Isobutyl alcohol IUPAC 2-methylpropan-1-ol 2--1-2-Methyl-1-Propanol, Isobutanol CH 3 H 3 C OH CAS 78-83-1 C 4 H 10 O log P ow ( C) ( C) (kpa) (g/l) 74.12 74.14 1) -108 2) 108 2) 1.2 2) 87 2) 0.8 2) (74.1214) 2) LD 50 : 3350 mg/kg EC 50 : 1250 mg/l/24 h 2) 1) kis-net 2) 1
1 (1) ODS GC/MS-SIM (2) Fluka -d 7 CDN Isotopes (2-methyl-d 3 -propyl-2,3,3,3,- d 4 -alcohol) 4-1000 μg/ml L(+)- Waters AC-2 ODS Waters C-18 300 ml 5 ml (3) 21 3 L- 1000 mg/l 100 mg 100 ml 2
(1000 µg/ml) (1000μg/mL) 1.00 μg/ml 100 μg/ml -d 7 100 mg 100 ml (1000 µg/ml) -d 7 (1000 μg/ml) 50.0 μg/ml 4- (1000 μg/ml) 5.00 μg/ml 8 (3.00 ng/ml 5.00 ng/ml 10.0 ng/ml 30.0 ng/ml 50.0 ng/ml 100 ng/ml 300 ng/ml 500 ng/ml) -d 7 50.0 ng/ml 4-50.0 ng/ml 200 ml -d 7 (50.0 μg/ml) 5 μl (250 ng)c-18 1AC-2 2 5 ml C-18 AC-2 10 ml 10 5 ml 1 ml 3 4- (5.00 μg/ml) 50 μl 3
GC/MS GC/MS GC QP2010 J&W DB-WAX (30 m 0.25 mm, 0.5 μm) 40 C (5 min) 5 C/min 80 C (0 min) 20 C/min 200 C(3 min) 200 C 1 min He 1.0 ml/min 2 μl 230 C EI SIM -d 7 33 4 74 50 81 4-174176 2 μl GC/MS -d 7 2 μl GC/MS -d 7 -d 7 -d 7 4- C (ng/l) C (ng/l) R Q / V 4
R Q (ng) V (L) IDL GC/MS IDL 15 1 IDL IDL (ng/ml) (L) (ml) IDL (ng/l) 0.71 0.200 5.0 18 (MDL) (MQL) MDL MQL 2 6 2 MDL MQL (L) (ml) MDL (ng/l) MQL (ng/l) 0.200 5.0 63 170 1 C-18 10 ml 20 ml 2 AC-2 20 ml 40 ml 3 4 m/z = 43 5
5 IDL 21 3 3 IDL(3.00 ng/ml) 1 3 IDL (L) 0.200 (ml) 5.0 (ng/ml) 3.00 (μl) 2.0 1 (ng/ml) 3.17 2 (ng/ml) 3.19 3 (ng/ml) 3.17 4 (ng/ml) 3.38 5 (ng/ml) 3.58 6 (ng/ml) 3.16 7 (ng/ml) 3.59 8 (ng/ml) 3.45 (ng/ml) 3.337 (ng/ml) 0.188 IDL (ng/ml)* 0.71 IDL (ng/l) 18 S/N 9.0 CV (%) 5.6 *:IDL = t (n-1, 0.05) σ n-1 2 6
m/z = 33 m/z = 74 -d 7 m/z = 50 m/z = 81 4- m/z = 174 m/z = 176 1 IDL (3.00 ng/ml) 7
6 MDL MQL 21 3 4 MDL 2 4 MDL MQL (%) (L) 0.200 (ml) 5.0 (ng) 50.0 (ng/l) 250 (ng/ml) 10.0 (μl) 2.0 (ng/l)* 1 0.00 (ng/l)* 2 0.00 1 (ng/l) 275 74 2 (ng/l) 275 74 3 (ng/l) 274 90 4(ng/L) 267 73 5(ng/L) 242 72 6 (ng/l) 245 71 7 (ng/l) 292 68 8 (ng/l) 274 71 (ng/l) 267.7 74.2 (ng/l) 16.66 6.6 MDL (ng/l)* 3 63 MQL (ng/l)* 4 170 S/N 20 CV (%) 6.2 9.0 *1: (n = 1) *2: MDL (n = 1) *3: MDL = t (n-1, 0.05) σ n-1 2 *4: MQL = σ n-1 10 8
m/z = 33 m/z = 74 -d 7 m/z = 50 m/z = 81 4- m/z = 174 m/z = 176 2 MDL 9
2 3 200 ml (200 mg) (-d7 250 ng) ODS () () 5 ml/min ODS 10 ml 5 ml 1 ml/min (4-250 ng) GC/MS-SIM 3 10
4 5 5 6 ( / ) 面積比 ( 対象物質 / 内標準物質 ) 1 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 y = 0.9213x - 0.002335 R 2 = 0.9996 0 0.2 0.4 0.6 0.8 1 1.2 濃度比 ( / ) ( 対象物質 / 内標準物質 ) (3) (5) (10) (30 ) (50) (ng/ml) 4 50.0 ng/ml 3.00 50.0 ng/ml ( / ) 面積比 ( 対象物質 / 内標準物質 ) 10 9 8 7 6 5 4 3 2 1 0 y = 0.8904x +0.0149 R 2 = 1.000 0 2 4 6 8 10 12 濃度比 ( 対象物質 / 内標準物質 ) ( / ) (30) (50) (100) (300 ) (500) (ng/ml) 5 50.0 ng/ml 30.0 500 ng/ml 11
