2,4-2,4-Dimethylaniline 2,4-2,4-Xylidine CH 3 CH 3 CAS 95-68-1 C 8 H 11 N 121.18 121.0892-14.3 C 2) 214 C 2) 0.9723 g/cm 3 2) 0.133 mmhg (25 C) 1) 1390 mg/l (25 C) 1) 3.710 3 mg/l 25 C WSKOWWIN 5) 6.0710 3 mg/l 25 C 5) log P ow 1.68 (ph = 7.5) 3) pka 4.89 (25 C) 4) NH 2 282
LD 50 250 mg/kg 3) LD 50 467 mg/kg 3) LC 50 739 mg/m 3 (7hr) 7) Leuciscas idas melanotus (48h) LC 50 196 mg/l 4) 出典 : 1) Philip H. Howard, William M. Meylan, Handbook of Properties of Organic Chemcals 2) Lide, D.R,(ed), CRC Handbook of Chemistry and Physics 84th Edition 3) Hansch, C., A. Leo and D. Hoeckman(1995): Exploring QSAR-Hydrophobic, Electronic, and Steric Constants, Washington DC,ACS Professional Reference Book:45 4) Supelco MSDS 5) U. S. Environmental Protection Agency, WSKOWWIN TM v. 1.41 6) Meylan,W. M., P. H. Howard and R. S. Boethling(1996): Improved method for estimating water solubility from octanol/water partition coefficient :Environ. Toxicol. Chem. 15:-106 7) US National Institute for Occupational Safety and Health, Registry of Toxic Effects of Chemical Substances (RTECS) Database 1 (1) 0.01 mol/l -70% 2 GC/MS-SIM /(8:2) 0.01 mol/l -70% 1 mol/l 283
-10% 2 GC/MS-SIM (2) 2,4- Supelco 99.9% -2,3,4,5,6-d 5 CIL 99% 5000 1 1 Milli-Q JISK0557(1998) A4 Waters Sep-Pak Plus PS-2 Agilent Bond Elute PRS,500 mg 3 ml 0.01 mol/l -70%PS-2 50 μl 50 ml 35 ml 50 ml 0.5 mol/l 15% 10 g 75 g 500 ml ml 10 0.01 mol/l -PRS 50 μl 50 ml 50 ml 1 mol/l -10%PRS 284
3.7 g 50 ml 30 ml 5 ml 50 ml 0.1 mol/l -10% 2.0 g 50 g 500 ml 1 L ml 10 10.0 mg10 ml 1.00 mg/ml 1.00 μg/ml 1.00 μg/ml -d 5 10.0 mg 10 ml 1.00 mg/ml 1.00 μg/ml 0.50010.0 ng/ml -d 5 10.0 ng/ml (10 ml) (50 ml) (10 ml) (1 L, ml) 285
Sep-Pak Waters Waters TAITEC (3) 21 3 3 ml 10 ml 20 ml 10 ml 20 ml 30 0.01 mol/l 70% 3 ml 0.5 mol/l 15% 8 ml 4 ml 5 5 0.5 g 1 4 ml 10.0 ng/ml 10 ml GC/MS 20 g 50 ml / (8:2) 20 ml 10 2500 rpm 10 ml / (8:2) 20 ml ml ml 10 ml 20 ml 10 ml 20 ml 30 286
5 ml 0.01 mol/l - 2 ml 0.01 mol/l- 70% 3 ml 0.01 mol/l - 2 ml 30 1 mol/l -10% 2 ml 0.5 mol/l -15% 8 ml 4 ml 5 5 0.5 g 1 4 ml 10.0 ng/ml 10 ml GC/MS GC/MS GC/MS GC6890Agilent MS5973Agilent Supelco SUPELCOWAX 10 30 m0.25 mm, 0.25 μm 50 C (1 min) 20 C /min 130 C (0 min) 3 C /min 163 C (0 min) 20 C /min 260 C (1 min) 1.0 min 210 C He (1.0 ml/min) 35 cm/sec 2 μl 270 C 230 C 150 C EI 70 ev 287
