N,N- N,N-Dimethylacetamide Acethyldimethylamine CAS 127-19-5 C 4 H 9 NO 87.12 ~ 87.14 87.68413 163-165 C 1) - 18.59 C 2) 1 mg/l 25 C 3) 3.3 hpa 2 C 4) log P ow -.77 2).9429 2/4 C 1) 3.1 4) 1.31E - 8 atm-m 3 /mol 25 C 5) 7 C open cup 5) 49 C 5) 71
6) 7) TC Lo 2 mg/m 3 LD 5 462 mg/kg LD 5 392 mg/kg LD 5 48 mg/kg 8) 1) Budavari, S.,(ed), The Merck Index Ver.12:2 2) Lide, D.R.,(ed), CRC Handbook of Chemistry and Physics 84th Edition 3) Philip H. Howard, William M. Meylan, Handbook of Physical Properties of Organic Chemicals 4) ICSC 259 5) Hazardous Substances Data Bank, National Library of Medicine 6) Webkis-plus http://db-out.nies.go.jp/kis-plus/ed_top2.php?cas_id=127-19-5&cas=127-19-5 7) (kis-net) http://www.k-erc.pref.kanagawa.jp/kisnet/hyouji.asp 8) (CHRIP) http://www.safe.nite.go.jp/japan/sougou/view/comprehensiveinfodisplay_jp.faces 1 (1) GC/MS-SIM (2) 1 N,N- 99.% 72
N,N--d 9 CDN isotopes 99.4% 4-1 mg/ml PCB 5 PCB 5 JISK557 (1998) A4 Waters Sep-Pak AC-2 N,N- 1 mg 1 ml 1 g/l N,N--d 9 1 mg 1 ml 1 mg/l 1. mg/l 4-1 mg/ml 1 ml 1 ml 1. mg/l 1. mg/l1. mg/l.1 mg/l 2 µg/l.1 mg/l 1. ml 5 ml ~ 15 µg/l1. mg/l 1.5 ml 1 ml 2 ml 1 µl 1 µl Waters 73
1 ml2 ml5 ml1 ml 25 µl 1 ml 1 ml1.5 ml (1 ml) PP (1 ml) 2 ml Agilent 1.5 ml (3) 21 3 1 ml 1. mg/l 1 µl 1 ml 1 ml 1 ml Sep-Pak AC-2 2 2 ml/min 1 ml (4 rpm1 min) (2 min) 2 ml 4-1. mg/l 1 µl 2 ml 3 GC/MS GCThermoFisher Scientific Trace GC ultra 74
MSThermoFisher Scientific DSQ ThermoFisher Scientific TG-WAX (3 m.25 mm,.25 μm) 5 C (5 min) 3 C /min 8 C 5 C /min 1 C 25 C /min 2 C (3 min) 1. min (16 kpa, 1. min) 15 C He 1. ml/min 1 µl 2 C EI 2 C 7 ev 25 µa SIM N,N- 4 m/z 86.9 m/z 44. N,N--d 9 4 m/z 96. m/z 5. 4- m/z 173.8 m/z 94.9 1 µl GC/MS 1 µl GC/MS 4- C (ng/l) C = RQ / V 75
R Q (ng) V (L) Q = 1 (ng) = (1. µg/ml) (1 µl) V =.1 (L) C = R 1 (ng/l) N,N--d 9 4-1 N,N- -d 9 4- (IDL) GC/MS IDL 1 5 1 IDL IDL IDL (µg/l) (L) (ml) (µg/l) N,N-.63.1 2..13 (MDL) (MQL) MDL MQL 2 6 2 MDL MQL MDL MQL (L) (ml) (µg/l) (µg/l) N,N-.1 2..12.31 76
1 2 C 18 C 18 2 ml 2 ml 2 ml 3 4N,N- m/z 44. CO 2 m/z 71.9 m/z 71.9 N,N--d 9 m/z 78. 6-1 6-2 77
