Review on Hair Analysis in the Wakayama Arsenic Case Jun KAWAI Department of Materials Science and Engineering, Kyoto University Sakyo-ku, Kyoto 606-8501, Japan Received 6 December 2014, Revised 29 December 2014, Accepted 31 December 2014 I review the hair analysis of Wakayama arsenic poisoning case, and discuss problems in this forensic analysis. (i) It has been said that two pieces of hair were analyzed, but I conclude that only one piece was analyzed. (ii) High concentration arsenic was said to be attached on the hair, but I conclude that the arsenic concentration was same level as those of ordinary Japanese. (iii) It was said that the discrimination of exogenous and endogenous arsenic in hair was possible by the line analysis of hair, but I conclude that the testimony has already been known by the witness to be fault before the death sentence. [Key words] Wakayama curry poisoning case, Hair, Arsenic X 2 1 3 1 2014 Kimura 1 2 3 p.895 1 20 1 M M T 5 606-8501 46 Adv. X-ray. Chem. Anal., Japan 46, pp.33-58 (2015) 33
4-7 1 1 2 99% 1% SEM-EDX - X Si Ca SEM-EDX SIMS 2 3 1 ppm % M M T 100 % 100 % Ba 1 % 91 % 9 % 9 % 1 % 87 % 13 % 13 % 1 % 64 % 36 % 36 % 1 % 34 46
SPring-8 X SEM-EDX SIMS SIMS SPring-8 8 3 1 7, 9 SPring-8 KEK PF 400 2 2 1 2 4 63 KEK-PF 1998 12 1 2 5 10-14 46 35
10 11 12 13, 14 5 15 16 2.1 10 I 3 mm ICP-MS 1998 10 20 1a 11 1a I 3 mm 11 ppm 17 2000 8 9 1999 2001 12-14 1, 3 2 2002 15 1998 2000 8 17 12 1998 11 1999 2002 4 2002 12 7 2000 8 2 1 3 2 I 11 ppm µg/g 1a 2 1998 12 1999 2 6 2000 4 2000 8 2000 10 2002 4 2002 12 KEK-PF 98U004 16 17 24 2001 15 3 36 46
10 a 11 0.08 / = 80 ppb p.19 1 11 = 11 ppm p.20 2 3 b p.21 p.22 54 1 ppm 78 81 2 11 ppm c 1 a I 3 mm ICP- MS 10 b 16 c 3 3 46 37
p.22 78 6 4 1 3 p.23 1a I 78-81 mm 11 ppm 15 cm 1 mg 18 3 mm 18 mg = 0.02 mg 11 ppm 0.02 mg 11 10 6 = 2.0 10 10 g I 1 1a 8.7 10 10 g I 10 8.7 10 10 g 100,000 10 4 g 2.2 12 1998 12 16 KEK-PF 4A BL-4A 4 mm X 4 2 30 37 17 p.62 10 12 9 p.72 12 11 12 15 cm 1 mg 18 3 a, c 10 cm 50 mg 2N- 2 ml 100 3 12 2 30 30 cm 15 cm 50 3 12 38 46
3 0.5 1 ppb p.33 3 3 159 ppb 69 ppb 3 32 ppb 37 ppb 3 90 ppb 60 159 ppb I 1/100 80 ppb 159 ppb 1980 19 110 230 ppb 1988 Yamato 20 100 140 340 ppb 7 159 ppb 3 As III 19 30 70 ppb 3 1980 1998 19, 20 19 5 3 3 4 3 3 90 ppb 3 5 21 19 3 5 6 3 900 ppb 53.2 ppm 5 200 ppb 124 ppm 15 3 50 ppb 30 70 ppb 5 120 ppb 80 200 ppb 3 As 3 + attached to the hair through exogenous contamination remains so attached to be slowly oxidized into As 5 + 19 5 3 5 20 3 11 ppm 5 39 ppm 3 30 70 ppb 15 15 5 120 ppb 3 3 19 3 46 39
ppm 100 1000 ppm 3 ppm X 22 ppm 23 DMA 100 0.020 DMA 37 17 p.76 3 12 0.020 100 0.026 0.029 0.031 0.037 ppm 3 1 ppb ppm 3 10 ppb 19, 20 3 1 4 DMA 10 ppb 1 1 3 3 3 2 3 pp.395-396 DMA 3 40 46