SIM 2,4- m/z 121.0 m/z 120.0m/z 106.0 -d 5 m/z 98.0 2 μl GC/MS 2 μl GC/MS C (ng/l) C RQ/V R : Q : (ng) = (ng/ml) (ml) V : (L) Q =.0 (ng) = (10.0 ng/ml) (10.00 ml) V = 0. (L) C = R 500 (ng/l) C (ng/g-dry) C RQ/V 288
R : Q : (ng) = (ng/ml) (ml) V : (g-dry) Q =.0 (ng) = (10.0 ng/ml) (10.00 ml) C = R /V (ng/l) (IDL) GC/MS IDL 1 2 1 IDL IDL *1 (ng/ml) (ml) IDL *2 0.20 0.20 10 9.9 2,4-0.20 20 10 0.099 *1 L g-wet *2 ng/l ng/g-wet (MDL) (MQL) MDL MQL 2 3 2 MDL MQL *1 MDL *2 MQL *2 (ml) 0.2 10 14 36 2,4-20 10 7.3 19 *1 L g-wet 68.6% *2 ng/l ng/g-dry 289
1 2IDL 21 3 3-1 3-2 1 3-1 IDL N- (N-EA) N--o- (N-Me-o-T) N--p- (N-Me-p-T) N--m- (N-Me-m-T) 2,6- (26XLD) o- (o-ea) (L) 0. 0. 0. 0. 0. 0. (ml) 10 10 10 10 10 10 (ng/ml) 1.00 1.00 1.00 1.00 1.00 1.00 (μl) 2 2 2 2 2 2 1 (ng/ml) 0.910 0.862 0.959 1.03 0.922 1.00 2 (ng/ml) 0.946 0.999 0.881 1.05 0.907 0.977 3 (ng/ml) 0.962 0.939 0.895 0.887 0.953 0.918 4 (ng/ml) 0.956 0.991 0.904 0.973 0.915 0.957 5 (ng/ml) 0.950 0.861 0.916 0.912 0.886 0.993 6 (ng/ml) 0.925 0.921 0.868 0.942 0.952 0.975 7 (ng/ml) 0.907 1.04 0.937 0.922 0.998 0.933 (ng/ml) 0.9365 0.9452 0.9086 0.9616 0.9334 0.9653 (ng/ml) 0.0225 0.0670 0.0319 0.0632 0.0371 0.0312 IDL (ng/ml) * 0.088 0.27 0.12 0.246 0.14 0.12 IDL (ng/l) 4.4 14 6.2 12 7.2 6.1 IDL (ng/g-wet) 0.045 0.14 0.062 0.12 0.072 0.061 S/N 23 13 24 17 12 22 CV (%) 2.4 7.4 3.5 6.6 5.2 3.2 *: IDL = t (n-1, 0.05) σ n-1 2 290
2,4- (24XLD) 3-2 IDL 2,5- (25XLD) p- (p-ea) m- (m-ea) 3,5- (35XLD) 2,3- (23XLD) 3,4- (34XLD) (L) 0. 0. 0. 0. 0. 0. 0. (ml) 10 10 10 10 10 10 1 (ng/ml) 1.00 1.00 1.00 1.00 1.00 1.00 1.00 (μl) 2 2 2 2 2 2 2 1 (ng/ml) 0.981 1.01 0.929 0.919 0.931 0.926 0.913 2 (ng/ml) 0.910 0.969 0.917 0.980 0.697 1.03 0.785 3 (ng/ml) 0.957 0.946 0.866 0.952 0.728 0.948 0.765 4 (ng/ml) 0.939 0.945 0.924 0.974 0.667 1.034 0.813 5 (ng/ml) 1.06 0.858 0.870 0.969 0.842 0.956 0.812 6 (ng/ml) 0.921 0.947 0.895 0.896 0.711 0.877 0.937 7 (ng/ml) 0.925 0.883 0.996 1.05 0.717 0.934 0.947 (ng/ml) 0.9559 0.9366 0.9137 0.9634 0.7561 0.9576 0.8531 (ng/ml) 0.0511 0.0511 0.0441 0.0503 0.0945 0.0560 0.0765 IDL (ng/ml) * 0.20 0.20 0.17 0.20 0.37 0.22 0.30 IDL (ng/l) IDL (ng/g-wet) 9.9 9.9 8.6 9.8 18 11 15 0.099 0.099 0.086 0.098 0.18 0.11 0.15 S/N 11 5.2 30 17 17 7.9 9.33 CV (%) 5.4 5.5 4.8 5.2 12 5.9 9.0 *: IDL = t (n-1, 0.05) σ n-1 2 291