5IDL 21 3 3 IDL N,N- (L).1 (ml) 2. (µg/l) 2. (µl) 1. 1 (µg/l) 2.12 2 (µg/l) 2.3 3 (µg/l) 1.73 4 (µg/l) 2.14 5 (µg/l) 1.88 6 (µg/l) 1.77 7 (µg/l) 1.96 (µg/l) 1.949 (µg/l).162 IDL (µg/l)*.63 IDL (µg/l).13 S/N 8.7 CV (%) 8.3 *IDL = t (n-1,.5) σ n-1 2 RT: 13.87-17.62 Relative Abundance 12 11 1 9 8 7 6 N,N- m/z 86.9 15.61 15.82 14.3 14.38 15.22 16.11 16.15 16.63 17.24 2.59E4 86.4-87.4 F: MS std1 5 14. 14.5 15. 15.5 16. 16.5 17. 17.5 Time (min) 1-1 IDL N,N- (2. µg/l) 78
N,N--d 9 RT: 13.26-17.95 1 Relative Abundance 8 6 4 2 15.52 m/z 96. 13.8 13.27 13.95 14.94 15.38 15.77 16.13 17.58 17.76 14 15 16 17 Time (min) 3.2E5 95.5-96.5 F: MS std1 1-2 IDL N,N--d 9 (5. µg/l) RT: 11.9-15.65 1 Relative Abundance 8 6 4 2 4- m/z 173.8 13.8 4.16E5 173.3-174.3 F: MS std1 12. 12.5 13. 13.5 14. 14.5 15. 15.5 Time (min) 1-3 IDL 4- (5. µg/l) 79
6MDL MQL 21 3 4 2 4 MDL MQL N,N- (%) (L).1 (ng) 5. (µg/l).5 (ml) 2. (µg/l) 2.5 (µl) 1. (µg/l) *1 <.12 (.56) *3 11 (µg/l) *2 <.12 (.85) *3 11 1 (µg/l).532 13 2 (µg/l).55 17 3 (µg/l).548 111 4 (µg/l).467 19 5 (µg/l).51 17 6 (µg/l).482 19 7 (µg/l).472 16 (µg/l).525 17 (µg/l).36 MDL (µg/l) *4.12 MQL (µg/l) *5.31 S/N 15 CV (%) 6.1 *1 (n = 2) *2MQL (n = 2) *3( ) *4MDL = t (n-1,.5) σ n-1 2 *5MQL = σ n-1 1 8
N,N- m/z 86.9 m/z 44. N,N- N,N--d 9 m/z 96. N,N--d 9 m/z 5. 4- m/z 173.8 4- m/z 94.9 2 MDL 81
2 3 1 ml N,N--d 9 1 ng SepPak AC-2 (4 mg) 2 ml/min 1 ml 4 rpm 1 min 2 min 2 ml 4-1 ng 2 ml GC-MS-SIM 3 4 5-1 5-2 2 3 面積比 1 y =.7649x - 3E-6 R² =.9997 面積比 2 1 y =.8287x -.1537 R² = 1.5 1 1.5 2 1 2 3 濃度比 濃度比 (2.) (5) (1) (µg/l) (1) (5) (1) (15) (µg/l) 4 N,N- N,N--d 9 5. µg/l 2. µg/l ~ 1 µg/l1 µg/l ~ 15 µg/l 82
5-1 N,N- N,N- N,N--d 9 (µg/l) (A s ) (A is ) (A s /A is ) (C s ) (m/z 86.9) (m/z 96.).4 2. 51863 1637411.32.1 5. 14761 1734774.81.2 1. 2178 1451981.145.4 2. 5568 17449.297 1 5. 1234135 1578639.782 2 1 2211816 145176 1.52 5. µg/l 5-2 N,N- N,N- N,N--d 9 (µg/l) (A s ) (A is ) (A s /A is ) (C s ) (m/z 86.9) (m/z 96.) 2 1 2211816 145176 1.52 4 2 5147154 163962 3.16 1 5 13777292 1688457 8.16 2 1 2645258 1595654 16.3 3 15 4364631 163173 24.8 5. µg/l N,N-N,N--d 9 4-5 83
N,N- m/z 86.9 m/z 44. N,N- N,N--d 9 m/z 96. N,N--d 9 m/z 5. 4- m/z 173.8 4- m/z 94.9 5 (5. ng/l) 6-1 6-3 84
6-1 N,N- 6-2 N,N--d 9 6-3 85
