30ml, 50ml 0.1N, 30+20 ml 5N 0.5N, 50ml 2 ph (6.5) GC/MS IS: -d10,50ml 2 30ml 2, 10 25g 15 3000rpm, 10 0.1N, 30ml, 50ml 0.1N, 30+20ml 5N 0.5N ph (6.5), 50ml 2 GC/MS IS: -d10 3 - IX-25 -
, No.5C, 17g 1N, 1ml, 2ml ODS, 5-10ml/min, 20ml 2M ph4.0, 2ml 0.2%, 4ml!! ph3.8-4.0!! 20, 2!!!! HPLC-, 2ml ODS 9% - (10:9) 395nm, : 480nm 2%, 20ml 2 10 25g O-, 1ml, 2ml, 10 0.1M (ph9.0), 10ml No.5C (ph4.0), 2ml 0.2%, 5ml, 17g 1N, 1ml, 2ml HPLC-, 20ml 40%, 2 4 ODS, 5-10ml/, 5 2 10 25g, 100ml, 10ml, 5ml, 1ml 70, 30 50ml 50ml 2 n- 10ml, 2.8% 12ml n-, 100ml 50ml, 2.8% 35ml 0.05M, 2ml 0.25% /, 0.1ml 0.1M, 0.5ml HPLC- ODS - IX-26 -
, 100g, 100ml, 1l, 10 3, 50ml 2, 50ml IS: 1mg/l, 1ml HPLC - [ 10%, 500ml 10~25g, 10 HPLC - IS: 1mg/l, 1ml 10ml 10% / 10ml, 50ml 2 10%, 500ml 10~25g, 10 10ml 10% / 10ml HPLC - IS: 1mg/l, 1ml 5 - IX-27 -
X-1
X-2
X-3
X-4
X-5
X-6
X-7 +
XI-1 -
XI-2
XI-3
XI-4
XI-5
XI-6
XI-7
XI-8
XI-9
XI-10