140 120 80 60 イオン 121.00 (120.50 ~ 121.50): 140403_1ppb_1.D\data.ms N-Me-mT 24XLD p-ea 35XLD N-Me-oT 26XLD m-ea 25XLD 23XLD o-ea N-EA N-Me-pT 34XLD イオン 120.00 (119.50 ~ 120.50): 140403_1ppb_1.D\data.ms 150 160 140 120 80 60 イオン 106.00 (105.50 ~ 106.50): 140403_1ppb_1.D\data.ms イオン 98.00 (97.50 ~ 98.50): 140403_1ppb_1.D\data.ms 400 300 -d 5 1 IDL (2 pg) 292
3MDL MQL 21 3 4-1 4-2 5-1 5-2 2 3 4-1 MDL MQL N- (N-EA) N--o- (N-Me-o-T) N--p- (N-Me-p-T) N--m- (N-Me-m-T) 2,6- (26XLD) o- (o-ea) (L) 0. 0. 0. 0. 0. 0. (ng) 20.0 20.0 20.0 20.0 20.0 20.0 (ng/l) (ml) 10 10 10 10 10 10 (ng/ml) 2.00 2.00 2.00 2.00 2.00 2.00 (μl) 2 2 2 2 2 2 (ng/l)* 1 ND ND ND ND ND ND (ng/l) *2 ND ND ND ND ND ND 1 (ng/l) 108 97.0 104 103 99.0 103 2 (ng/l) 107 97.2 102 98.2 3 (ng/l) 104 101 96.4 99.0 99.1 95.2 4 (ng/l) 99.6 98.4 95.4 99.6 89.0 92.0 5 (ng/l) 101 103 97.5 102 87.9 96.6 6 (ng/l) 101 96.9 94.6 94.5 91.4 93.3 7 (ng/l) 99.2 94.6 95.4 96.3 93.3 94.4 (ng/l) 102.8 98.70 97.21 99.49 93.99 96.36 (ng/l) 3.55 2.84 3.17 3.17 4.80 3.89 MDL (ng/ml) *3 14 11 12 12 19 15 MQL (ng/ml) *4 36 28 32 32 48 39 S/N 45 18 41 44 25 57 CV (%) 3.5 2.9 3.3 3.2 5.1 4.0 *1(n=1) *2MDL (n=1) *3MDL = t (n-1,0.05) σ n-1 2 *4MQL = σ n-1 10 293
4-2 MDL MQL 2,4- (24XLD) 2,5- (25XLD) p- (p-ea) m- (m-ea) 3,5- (35XLD) 2,3- (23XLD) 3,4- (34XLD) (L) 0. 0. 0. 0. 0. 0. 0. (ng) 20.0 20.0 20.0 20.0 20.0 20.0 20.0 (ng/l) (ml) 10 10 10 10 10 10 10 (ng/ml) 2.00 2.00 2.00 2.00 2.00 2.00 2.00 (μl) 2 2 2 2 2 2 2 (ng/l)* 1 ND ND ND ND ND ND ND (ng/l) *2 ND ND ND ND ND ND ND 1 (ng/l) 103 101 106 104 103 104 111 2 (ng/l) 95.8 98.2 101 99.9 101 99.1 111 3 (ng/l) 101 95.5 96.2 96.3 96.5 98.1 99.5 4 (ng/l) 101 89.4 98.2 93.6 98.5 97.2 99.8 5 (ng/l) 97.6 97.0 96.7 93.5 98.4 94.4 98.5 6 (ng/l) 92.8 86.0 91.9 92.7 94.3 94.1 98.9 7 (ng/l) 96.0 92.0 97.0 95.0 94.9 94.5 102 (ng/l) 98.17 94.16 98.14 96.43 98.09 97.34 103.0 (ng/l) 3.63 5.27 4.40 4.12 3.16 3.54 5.61 MDL (ng/l) *3 14 20 17 16 12 14 22 MQL (ng/l) *4 36 52 44 41 32 35 56 S/N 21 21 42 18 25 21 9.1 CV (%) 3.7 5.6 4.5 4.3 3.2 3.6 5.4 *1(n=1) *2MDL (n=1) *3MDL = t (n-1,0.05) σ n-1 2 *4MQL = σ n-1 10 294
150 121.00 (120.50~121.50): 140109_L1_2.D\data.ms 35XLD N-Me-oT N-Me-mTo-EA 25XLD N-EA 24XLD m-ea 23XLD N-Me-pT 26XLD p-ea 34XLD 50 8.00 120.00 (119.50~120.50): 140109_L1_2.D\data.ms 150 50 8.00 106.00 (105.50~106.50): 140109_L1_2.D\data.ms 150 50 8.00 98.00 (97.50~98.50): 140109_L1_2.D\data.ms 400 -d 5 300 8.00 2 MDL 295