1 I 100 10,000 1c 63 37 17 p.83 63 X 63 SPring-8 SPring-8 43 24 p.29 2.3 11-14 1999 3 2000 3 46 41
2000 8 2000 10 15 16 1999 2001 98U004 KEK-PF BL-4A U 98U004 1999 2 6 3 120 98U004 2001 15 X X 2000 4 16 4 5 1b 75 80 mm 65 75 mm MA DMA TMA DMA DMA 42 46
a 2 KEK-PF BL-4A a b 16 8 9 b 1a 1a I 3 mm 3 mm 1 98U004 1999 6 16 1999 2000 4 2000 8 10 2 2 3 2002 12 11 2.4 KEK-PF Photon Factory News 4 1999 8 Photon Factory News 46 43
Vol.17 No.2 5 98U004 97G172 Web 25 6 5 5 BL-11B 98G120 BL-4A 1998 12 1999 10 4 4 1998 12 2000 12 BL-4A Photon Factory News Vol.16, No.4 1999 2 Vol.17, No.1 1999 6 Vol.17, No.2 1999 8 Vol.17, No.4 2000 2 Vol.18, No.1 2000 5 Vol.18, No.2 2000 8 Vol.18, No.4 2001 2 1998 10 12 1999 1 2 1999 4 7 1999 10 12 2000 1 2 2000 4 7 2000 10 12 A B C D E 5 1999 5 13 9 5 17 9 BL-4A 44 46
6 Web 25 97G172 X 98U004 98G187 2 98G391 00G336 A B C D E 5 A 12 1998 12 16 1 KEK-PF BL-4A 3 37 17 p.80 SPring-8 KEK-PF 12 3 1 1998 12 KEK-PF 13 4 2 1998 12 14 16 X BL-4A X 12 7 4 5 C 12 12 3a 3a 0 10 cm 10 cm 4 mm X 0 mm 96 mm 0 100 mm 2 3a 1 2 52 mm X ULD LLD 1 X 46 45
1 1 XY 4 mm 3 mm X 1 X 200 4 mm a 0 mm 10 cm 1 200 5 cm 1 3a 3c Kα X X b c d 3 a 12 4 mm b 13 1 mm c 12 3a d 12 13 46 46
3c X 12 16 mm 33495 16 20 mm 55612 X X 3a 1 5947 501 804 5947 1 13 C 3b 3b 1 mm 2 3a 3 2 mm 52 mm 1 3d 3ab 3 3a 17 12 1 B 1999 2 5 9 2 11 9 2 8 9 9 M 97G172 98U004 5 120 2 C 5 13 9 5 17 9 4 98U004 97G172 13 5 17 1 mm 12.2 kev 12.9 kev X 1 50 1 mm 1 1 2 3 1 1 13 12 43 24 p.40 p.41 A 46 47
63 1232 26 p.2 12 13 1 2 3b 45 mm 59 mm A C 45 mm 1 50 3b 15 0 45 mm 5 5 13 9 5 16 24 5 17 0 9 9 2 25 mm 7 X 12 X 5 X X D 6 22 9 6 26 9 4 98U004 98G187 98G391 E 10 10 9 10 15 9 9 9 24 4 98G391 98G187 5 1 14 14 10 13 1 mm 12.25 kev X 1 50 1 mm 1 A E 3 97G172 X 98U004 C 98G187 2 E 2000G336 48 46
6 2000 11 21 9 22 21 2000 12 8 9 11 9 2 A E A E KEK-PF 4 / 400 1600 2.5 A E 1a 3ab 7 X 7 Web i vi i 12 1 3a X 27 Appendix D 30 X SEM SEM SEM 3a ii 12 A 1 1 1999 2 B 5 120 4 1 2 46 49
2 120 iii 5 C B 4 20 5 5 13 5 mm 1988 Yamato 20 1 C 12 A 4 mm 1 mm 45 60 mm 5 C 96 12 2 13 63 4 1 2 16 B E 1999 2000 16 A D 2 2 iv 5 6 D 96 v 12 A 5 C 10 E 96 5 X C 98U004 98G187 98U004 2 98G187 5 vi 98U004 2 9 9 48 5 13 9 36 6 22 9 36 120 6 1998 12 1999 10 a X b c 5 3 d 4 mm e X f 1 mm 3 2 d e 50 46
f 1 3 13 5% 28 KEK-PF BL 4A 29 13 kev X X 1.5 63 13 X 7 4 Kα Kα 2.3 kev 0.1% 7, 9 X 4 5 C 1998 12 A 5 30 X 7 4 Kα 100 ppb < I 10 ppm < 0.1% 1 2 100 1 ppm 1,000,000 1 1 ppb 1,000,000,000 1 12 37 4 16 46 51
5 1998 12 16 KEK BL-4A 30 17 13 14 I 2 13 4 63 4 2 I 100 ppb 10 ppm 0.1 % 100 3 10 10 g Appendix 2 mm 52 46
10 12 g 2 10 10 g 3 3 µm 1 11 µm 50 1 1 PM 2.5 PM10 PM 2.5 I 10 9 g 1 10 10 g 3 1 159 ppb 100 7 140 340 ppb 20 3 19 3 3 3 4 3 X X 43 22 p.29 SPring-8 4 2 2 1 3 2 KEK-PF 1 SPring-8 1 KEK-PF 46 53