5 / (min) (ng/ml) -d 7 % (m/z = 33) (m/z = 50) 3.00 11.08 1286 22920 0.05611 3.17 5.7 5.00 11.10 2078 22403 0.09276 5.16 3.2 10.0 11.07 3999 22042 0.1814 9.97-0.27 30.0 11.07 11960 22256 0.5374 29.3-2.4 50.0 11.07 19891 21470 0.9265 50.4 0.81 *50.0 ng/ml 6 / (min) (ng/ml) -d 7 % (m/z = 33) (m/z = 50) 30.0 11.07 11960 22256 0.5374 29.3-2.2 50.0 11.07 19891 21470 0.9265 51.2 2.4 100 11.08 39797 22343 1.781 99.2-0.82 300 11.07 119408 22250 5.367 301 0.17 500 11.09 198485 22264 8.915 500-0.045 *50.0 ng/ml 12
6 7 -d 7 8 4-13
9 m/z = 33 m/z = 74 -d 7 m/z = 50 m/z = 81 4- m/z = 174 m/z = 176 9 14
7 8 10 11 12 13 7 (%) (L) 0.200 - (ml) 5.0 - (ng) 250 - (μl) 2.0 - (ng/l) * 1 0.00 - (ng/l) * 2 0.00-1 (ng/l) 1070 58 2 (ng/l) 1050 62 3 (ng/l) 1110 60 4 (ng/l) 1040 62 5 (ng/l) 1220 56 (ng/l) 1098 59 (ng/l) 75.13 2.3 CV (%) 6.8 3.9 *1: (n = 1) *2: (n = 1) 15
8 (%) (L) 0.200 - (ml) 5.0 - (ng) 250 - (μl) 2.0 - (ng/l) * 1 0.00 - (ng/l) * 2 0.00-1 (ng/l) 1050 66 2 (ng/l) 1020 58 3 (ng/l) 991 57 4 (ng/l) 1050 55 5 (ng/l) 1160 64 (ng/l) 1053 60 (ng/l) 65.48 4.5 CV (%) 6.2 7.5 *1: (n = 1) *2: (n = 1) 16
m/z = 33 m/z = 74 -d 7 m/z = 50 m/z = 81 4- m/z = 174 m/z = 176 10 0.20 L 250 ng 17
m/z = 33 m/z = 74 -d 7 m/z = 50 m/z = 81 4- m/z = 174 m/z = 176 11 0.20 L 250 ng 18
m/z = 33 m/z = 74 -d 7 m/z = 50 m/z = 81 4- m/z = 174 m/z = 176 12 0.20 L 19
m/z = 33 m/z = 74 -d 7 m/z = 50 m/z = 81 4- m/z = 174 m/z = 176 13 0.20 L 20
9 7 67% 9 (n = 2) ph 1 7 (%) (ng/l) (%) 5 500 100 100 7 500 100 98 67 9 500 100 100 1) A B ph 2 5 7 10 7 ph 7 ph 2 10 No.1 (n = 2) (%) (ng/l) 7 A 120 (ph 2) 59 (ph 7) 500 B 190 (ph 2) 74 (ph 5) 52 (ph 7) 500 130 (ph 2) 140 (ph 5) 60 (ph 7) 21
ph 2 1 2 11 11 No.2 (n = 2) (%) (ng/l) 1 2 3 4 5 6 (ph 2) 500 91 110 130 140 110 130 ph 2 L- 100 mg/l 12 54% 70% 12 No.3 (n = 2) (ng/l) L- 500 20 mg (100 mg/l) 20 mg (100 mg/l) (%) 7 54 (ph ) 70 (ph ) 200 (ph 2) L- 1000 mg/l 1 13 3 4 90% 22
13 No.4 (n = 2) (%) (ng/l) 1 2 3 4 5 6 7 500 96 93 90 78 75 67 69 500 110 100 100 95 82 86 83 L- ph ph 3.73 ph 3.81 2) 14 14 (n = 2) (%) (ng/l) 14 500 98 500 100 3) 15 15 (n = 2) (%) (ng/ml) 1 MDL 10 50.0 97 500 96 23
ODS (C-18) ODS 5 ml 0% ODS (AC-2) 1 ml 1 ml 100%0%14 回収率 100% 90% 80% 70% 60% 50% 40% 30% 20% 10% 0% 100% 0% 0% 0% 0% 0~1mL 1~2mL 2~3mL 3~4mL 4~5mL 14 24
2 3.0 ng/ml 50 ng/ml r 2 > 0.999 IDL 18 ng/l MDL 63 ng/l 0.2 L n = 5 250 ng 55 66% 6.2 6.8% 0.2 μg/l L- 59 7 1,4-239-0806 10 6 TEL 044-288-4905 FAX 044-288-5232 E-mail horiuchi@jesc.or.jp 25