5-1 MDL MQL N- (N-EA) N--o- (N-Me-o-T) N--p- (N-Me-p-T) N--m- (N-Me-m-T) 2,6- (26XLD) o- (o-ea) (g-dry) 6.28 6.28 6.28 6.28 6.28 6.28 (ng) (ng/g-dry) 32 32 32 32 32 32 (ml) 10 10 10 10 10 10 (ng/ml) 20.0 20.0 20.0 20.0 20.0 20.0 (µl) 2 2 2 2 2 2 (ng/g-dry)* 1 ND ND ND ND ND ND (ng/g-dry) *2 ND ND ND ND ND ND 1 (ng/g-dry) 12.1 10.9 5.29 7.84 13.2 12.8 2 (ng/g-dry) 12.1 11.0 4.92 7.87 13.8 13.4 3 (ng/g-dry) 12.6 10.9 5.34 8.13 13.5 13.3 4 (ng/g-dry) 11.1 10.3 3.50 6.58 12.5 12.0 5 (ng/g-dry) 10.2 8.65 2.95 5.22 11.0 11.0 6 (ng/g-dry) 8.66 7.37 1.51 3.52 9.80 8.89 7 (ng/g-dry) 8.65 7.42 1.59 3.92 9.82 9.57 (ng/g-dry) 10.77 9.491 3.587 6.153 11.94 11.57 (ng/g-dry) 1.65 1.64 1.66 1.94 1.72 1.81 MDL (ng/g-dry) *3 6.4 6.4 6.4 7.6 6.7 7.0 MQL (ng/g-dry) *4 16 16 17 19 17 18 S/N 160 83 56 84 86 CV (%) 15 17 46 32 14 16 *1(n=1) *2MDL (n=1) *3MDL = t (n-1,0.05) σ n-1 2 *4MQL = σ n-1 10 296
5-2 MDL MQL 2,4-2,5-3,5- p- m- (p-ea) (m-ea) (24XLD) (25XLD) (35XLD) 2,3- (23XLD) 3,4- (34XLD) (g-dry) 6.28 6.28 6.28 6.28 6.28 6.28 6.28 (ng) (ng/g-dry) 32 32 32 32 32 32 32 (ml) 10 10 10 10 10 10 10 (ng/ml) 20.0 20.0 20.0 20.0 20.0 20.0 20.0 (μl) 2 2 2 2 2 2 2 (ng/g-dry)* 1 ND ND ND ND ND ND ND (ng/g-dry) *2 ND ND ND ND ND ND ND 1 (ng/g-dry) 7.73 10.8 5.66 7.27 6.64 10.7 4.39 2 (ng/g-dry) 7.90 10.9 5.60 7.30 5.12 11.5 4.09 3 (ng/g-dry) 8.01 11.6 5.86 7.29 6.67 11.3 4.35 4 (ng/g-dry) 6.30 10.1 4.92 6.64 4.71 10.1 3.37 5 (ng/g-dry) 6.23 9.11 4.42 5.86 5.42 9.11 3.18 6 (ng/g-dry) 3.38 6.35 2.27 3.83 2.63 6.71 1.28 7 (ng/g-dry) 4.00 7.19 2.96 4.60 3.96 7.51 1.69 (ng/g-dry) 6.222 9.441 4.527 6.114 5.021 9.553 3.191 (ng/g-dry) 1.88 2.00 1.41 1.41 1.44 1.86 1.26 MDL (ng/g-dry) *3 7.3 7.8 5.5 5.5 5.6 7.2 4.9 MQL (ng/g-dry) *4 19 20 14 14 14 19 13 S/N 14 17 24 54 72 59 26 CV (%) 30 21 31 23 29 19 40 *1(n=1) *2MDL (n=1) *3MDL = t (n-1,0.05) σ n-1 2 *4MQL = σ n-1 10 297
600 500 400 300 500 400 300 0 800 600 400 m/z 121 NN-DMA m/z 120 m/z 106 イオン 121.00 (120.50 ~ 121.50): 140403_MDL_A.D\data.ms 26XLD N-Me-o-T o-ea 25XLD N-Me-m-T 35XLD 24XLD N-EA N-Me-p-T m-ea 23XLD p-ea 34XLD イオン 120.00 (119.50 ~ 120.50): 140403_MDL_A.D\data.ms イオン 106.00 (105.50 ~ 106.50): 140403_MDL_A.D\data.ms イオン 98.00 (97.50 ~ 98.50): 140403_MDL_A.D\data.ms 600 500 400 300 m/z 98 -d 5 -d 5 3 MDL 298
2 4-1 4-2 ml 20 ml Sep-Pak Plus PS-2 10 ml/min 2 30 0.01 mol/l- 70% 3 ml 0.5 mol/l- 15% 8 ml 4 ml 5 5 0.5 g GC/MS-SIM 10 ml -d5 ng 4-1 299
