平成26年度 化学物質分析法開発報告書

2,2-2,2 -Iminodiethanol Diethanol amine CAS 111-42-2 C 4 H 11 NO 2 105.1356-105.0790-28 C 1) 1.0881 g/cm 3 1) <0.0075 mmhg (20 C) 2) 95.40% (20 C) 3) log P ow -1.43 2) pka 8.88 4) LD 50 2300 mg/kg 5) LD 50 3300 mg/kg 5) LD 50 3553 mg/kg 5) LD 50 2300 mg/kg 5) LD 50 12200 mg/kg 5) LD 50 2000 mg/kg 5) LD 50 710 mg/kg 5) 529

6) 1) Budavari,S., (Ed), The Merck Index Ver.12:2 2) International Chemical Safety Cards ICSC0618 3) Lide, D.R, (Ed), CRC Handbook of Chemistry and Physics 84th Edition 4) HP PubChem Compound 5) HP (kis-net) 6) HP (CHRIP) 1 (1) 100 ml 10 100 ml 25% (5:95) LC/MS/MS-SRM(ESI+) (2) 2,2-99.0% 2,2 --d 8 CDN ISOTOPES 98% Waters Oasis MCX 1 g/20 cc LCMS LCMS Milli-Q LCMS 1 mol/l HPLC 25% 530

25% (5:95) 25% 50 ml 1000 ml 2,2-50.0 mg 50 ml 2,2-1000 mg/l 2,2 --d 8 50.0 mg 50 ml 2,2 --d 8 1000 mg/l 1000 mg/l 10.0 g/ml 2,2-1000 mg/l / (1:999) 0.100 ng/ml 100 ng/ml 2,2 --d 8 1000 mg/l 100 ng/ml 1 (100 ml)(10-100 L) (100-1000 L) PP 15 ml10 ml LC PP (3) 1 21 3 531

100 ml 100 ml 900 ml 100 ml 2 2,2 --d 8 10.0 g/ml 100 L ph 5~7 3 4 Oasis MCX 10 ml/min 100 ml 20 ml 25% (5:95) 8 ml 45 C 0.5 ml 5 / (1:999) 10 ml LC/MS 6 LC/MS Waters 2695/ Quattro micro API LC LC Waters 2695 Waters XBridge Amide 2.1 mm 100 mm, 3.5 m A:5 mmol/l / (2:8) B:// (1:899:100) 0 7 min A:100% B: 0% 7 12 min A: 0% B:100% 12 20 min A:100% B: 0% 0.2 ml/min 40 C 10 L /(1:1) / (1:999) MS MS Waters Quattro micro API 3.0 kv 532

120 C 300 C 50 L/Hr 800 L/Hr ESI-Positive SRM 2,2 m/z 106.0>88.0 m/z 106.0>70.0 2,2 --d 8 m/z 114.1>96.0 2,2 20 V 20 V 2,2 --d 8 20 V 2,2 12 ev 14 ev 2,2 --d 8 12 ev 10 L LC/MS 2,2-10 L LC/MS 2,2 - C ( g/l) C = R Q / V R : Q : ( g) ( g/ L) ( L) V : (L) 533

Q = 1( g) = (0.01 g/ L) (100 L) V = 0.01 (L) (= {(0.1 L) / [(0.1 L)+(0.9 L)]} 0.1 L C = R 100 ( g/l) (IDL) LC/MS/MS IDL 1 7 1 IDL IDL (ng/ml) (L) (ml) IDL ( g/l) 2,2'- 0.089 0.1 0.01 10 10 0.0089 0.089 (MDL) (MQL) MDL MQL 2 8 2 MDL MQL (L) (ml) MDL ( g/l) MQL ( g/l) 2,2'- 0.100 0.0100 10.0 10.0 0.014 0.14 0.037 0.37 534

1 2,2-2(Oasis MCX) 0 100 ml 2,2-2,2 - -d 8 2,2-2,2 - -d 8 70% 10 ml 10mL 10 100 ml 3 ph 1 mol/l 1 mol/l ph7 4 25% (5:95) 20 ml 20 ml 5 LC/MS/MS 0.5 ml 6 LC/MS Waters Quattro micro API 535

7 IDL 21 3 3 1 IDL 3 IDL 2,2'- (L) 0.100 0.0100 (ml) 10.0 (ng/ml) 0.300 ( L) 10.0 1 (ng/ml) 0.253 2 (ng/ml) 0.280 3 (ng/ml) 0.235 4 (ng/ml) 0.249 5 (ng/ml) 0.294 6 (ng/ml) 0.289 7 (ng/ml) 0.251 (ng/ml) 0.2644 (ng/ml) 0.0229 IDL (ng/ml)* 0.089 IDL g/l) 0.0089 0.089 S/N 9.4 CV(%) 8.6 * IDL=t(n-1,0.05) n-1 2 536