N,N- MDL 7 RT: 13.87-17.62 Relative Abundance 1 8 6 4 2 N,N- 15.85 m/z 86.9 15.62 15.98 13.97 14.21 15.24 16.67 17.23 5.69E4 86.4-87.4 F: MS Sp_Blank 14. 14.5 15. 15.5 16. 16.5 17. 17.5 Time (min) 7 6 8-1 ~ 8-4 6 (L) (ng) (µg/l) (%) (%) (%).1 2 <.12 - - 19.1 5. 7.53 11 6.1 18.1 2 <.12 - - 81.1.1 3. 5.273 91. 4.3 86.7 86
RT: 11.6-17. 1 5 N,N- 13.78 m/z 86.9 15.8 15.97 2.11E4 86.4-87.4 F: MS mutenka1 1 5 N,N--d 9 m/z 96. 15.5 1.5E5 95.5-96.5 F: MS mutenka1 1 5 13.78 4- m/z 173.8 12 13 14 15 16 17 Time (min) 2.2E5 173.3-174.3 F: MS mutenka1 8-1 RT: 11.6-17. 1 5 1 5 1 5 N,N- 13.79 13.78 m/z 86.9 N,N--d 9 m/z 96. 15.6 15.5 15.81 4- m/z 173.8 12 13 14 15 16 17 Time (min) 3.37E4 86.4-87.4 F: MS tenka1 1.55E5 95.5-96.5 F: MS tenka1 2.29E5 173.3-174.3 F: MS tenka1 8-2 5. ng 87
N,N- RT: 11.6-17. 1 5 13.42 m/z 86.9 13.87 15.68 15.89 6.81E4 86.4-87.4 F: MS sea_mutenka_1 1 5 N,N--d 9 m/z 96. 15.6 1.25E5 95.5-96.5 F: MS sea_mutenka_1 1 5 13.87 4- m/z 173.8 1.76E5 173.3-174.3 F: MS sea_mutenka_1 12 13 14 15 16 17 Time (min) 8-3 RT: 11.6-17. 1 N,N- 5 m/z 86.9 15.69 15.89 6.79E4 86.4-87.4 F: MS sea_tenka_1 1 5 N,N--d 9 m/z 96. 15.6 1.38E5 95.5-96.5 F: MS sea_tenka_1 1 5 13.88 4- m/z 173.8 12 13 14 15 16 17 Time (min) 1.98E5 173.3-174.3 F: MS sea_tenka_1 8-4 3. ng ph 7 88
ph 7 7 (%) (µg/l) 5 2.5 11 7 2.5 13 14 9 2.5 13 8.1 µg/l (4 C) 7 1 MDL 1 5. µg/l 1 µg/l 15 µg/l N,N- 7 1 8 * (%) (µg/l) 7 1 2.1 93.5 2.1 96.9 2 5. 15 2 1 12 2 15 95.5 * MDL 1 4 C 1 9 1 89
9 1 * (µg/l) (%) 2.1 117 2.1 128 * 5 ~ 2 ml/min 1 2 ml/min 2 ml/min 1 N,N--d 9 (ml/min) (%) 5 98.5 1 84.1 15 94. 2 96.3 C 18 C 18 C 18 C 18 9 1 9
RT: 6. - 25.46 7.77 1 Relative Abundance 8 6 4 2 C 18 18.72 2.88 22.92 6.89 16. 23.53 2.65 21.1 7.95 1.35 9.45 11.32 13.83 17.75 24.8 2.5E7 TIC F: MS tenka1_sc an 1 8 6 4 2 6.9 7.78 C 18 7.94 1.35 11.33 13.83 12.72 18.72 16.2 19.14 17.75 2.65 21.69 22.4 22.78 2.5E7 TIC F: MS AC2_only_s can 6 8 1 12 14 16 18 2 22 24 Time (min) 9 C 18 TIC (4-2 m/z) RT: 12.5-17.3 1 5 N,N- AA: 42783 2.64E4 86.4-87.4 F: MS ICIS tenka1 RT: 12.5-17.3 1 5 N,N- AA: 4946 2.42E4 86.4-87.4 F: MS ICIS AC2_only 1 5 N,N- -d 9 AA: 1276 1.87E5 95.5-96.5 F: MS ICIS tenka1 1 5 AA: 1197148 N,N- -d 9 2.2E5 95.5-96.5 F: MS ICIS AC2_only 1 5 AA: 132527 4-13 14 15 16 17 Time (min) 2.35E5 173.3-174.3 F: MS ICIS tenka1 1 5 AA: 1537598 4-13 14 15 16 17 Time (min) 2.98E5 173.3-174.3 F: MS ICIS AC2_only 1 C 18 C 18 C 18 9 TIC C 18 1 C 18 91