2 20 g-wet /(8:2) 20 ml 10 2500 rpm10 10 ml 20 ml Sep-Pak Plus PS-2 10 ml/min 30 Bond Elute PRS 0.01 mol/l- 70% 3 ml Sep-Pak Plus PS-2 0.01 mol/l- 2 ml 30 1 mol/l- 10% 2 ml 2 0.5 mol/l- 15% 8 ml 4 ml 5 5 0.5 g GC/MS-SIM -d5 ng 10 ml 4-2 300
6 5 6 2,4- (A s ) (ng/ml) 2,4- (A is ) (A s /A is ) (C s ) (m/z 121) -d 5 (m/z 98) 0 0 13202 0.50 861 13216 0.065 1.00 1610 13715 0.117 2.00 3168 13542 0.234 5.00 8091 13878 0.583 10.0 15095 13908 1.085 20.0 29117 13597 2.141 50.0 74019 14004 5.286 165899 13669 9.942 298202 13797 21.61 *10.0 ng/ml (ng/ml) (0.5)(1)(2) (5) (10) (ng/ml) (10) (20) (50) () () 5 0.510 ng/ml10 ng/ml 301
2,4-6 500 400 300 NN- DMA イオン 121.00 (120.50 ~ 121.50): 140403_5ppb_1.D\data.ms N-Me-pT o-ea N-Me-mT 25XLD 35XLD N-Me-oT - -24XLD 23XLD m- EA 26XLD N-EA 34XLD p-ea イオン 120.00 (119.50 ~ 120.50): 140403_5ppb_1.D\data.ms 600 500 400 300 イオン 106.00 (105.50 ~ 106.50): 140403_5ppb_1.D\data.ms 500 400 300 イオン 98.00 (97.50 ~ 98.50): 140403_5ppb_1.D\data.ms 500 400 -d 5 300 6 5 ng/ml) 302
2,4- ng/ml -d 5 7-17-2 0 900 スキャン 1395 (9.602 min): scan_24xldppb_d_1.d\data.ms (-1344) (-) 120.0 106.0 800 700 600 500 400 300 58.9 77.1 91.0 m/z--> 0 50 55 60 65 70 75 80 85 90 95 105 110 115 120 125 7-1 2,4- スキャン 2570 (11.470 min): SCAN_ANILINED5.D\data.ms (-2487) (-) 98.1 45000 40000 35000 30000 25000 00 15000 71.1 00 m/z--> 5000 0 42.1 49.1 56.1 64.0 80.0 35 40 45 50 55 60 65 70 75 80 85 90 95 105 7-2 -d 5 303
8-1 8-2 55 イオン 121.00 (120.50 ~ 121.50): 131031_BL_PS_2_1.D\data.ms 2,4-XLD 50 8.00 イオン 120.00 (119.50 ~ 120.50): 131031_BL_PS_2_1.D\data.ms 50 48 46 8.00 イオン 106.00 (105.50 ~ 106.50): 131031_BL_PS_2_1.D\data.ms 50 8.00 イオン 98.00 (97.50 ~ 98.50): 131031_BL_PS_2_1.D\data.ms 400 -d 5 300 8.00 8-1 304
イオン 121.00 (120.50 ~ 121.50): 140305_BL_1.D\data.ms 55 2,4-XLD 50 イオン 120.00 (119.50 ~ 120.50): 140305_BL_1.D\data.ms 55 50 45 イオン 106.00 (105.50 ~ 106.50): 140305_BL_1.D\data.ms 70 65 60 55 50 45 400 350 300 250 150 イオン 98.00 (97.50 ~ 98.50): 140305_BL_1.D\data.ms -d 5 9.00 900 10.00 00 11.00 12.00 13.00 14.00 15.00 16.00 8-2 305
2 1 2 7-1 7-2 9-14 7-1 (ml) (ng) (ng/l) (%) CV (%) 2,4-1 ND - - 2 923 92.3-1 ND - - 3 996 99.6 7.2 1 ND - - 2 1020 102-7-2 (g-wet) (ng) (ng/ g-wet) (%) CV (%) 2,4-20 1 ND - - 20 3 5.8 57.6 1.6 20 1 ND - - 20 20 7 0.48 48.3 10.2 20 1 ND - - 20 1 7.5 75.5-306
イオン 121.00 (120.50 ~ 121.50): 140304_ 茨戸河川水無添加.D\data.ms 140 120 80 60 2,4-XLD イオン 120.00 (119.50 ~ 120.50): 140304_ 茨戸河川水無添加.D\data.ms 60 55 50 イオン 106.00 (105.50 ~ 106.50): 140304_ 茨戸河川水無添加.D\data.ms 55 50 500 400 300 イオン 98.00 (97.50 ~ 98.50): 140304_ 茨戸河川水無添加.D\data.ms 9-1 307