Isobutyl alcohol (2-Methyl-1-Propanol, Isobutanol) An analytical method has been developed for the determination of isobutyl alcohol in water by gas-chromatography mass spectrometry (GC/MS). Surrogate is added to a water sample containing ascorbic acid (1000 mg/l) and the sample is passed through an ODS cartridge column joined on the upper of an activated carbon (AC) cartridge column. The ODS column is removed from the AC column. The AC column is washed with 10 ml of purified water and then is sucked to dry, and eluted with 5 ml of acetone. The eluate is measured by GC/MS-SIM after adding an internal standard. The instrument detection limit (IDL) is 18 ng/l. The method detection limit (MDL) and the method quantification limit (MQL) is 63 ng/l and 170 ng/l, respectively. The average recoveries of environmental waters containing 250 ng of isobutyl alcohol were 59% in river water and 60% in seawater, respectively. Water sample Solid-Phase Extraction 200 ml ascorbic acids (200 mg) surrogate (Isobutyl alchole-d7 250 ng) ODS cartridge column (upper)+ activated carbon cartridge column (lower) 5 ml/min remove ODS column Wash purified water 10 ml Dehydration aspiration Elution acetone 5 ml 1 ml/min syringe spike (4-Bromofluorobenzene 250 ng) GC/MS-SIM 26
GC/MS-SIM 2- -1-200 ml (200 mg) (-d7 250 ng) ODS () () 5 ml/min (ng/l) 63 ODS 10 ml GC/MS: GC/MS-SIM QP2010 5 ml 1 ml/min (4-250 ng) DB-WAX 30 m 0.25 mm, 0.5 μm 27
(VOC) GC/MS-SIM 50.0 ml -d 7 GC/MS-SIM Trap 5 ml GL AQUA Trap-2 150 C 150 C 40 C 40 ml/min 8 min 40 ml/min 3 min 250 C 2 min 80 ml/min 250 C 18 min He (90 kpa) GC/MS GC/MS QP2010 GL AQUATIC (60 m 0.25 mm, 1.0 μm) GC 35 C (5 min) 6 C/min 90 C (0 min) 10 C/min 200 C (3 min) 150 C 200 C 200 C EI SIM -d 7 3374 5081 28
IDL GC/MS IDL 1 IDL (3.00 ng/ml) 1 1 IDL (L) 0.050 (ng/ml) 3.0 1 (ng/ml) 3.1 2 (ng/ml) 2.9 3 (ng/ml) 3.0 4 (ng/ml) 3.0 5 (ng/ml) 2.9 6 (ng/ml) 3.0 7 (ng/ml) 3.1 8 (ng/ml) 3.1 (ng/ml) 3.01 (ng/ml) 0.07 IDL (ng/ml)* 0.25 IDL (μg/l) 0.25 S/N 10 CV (%) 2.2 *:IDL = t (n-1, 0.05) σ n-1 2 m/z = 33 m/z = 74 -d 7 m/z = 81 m/z = 50 1 IDL (3.00 ng/ml) 29
2 3 面積比 ( 対象物質 / 内標準物質 ) 2 1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 y = 0.8584x + 0.007459 R 2 = 0.9999 0 0.5 1 1.5 2 2.5 (3)(5)(10) (30 ) 濃度比 (50) ( 対象物質 / 内標準物質 (100) ) (ng/ml) 2 30.0 ng/ml 3.00 100 ng/ml 3 / (ng/ml) (min) % 3.00 14.83 1180 21258 0.05551 2.80-6.7 5.00 14.82 1993 20963 0.09507 5.10 2.1 10.0 14.82 3865 20910 0.1848 10.3 3.3 30.0 14.81 10916 21206 0.5148 29.5-1.5 50.0 14.83 18356 21103 0.8698 50.2 0.46 100 14.82 37046 21487 1.724 100-0.012 VOC GC GC GC IDL 0.25 μg/l 30