1 I 1 1 KEK-PF A BL-4A LC-ICP/MS 1 Y. Kimura: Forensic analysis in the Wakayama Arsenic Case, Forensic Sci. Rev., 26 (2), 145-152 (2014). www.forensicsciencereview.com 2 86 (10), 96-103 (2014). 3 14 12 11 2002 No.1122 2003.8.30 pp.464 (1)-122 (343) (2003). 4 X X 45, 71-85 (2014). 5 Anthony T. Tu X 45, 87-98 (2014). 6 6 No.519 6 64-66 (2014). 7 27 (2), 111-123 (2014). http://www.oceanochemistry.org/publications/trioc/ PDF/trioc_2014_27_113.pdf 8 2009 http//www.courts.go.jp/hanrei/pdf/20090422180047.pdf 9 35 54 46
2014 9 15 2014 10 627 11 2 9 1999 11 652 10 12 22 1998 12 63 11 3 29 1999 13 1232 11 7 23 1999 14 1294 12 3 28 2000 15 2001 2002 http://research-er.jp/projects/view/127346 11 1999 2000 4 http://mhlw-grants.niph.go.jp/niph/search/nidd02. do?resrchnum=199900701a 12 2000 2001 4 h t t p : / / m h l w - g r a n t s. n i p h. g o. j p / n i p h / s e a r c h / NIDD02.do?resrchNum=200000759A 13 2001 79.200100953A http://mhlw-grants.niph.go.jp/niph/search/nidd00. do?resrchnum=200100953a http://mhlw-grants.niph.go.jp/niph/search/nidd00. do?resrchnum=200100953a 16 X 11 pp. 24-41 (2000). http://mhlw-grants.niph.go.jp/niph/search/nidd02. do?resrchnum=199900701a 17 37 12 8 9 2000 18 P&G http://oita-kaku.lolipop.jp/w_b_theory.htm Web 73 (2), 114-127 (1963) 1 mg/15 cm 80 µm 70 µm 19 Y. Yamaura, H. Yamauchi: Arsenic metabolites in hair, bolood and urine in workers exposed to arsenic trioxide, Industrial Health, 18, 203-210 (1980). 20 N. Yamato: Concentrations and chemical species of arsenic in human urine and hair, Bull. Environ. Contam. Toxicol., 40, 633-640 (1988). 21 M. Bissen, F. H. Frimmel: Arsenic - a review. Part II: Oxidation of arsenic and its removal in water treatment, Acta Hydrochim. Hydrobiol., 31 (2), 97-107 (2003). 22 X 2014 23 X X 45, 203-209 (2014) 24 43 12 10 4 2000 25 PAC http://pfwww.kek.jp/users_info/pac_proposals/ 26 24 3 23 2012 27 X 44, 165-184 (2013). 28 X 36, 301-305 (1987). 29 7 KEK-PE A 46 55
Elements Fluor. Y. 7 13 kev X K/L excitation prob. Kα emis. prob. Mass abs. coef. Product S 0.08 0.91 0.94 22 1.53 As 0.57 0.86 0.87 149 63 30 1170 11 2 19 1999 Appendix 3 3 90 ppb 3 1 50 1 1 3ab 90 ppb 3 A 2 mm 15 cm 1 15 cm = 1 mg 18 90 ppb 51-53 mm A1 3 As 9 10 11 g I 1 8.7 10 10 g 1 I 1 80 ppb 15 cm 1 8 10 11 g 2 mm 80 ppb 2 mm A2 A I 1 8.7 10 10 g 1 9 10 11 g 10 1/4 1 9 10 11 g A3 I 10 4 g 2 50 1 A1 50 4.5 10 9 g 50 1 2 mm KEK-PF 1 3a 1/50 56 46
A As 2O 3 3.74 g/cm 3 = 1.10 1 As 76% As 2O 3 100% As As 2O 3 A4 A4 d 3a 48 52 mm 3b 51 53 mm 4 52 mm 1 12 13 4 4 Fig.3a 48 52 mm X 80 ppb 4 4 2 KEK-PF BL-4A MDL sub-ppm ppb 48 mm 52 mm 2 As 1 2 As 2 46 57
As 1 3 4 2 1998 10 4 20 As ppm As 3a b 3 2 3 As KEK-PF 1 3 4 2 3 4 58 46