1400 1 0 800 600 400 121.00 (120.50~121.50): 140304_ 茨戸 A_day0.D\data.ms N-Me-o-T o-ea 25XLD N-Me-m-T 35XLD 24XLD N-EA N-Me-p-T 26XLD m-ea 23XLD p ĒA 34XLD 120.00 (119.50~120.50): 140304_ 茨戸 A_day0.D\data.ms 1500 0 500 106.00 (105.50~106.50): 140304_ 茨戸 A_day0.D\data.ms 1500 0 500 500 400 300 98.00 (97.50~98.50): 140304_ 茨戸 A_day0.D\data.ms -d 5 9-2 308
65 イオン 121.00 (120.50 ~ 121.50): 140304_ 茨戸無添加 _0227.D\data.ms 2,4-XLD 60 55 イオン 120.00 (119.50 ~ 120.50): 140304_ 茨戸無添加 _0227.D\data.ms 55 50 イオン 106.00 (105.50 ~ 106.50): 140304_ 茨戸無添加 _0227.D\data.ms 90 80 70 60 50 イオン 98.00 (97.50 ~ 98.50): 140304_ 茨戸無添加 _0227.D\data.ms 500 400 -d 5 300 9-3 309
700 600 500 400 300 イオン 121.00 (120.50 ~ 121.50): 140304_ 茨戸 A_day0.D\data.ms N-Me-oT N-EA N-Me-mT o-ea 25XLD 35XLD 23XLD 26XLD m-ea 24XLD p-ea 34XLD N-Me-pT イオン 120.00 (119.50 ~ 120.50): 140304_ 茨戸 A_day0.D\data.ms 800 600 400 1 0 800 600 400 イオン 106.00 (105.50 ~ 106.50): 140304_ 茨戸 A_day0.D\data.ms イオン 98.00 (97.50 ~ 98.50): 140304_ 茨戸 A_day0.D\data.ms 500 400 300 -d 5 9-4 ph 1 L 500 ng 1 310
1 L 8 26 8 2,4-8 ph 1 (%) 8 26 (ng/l) (%) 5 2 500 87.3 104-95.0-7 2 500 85.3 106 97.9 95.2 92.5 9 2 500 88.6 105-97.3-80% 10-1 10-2 2,4-XLD 10-1 (%) (ng/l) 3 7 2 0 92.3 107 107 3 0 83.7 103 91.6 2 0 102 103 104 2,4-XLD 10-2 (ng/g-wet) (%) 3 7 1 5 75.5 33.7 15.0 1 5 - - 60.2 1 10 57.6 15.1 15.0 2 10-95.5 91.3 311
10-3 (%) 7 14 (ng/g-wet) 2,4-XLD 2 5 88.9 108 104 PS-2 1 μg/ml μl 10 ml PS-2 2 ml 1 ml 0.1 mol/l -10% 4 ml 1 ml 5 GC/MS 10 N- N--o- 70% 2 ml90% 1 ml 70% 3 ml 312
10 PS-2 Bond Elute PRS 1 μg/ml μl 0.01 mol/l 2 ml Bond Elute PRS 2 ml 1 ml 0.1 mol/l -10% 4 ml 1 ml 5 GC/MS 11-1 11-2 1 1 mol/l KCl 1 mol/l KCl-20% 24XLD 5% 2 1 313
mol/l KCl-10%1 2 3 ml 30% 3 2 ml 11-1 1 mol/l KCl 20% Bond Elute PRS 11-2 1 mol/l KCl-10% 1 mol/l KCl-30% Bond Elute PRS 314
2,4-13 9-1 9-3 11-1 (ml) (ng) N-(N-EA) CV (ng/l) (%) (%) 0.97 97 2.1 N--o-(N-Me-o-T) 0.78 78 7.9 N--p-(N-Me-p-T) 0.68 68 17 N--m-(N-Me-m-T) 0.82 82 9.3 2,6-シ メチルアニリン (26XLD) 0.78 78 5.3 o-(o-ea) 0.94 94 2.9 2,4-シ メチルアニリン (24XLD) 3 0.80 79 6.2 2,5-シ メチルアニリン (25XLD) 0.88 88 4.0 p-(p-ea) 0.93 93 4.9 m-(m-ea) 0.82 82 4.2 3,5-シ メチルアニリン (35XLD) 1.00 4.4 2,3-シ メチルアニリン (23XLD) 0.92 91 2.6 3,4-シ メチルアニリン (34XLD) 0.80 80 5.0 315