2,2-2,2-2,2 - -d 8 1 IDL (2,2 0.300 ng/ml) 537

8 MDL MQL 21 3 4-1 4-2 2-1 2-2 MDL 4-1 MDL MQL 2,2'- (%) - (L) 0.100 - ( g) 0.0100 - ( g/l) 0.100 - (ml) 10.0 - (ng/ml) 1.00 - ( L) 10.0 - ( g/l) *1 < 0.014 101 ( g/l) *2 < 0.014 99 1 ( g/l) 0.102 *5 101 2 ( g/l) 0.100 99 3 ( g/l) 0.105 99 4 ( g/l) 0.110 101 5 ( g/l) 0.104 100 6 ( g/l) 0.099 101 7 ( g/l) 0.105 100 ( g/l) 0.1036 100.1 ( g/l) 0.00369 MDL( g/l) *3 0.014 MQL( g/l) *4 0.037 S/N 14 CV(%) 3.6 *1 (n = 3) *2 MDL (n = 3) *3 MDL = t (n-1, 0.05) n-1 2 *4 MQL = n-1 10 *5 538

4-2 MDL MQL 2,2'- - () (L) 0.0100 - ( g) 0.0100 - ( g/l) 1.00 - (ml) 10.0 - (ng/ml) 1.00 - ( L) 10.0 - ( g/l) *1 < 0.14 101 ( g/l) *2 < 0.14 72 1 ( g/l) 1.17 *5 69 2 ( g/l) 1.10 70 3 ( g/l) 1.18 70 4 ( g/l) 1.12 73 5 ( g/l) 1.15 73 6 ( g/l) 1.15 69 7 ( g/l) 1.08 70 ( g/l) 1.136 70.6 ( g/l) 0.0369 MDL( g/l) *3 0.14 MQL( g/l) *4 0.37 S/N 26 CV(%) 3.2 *1 (n = 3) *2 MDL (n = 3) *3 MDL = t (n-1, 0.05) n-1 2 *4 MQL= n-1 10 *5 539

2,2-2,2-2,2 - -d 8 2-1 MDL 0.100 g/l 2,2-2,2-2,2 - -d 8 2-2 MDL 1.00 g/l 540

2 ph 0.100 L 1 mol/l HCl Oasis MCX 1 g 0.100 L + 0.900 L 0.100 L or 1 mol/l NaOH 10 ml/min ph5-7 (2,2 - -d 8 1.00 g 100 ml 20 ml 25% (5:95) 8 ml 0.5 ml (1 999) 10 ml 3 LC/MS/MS SRM ESI+ 541

/ (1:999) 0.100 100 ng/ml 2,2 - -d 8 100 ng/ml 10 L LC/MS 5 4 5 (Cs) (As) (Ais) (As/Ais) (ng/ml) m/z 106.0>88.0 m/z 114.0>96.0 0.00000 0.000 0 16189 0.00000 0.00100 0.100 44 15509 0.00284 0.00300 0.300 146 16217 0.00900 0.00500 0.500 268 14961 0.0160 0.00700 0.700 355 16128 0.0220 0.0100 1.00 473 16116 0.0293 0.0300 3.00 1398 16223 0.0862 0.100 10.0 4348 15728 0.276 0.300 30.0 13643 15957 0.855 1.00 100.0 40923 15667 2.61 * 100 ng/ml 542

(ng/ml) (50) (100) (ng/ml) (0.5) (1) 4 2,2-0.1 100 ng/ml0.1 1 ng/ml 2,2 - (10 ng/ml) 5 2,2-2,2-2,2 - -d 8 5 2,2-10 ng/ml 543

2,2-2,2 --d 8 6 7 2,2-2,2 - -d 8 6 2,2-2,2 --d 8 2,2-2,2 - -d 8 7 2,2 - : m/z 106 2,2 --d 8 : m/z 114 544

6 8 6 ( g/l) 2,2'- 3 <0.014 2,2-2,2-2,2 - -d 8 8 100 ml 545

7 9-1 9-4 2,2'- ( g) (L) 7 (ml) *1 *1 ( g/l) (%) (%) (%) 0.100 10.0 3 <0.014 - - 101 0.100 0.120 10.0 5 1.11 93 0.9 109 0.100 10.0 3 <0.014 - - 99 0.100 0.0100 10.0 7 0.104 104 3.6 100 0.100 0.120 10.0 5 1.16 97 1.1 98 0.010 10.0 1 <0.14 - - 72 0.010 0.0100 10.0 7 1.14 114 3.2 71 0.010 0.120 10.0 5 12.5 103 1.0 71 *1 546