C 18 C 18 5 6 MDL MDL 8-3 N,N- MDL.12 µg/lmql.31 µg/l 5. ng 11 18% 6.1% 3. ng 91.% 86.7% 4.3%.2 µg/l N,N- 1) N,N- 9 141-152 (1998) 2) 14 Vol.3No.115-23(1993) 338-13 7-5-12 TEL48-84-2266 FAX48-84-2267 E-mail aea47-u1u1@city.saitama.lg.jp 92
N,N-Dimethylacetamide This method provides procedures for the determination of N,N-dimethylacetamide in water samples by gas-chromatography/mass-spectrometry with selected ion monitoring (GC/MS-SIM). A water sample (.1 L) is spiked with N,N-Dimethylacetamide-d 9 (1. ng) as a surrogate. The sample is then extracted by solid-phase extraction with a solid-phase extraction cartridge (Sep-Pak Plus AC-2) at a flow rate of 2 ml/min. After sample loading, water in the cartridge is removed by centrifugation and suction. The cartridge is backflush-eluted with 2 ml of ethyl acetate. Then 1. ng of 4-bromofluorobenzene is spiked into the extract as a syringe spike. The concentration of N,N-dimethylacetamide is determined by GC/MS-SIM. The instrument detection limit (IDL) is.63 µg/l. The method detection limit (MDL) and method quantification limit (MQL) are.12 µg/l and.31 µg/l, respectively. The average recovery (n = 7) from 5. ng of N,N-dimethylacetamide added to river water was 11%, and the relative standard deviation was 6.1%. The average recovery (n = 5) from 3. ng of N,N-dimethylacetamide added to seawater was 91.%, and the relative standard deviation was 4.3%. Water Sample Solid phase extraction 1 ml surrogate SepPak AC-2 (4 mg) (N,N-dimethylacetamide-d 9 1 ng) 2 ml/min Wash Purified water 1 ml Dehydration Centrifugation 4 rpm, 1 min Suction 2 min Elution Back-flush elution Ethyl acetate about 2 ml Making up volume GC-MS-SIM syringe spike (4-Bromofluorobenzene 1 ng) Ethyl acetate to 2 ml 93
N,N- 1 ml N,N--d 9 1 ng SepPak AC-2 2 ml/min 1 ml GC/MS-SIM (µg/l).12 4 rpm 1 min 2 min 2 ml 2 ml 4-1 ng GCTrace GC ultra GC-MS-SIM (ThermoFisher Scientific) MSDSQ (ThermoFisher Scientific) TG-WAX (ThermoFisher Scientific) 3 m.25 mm,.25 μm 94