N-(N-EA) 11-2 (g-dry) (ng) (ng/ g-dry) (%) o-(o-ea) 22 70 1.0 2,4-シ メチルアニリン (24XLD) 6.28 3 18 58 1.6 2,5-シ メチルアニリン (25XLD) 21 66 1.7 CV (%) 21 66 3.5 N--o-(N-Me-o-T) 18 57 4.5 N--p-(N-Me-p-T) 17 54 5.7 N--m-(N-Me-m-T) 19 58 4.3 2,6- シ メチルアニリン (26XLD) 20 62 3.7 p-(p-ea) 18 57 2.1 m-(m-ea) 17 53 0.9 3,5- シ メチルアニリン (35XLD) 22 70 9.4 2,3- シ メチルアニリン (23XLD) 21 66 1.6 3,4- シ メチルアニリン (34XLD) 12 37 1.6 316
12-1 (%) *1 (ng/l) *2 3 *2 7 *2 28 *2 N-(N-EA) 97 99 92 34 N--o-(N-Me-o-T) 78 107 103 13 N--p-(N-Me-p-T) 68 110 92 2.8 N--m-(N-Me-m-T) 82 101 88 5.7 2,6-シ メチルアニリン (26XLD) 78 105 103 45 o-(o-ea) 94 101 96 69 2,4-シ メチルアニリン (24XLD) 0 79 103 92 13 2,5-シ メチルアニリン (25XLD) 88 102 89 36 p-(p-ea) 93 95 76 14 m-(m-ea) 82 97 84 32 3,5-シ メチルアニリン (35XLD) 90 76 11 2,3-シ メチルアニリン (23XLD) 91 99 89 40 3,4-シ メチルアニリン (34XLD) 80 92 67 7.1 *1 % *2 3 7 28 n=3 317
12-2 (%) *1 (ng/g-wet) *2 3 *2 7 *2 7 *2 N-(N-EA) 66 18 15 71 N--o-(N-Me-o-T) 57 18 14 84 N--p-(N-Me-p-T) 54 11 13 64 N--m-(N-Me-m-T) 58 9.8 8.9 52 2,6-シ メチルアニリン (26XLD) 62 37 27 98 o-(o-ea) 70 21 17 63 2,4-シ メチルアニリン (24XLD) 10 58 15 15 60 2,5-シ メチルアニリン (25XLD) 66 20 16 58 p-(p-ea) 57 9.7 11 49 m-(m-ea) 53 11 12 50 3,5-シ メチルアニリン (35XLD) 70 5.8 6.4 43 2,3-シ メチルアニリン (23XLD) 66 18 15 57 3,4-シ メチルアニリン (34XLD) 37 8.7 15 61 *1 % *2 3 7 7 n=3n=1 n=1n=1 318
12-3 (%) *1 (ng/g-wet) *2 3 *2 7 *2 14 *2 N-(N-EA) 96 111 109 97 N--o-(N-Me-o-T) 85 113 115 98 N--p-(N-Me-p-T) 86 109 109 106 N--m-(N-Me-m-T) 88 112 110 99 2,6-シ メチルアニリン (26XLD) 87 113 111 96 o-(o-ea) 97 111 111 2,4-シ メチルアニリン (24XLD) 10 89 107 103 104 2,5-シ メチルアニリン (25XLD) 96 109 103 98 p-(p-ea) 102 102 113 m-(m-ea) 89 104 101 107 3,5-シ メチルアニリン (35XLD) 77 125 127 79 2,3-シ メチルアニリン (23XLD) 96 110 104 3,4-シ メチルアニリン (34XLD) 97 93 85 111 *1 % *2 3 7 7 n=2n=1 n=2n=3 2,4- MDL MQL 14 ng/l 36 ng/l 7.3 ng/g-dry 19 ng/g-dry 2,4-1 ng/ml ng/ml (R=0.998) 10 μg/l ng/g-wet 2,4-12 MDL MQL 11 ng/l22 ng/l 28 ng/l56 ng/l 5.5 ng/g-dry7.8 ng/g-dry 14 ng/g-dry20 ng/g-dry 2,4-13 78% 7 3770% 7 6.427% 77102% 7 319
2,4-13 1) 2 6 2) N-N,N- 15 3 003-8505 9 1 5-22 TEL011-841-9596 FAX011-841-7073 E-mail atsuko.abe@city.sapporo.jp 320