2,2-2,2-2,2 - -d 8 9-1 100 ml 2,2-2,2-2,2 - -d 8 9-2 100 ml 0.120 g 547

2,2-2,2-2,2 - -d 8 9-3 10 ml 2,2-2,2-2,2 - -d 8 9-4 10 ml 0.120 g 548

8 2,2'- 8 ph 1 7 (%) (ng/ml) (%) 5 10.0 106 92-7 10.0 102 102 101 9 10.0 100 100-9 2,2'- 7 14 PP 1 2,2'- 9 (%) (ng/ml) 7 14 1 1.20 88 - - 12.0 95 - - 11.6-98 - 12.5-96 - MDL 10 1.00 - - 104 10.0 - - 100 100 - - 97 2,2 - MDL 9-1 9-3 549

1. (1) ph (Oasis MCX) 2,2'- ph 3 5 7 8 9 2,2'- 0.1 g (Oasis MCX) 2,2 - -d 8 10 ph3-9 85% ph3 ph9 ph5-8 85% 2,2 - ph5~7 (Oasis MCX) 120 100 (%) 80 60 40 20 10 ml 100 ml 0 2 4 6 8 10 ph 10 ph 2,2'- (2) Oasis MCX 2,2-0.2 g (Oasis MCX) 25% (5:95) 2 ml LC/MS/MS 11 2,2-0-6 ml 0-8 ml 550

(%) No. 2 ml 11 (Oasis MCX) 2,2 - (3) (Oasis MCX) (Oasis MCX) 0 10 20 50 100 ml 2,2-0.1 g 12 2,2-2,2 --d 8 70% 10 ml (%) (ml) 12 (Oasis MCX) (4) (Oasis MCX) (Oasis MCX) 0.5 ml / (1:999) 10 ml 551

13 10 5 ml 10 ml 30 mg/l LC/MS/MS (%) (ml) 13 (Oasis MCX) LC/MS/MS 2,2 - IDL 0.089 ng/ml 0.0089 0.089 g/l0.1 100 ng/ml (r 2 >0.99) MDL MQL 0.014 0.037 g/l 0.14 0.37 g/l 100 ml 10 ml 0.12 g 97 103% 1.1 1.0% 1 2,2 - MDL 0.1 g/l 2,2-552

650-0046 4-6 TEL 078-302-6302 FAX 078-302-6291 E-mail masahiro_yagi@office.city.kobe.lg.jp kengo_mukai@office.city.kobe.lg.jp 553

2,2 -Iminodiethanol This method provides a procedure for the determination of 2,2 -iminodiethanol in water samples by liquid chromatography-tandem mass spectrometry (LC/MS/MS). After 100 L of 2,2 -iminodiethanol-d 8 (surrogate, 10 ng/ L) is spiked into 100 ml of a water sample (in the case of sea water, 100 ml of that diluted 10-fold with purified water), the sample is passed through a preconditioned solid phase extraction cartridge (Oasis MCX). The extract is eluted with 8 ml of 25% anmonia aq. and methanol (5:95). The solution is analyzed by LC/MS/MS-SRM (ESI positive). Method detection limits (MDL) of 2,2 -iminodiethanol in river water and sea water were 0.014 and 0.14 g/l, respectively. The averages of recoveries (and those of relative standard deviations) from 0.12 g of 2,2 -iminodiethanol added to river water and sea water were 97% (1.1%) and 104% (1.0%), respectively. 2,2 -Iminodiethanol was not detected in river water and sea water (Kobe) by the method. Water sample ph adjustment Solid Phase Extraction River Water 0.1 L 1 mol/l HCl Oasis MCX 1 g Sea Water + Pure WaterAliquot or 1 mol/l NaOH 10 ml/min 0.1 L 0.9 L 0.1 L ph5-7 Surrogate: (2,2'-iminodiethanol-d 8 1 g) Wash milliqwater 100 ml methanol 20 ml Dehydration pressurized air Elution 25%anmonia aq. and methanol(5:95) 8 ml Concentration N 2 gas to 0.5 ml Volume adjustment Formic Acid:Acetonitrile (1:999) 10 ml LC/MS/MS SRM ESI+ 554

[1] 2,2'- ph 0.100 L 1 mol/l HCl Oasis MCX 1 g 0.100 L or 1 mol/l NaOH 10 ml/min + 0.900 L ph5-7 0.100 L (2,2 - -d 8 1.00 g : LC/MS/MS-SRM ESI- : ( g/l) [1] 0.037 [2] 0.37 100 ml 20 ml 25% : (5:95) 8 ml LC: waters 2695 MS: waters Quattro micro API LC/MS/MS SRM XBridge Amide ESI+ 2.1 mm 100 mm, 3.5 m 0.5 ml (1 999) 10 ml 555