平成26年度化学物質分析法開発報告書

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1 N,N- N,N-Dimethylacetamide Acethyldimethylamine CAS C 4 H 9 NO ~ C 1) C 2) 1 mg/l 25 C 3) 3.3 hpa 2 C 4) log P ow ) /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

2 6) 7) TC Lo 2 mg/m 3 LD mg/kg LD 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 7) (kis-net) 8) (CHRIP) 1 (1) GC/MS-SIM (2) 1 N,N- 99.% 72

3 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

4 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) ml 1. mg/l 1 µl 1 ml 1 ml 1 ml Sep-Pak AC 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

5 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 m/z m/z µl GC/MS 1 µl GC/MS 4- C (ng/l) C = RQ / V 75

6 R Q (ng) V (L) Q = 1 (ng) = (1. µg/ml) (1 µl) V =.1 (L) C = R 1 (ng/l) N,N--d N,N- -d 9 4- (IDL) GC/MS IDL IDL IDL IDL (µg/l) (L) (ml) (µg/l) N,N (MDL) (MQL) MDL MQL MDL MQL MDL MQL (L) (ml) (µg/l) (µg/l) N,N

7 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

8 5IDL IDL N,N- (L).1 (ml) 2. (µg/l) 2. (µl) 1. 1 (µg/l) (µg/l) (µg/l) (µg/l) (µg/l) (µg/l) (µg/l) 1.96 (µg/l) (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: Relative Abundance N,N- m/z E F: MS std Time (min) 1-1 IDL N,N- (2. µg/l) 78

9 N,N--d 9 RT: Relative Abundance m/z Time (min) 3.2E F: MS std1 1-2 IDL N,N--d 9 (5. µg/l) RT: Relative Abundance m/z E F: MS std Time (min) 1-3 IDL 4- (5. µg/l) 79

10 6MDL MQL 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) * (µg/l) (µg/l) (µg/l) (µg/l) (µg/l) (µg/l) (µg/l) (µg/l) (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

11 N,N- m/z 86.9 m/z 44. N,N- N,N--d 9 m/z 96. N,N--d 9 m/z m/z m/z MDL 81

12 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 面積比 1 y =.7649x - 3E-6 R² =.9997 面積比 2 1 y =.8287x R² = 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

13 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.) 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.) µg/l N,N-N,N--d

14 N,N- m/z 86.9 m/z 44. N,N- N,N--d 9 m/z 96. N,N--d 9 m/z m/z m/z (5. ng/l)

15 6-1 N,N- 6-2 N,N--d

16 N,N- MDL 7 RT: Relative Abundance N,N m/z E F: MS Sp_Blank Time (min) ~ (L) (ng) (µg/l) (%) (%) (%).1 2 < <

17 RT: N,N m/z E F: MS mutenka1 1 5 N,N--d 9 m/z E F: MS mutenka m/z Time (min) 2.2E F: MS mutenka1 8-1 RT: N,N m/z 86.9 N,N--d 9 m/z m/z Time (min) 3.37E F: MS tenka1 1.55E F: MS tenka1 2.29E F: MS tenka ng 87

18 N,N- RT: m/z E F: MS sea_mutenka_1 1 5 N,N--d 9 m/z E F: MS sea_mutenka_ m/z E F: MS sea_mutenka_ Time (min) 8-3 RT: N,N- 5 m/z E F: MS sea_tenka_1 1 5 N,N--d 9 m/z E F: MS sea_tenka_ m/z Time (min) 1.98E F: MS sea_tenka_ ng ph 7 88

19 ph 7 7 (%) (µg/l) µg/l (4 C) 7 1 MDL 1 5. µg/l 1 µg/l 15 µg/l N,N * (%) (µg/l) * MDL 1 4 C

20 9 1 * (µg/l) (%) * 5 ~ 2 ml/min 1 2 ml/min 2 ml/min 1 N,N--d 9 (ml/min) (%) C 18 C 18 C 18 C

21 RT: Relative Abundance C E7 TIC F: MS tenka1_sc an C E7 TIC F: MS AC2_only_s can Time (min) 9 C 18 TIC (4-2 m/z) RT: N,N- AA: E F: MS ICIS tenka1 RT: N,N- AA: E F: MS ICIS AC2_only 1 5 N,N- -d 9 AA: E F: MS ICIS tenka1 1 5 AA: N,N- -d 9 2.2E F: MS ICIS AC2_only 1 5 AA: Time (min) 2.35E F: MS ICIS tenka1 1 5 AA: Time (min) 2.98E F: MS ICIS AC2_only 1 C 18 C 18 C 18 9 TIC C 18 1 C 18 91

22 C 18 C 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 (1998) 2) 14 Vol.3No (1993) TEL FAX [email protected] 92

23 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

24 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

<4D F736F F D F90858C6E5F C B B B838B>

<4D F736F F D F90858C6E5F C B B B838B> 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)

平成26年度 化学物質分析法開発報告書

平成26年度化学物質分析法開発報告書