2,4-Dimethylaniline A simultaneous analysis method for the determination of 6 isomers of xylidine (XLD), 3 isomers of N-methyltoluidine,4 isomers of ethylaniline in water and sediment samples has been developed by gas chromatography/mass spectrometry with selected ion monitoring. A ml of water sample is passed through a preconditioned solid-phase extraction cartridge (PS-2) to collect previously described 13 isomers and then eluted with 3 ml of 0.01 mol/ml HCl - 70% methanol solution. The eluate is diluted with alkaline sodium chloride solution, and 13 isomers are extracted with 4 ml of hexane twice. Sediment samples are extracted by methanol / pure water (8:2) solution using sonication and centrifuge. Crude extract is diluted with pure water and solid-phase extracted in the same way as water samples. MDL, MQL of 2,4-dimethylaniline in water samples and sediment samples are 13 ng/l, 35 ng/l and 7.3 ng/g-dry, 19 ng/ g-dry, respectively. The recoveries of 2,4-dimethylaniline spiked to river water, seawater and river sediment were 92.3%-102%, 102% and 48.3%-75.5%, respectively. None of 13 isomers was detected in environmental samples. Water Sample Solid phase extraction ml wash:purifried water 20 ml Sep-Pak Plus PS-2 10 ml/min Dehydration over 30 sec Elution 0.01 mol/l HCl- 70%methanol 3 ml 0.5 mol/lnaoh-15%nacl 8 ml Shaking Extraction hexane 4 ml 5 min 2 times Phase partitioning more than 5 min Dehydration anhydrous Na2SO4 0.5 g syringe spike aniline-d 5 ng Make up volume hexane 10 ml GC/MS-SIM 321
Sediment sample Ultrasonic extraction 20 g-wet methanol/pure water (8:2) 20 ml 10 min 2 times Centrifugation 2500 rpm, 10 min Make up volume pure water ml Solid phase extraction rince the bottle: pure water 20 ml Sep-Pak Plus PS-2 10 ml/min Dehydration 30 min Clean up connect to cation exchange cartridge Bond Elute PRS Elution 0.01 mol/lhcl- 70%methanol 3 ml Wash 0.01 mol/lhcl-methanol discard 2 ml Sep-Pak Plus PS-2 Dehydration 30 min Elution 1 mol/lhcl-10%methanol 2 ml 2 times Liquid-liquid extraction 0.5 mol/lnaoh-15%nacl 8 ml hexane 4 ml 5 min Phase partitioning more than 5 min Dehydration anhydrous Na2SO4 0.5 g syringe spike aniline-d5 ng Make up volume hexane 10 ml GC/MS-SIM 322
2,4-2,4-Dimethylaniline 2,4-2,4-Xylidine ml 20 ml Sep-Pak Plus PS-2 10 ml/min 30 GC/MS-SIM ( ng/l) 13 0.01 mol/l- 70% 3 ml 0.5 mol/l- 15% 8 ml (ng/g-dry) 7.3 2 4 ml 5 5 0.5 g GC 6890 (Agilent) MS 5973 (Agilent) -d5 ng 10 ml GC/MS-SIM SUPELCOWAX 10 30 m 0.25 mm, 0.25 µm 323
2 20 g-wet /(8:2) 20 ml 10 2500 rpm10 ml 20 ml Sep-Pak Plus PS-2 10 ml/min 30 Bond Elute PRS 0.01 mol/l- 70% 3 ml Sep-Pak Plus PS-2 0.01 mol/l- 2 ml 30 2 1 mol/l- 10% 2 ml 0.5 mol/l- 15% 8 ml 4 ml 5 5 0.5 g GC/MS-SIM -d5 ng 10 ml 324