X線分析の進歩36 別刷

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1 X X X-Ray Fluorescence Analysis on Environmental Standard Reference Materials with a Dry Battery X-Ray Generator Hideshi ISHII, Hiroya MIYAUCHI, Tadashi HIOKI and Jun KAWAI Copyright The Discussion Group of X-Ray Analysis, The Japan Society for Analytical Chemistry

3 X X X-Ray Fluorescence Analysis on Environmental Standard Reference Materials with a Dry Battery X-Ray Generator Hideshi ISHII, Hiroya MIYAUCHI, Tadashi HIOKI and Jun KAWAI Department of Materials Science and Engineering, Kyoto University Sakyo-ku, Kyoto , Japan Kyoto Prefectural Comprehensive Center for Small & Medium Enterprises 134, Chudoji-Minamimachi, Shimogyo-ku, Kyoto , Japan (Received 4 November 2004, Revised 6 December 2004, Accepted 6 December 2004) X-ray fluorescence analysis on environmental standard reference materials has been performed by using a dry battery X-ray fluorescence (XRF) spectrometer with the combination of a pyroelectric X-ray generator and a potable Si PIN X-ray detector. This dry battery spectrometer detected K, Ca, Ti, Mn, Fe, Zn and Pb (~ hundred ppm order). Similar analysis with a commercial energy dispersion XRF spectrometer achieved the additional detection of Cu, Br and Rb. However, the limit of the detection was similar. This difference of detected elements is mainly due to the difference between characteristic X-rays from both X-ray sources and not due to the difference of intensities of excited X-rays. Thus, the dry battery XRF spectrometer has sufficient capability for XRF analysis on environmental materials as commercial spectrometers. [Key words] X-ray fluorescence analysis, Potable, Environmental samples, Standard reference materials, Dry battery X Si PIN X X 3 X Adv. X-Ray. Chem. Anal., Japan 36, pp (2005)

4 K, Ca, Ti, Mn, Fe, Zn, Pb Cu, Br Rb 100 ppm X X X 100 ppm X X 1. X X 1-4 X Amptek COOL- X X X Cd, Pb 5 Al Fe 6 Cr X Si PIN Amptek XR-100CR X X EDX NIES No.1 pepperbush NIES No.2 pond sediment NIES No. 8 vehicle exaust particles 3 X 100 mg 200 mg X Amptek COOL-X Si PIN XR-100CR X COOL-X XR-100CR 5-9, 11 X 90 COOL-X XR-100CR 3 cm 33 mm 33 mm, 3.5 mm % 200 ev

5 X EDX-700 X Rh 50 kv, 1 ma, 50 W X 10 mmφ X Si(Li) 10 mm 2 6 µm 25 mm Na-U 50 kv, 100 µa % 1 3. Fig.1 pepperbush X Fig.1a X Fig.1b X EDX a) Ca Kα Ta Lα Cu Kα Intensity (counts) 500 K Kα Mn Kα Mn Kβ Fe Kα Ca Kβ Ta Lβ Cu Kβ Ta Lγ Ar Kα Mn Kα Ca Kα Energy (kev) b) Intensity (counts) 2000 K Kα Ar Kα Ca Kβ Mn Kβ Fe Kα Zn Kα Rh Lα Fe Kβ Cu Kα Zn Kβ Rb Kα Energy (kev) Fig.1 a) XRF spectrum of pepperbush measured with the potable XRF spectrometer in combination of a dry battery X-ray generator and a Si PIN detector. b) XRF spectrum of pepperbush measured by using a commercial XRF spectrometer

6 X LaTaO 3 Ta Lα, Lβ, Lγ 8~11 kev Be Cu Cu Kα 8 kev 8 kev X Ta Lα, Cu Kα 900 counts Ar 2.96 kev X Rh Kα kev kev 1400 counts, 3500 counts X X X 8 kev 4 kev 4 kev X 8 kev X 8 kev X Ca Kα X X 800 counts 4800 counts Zn, Mn, Co, Ni, Cd K 1.51 wt % Ca 1.38 wt% Mn wt% Mg wt% Fe 205 ppm Fe Kα 6.4 kev Mn Kβ 6.5 kev X Fe Kβ 7.06 kev X Fe Kβ 7.06 kev X Mn Kα 5.9 kev 6.4 kev Fe Kα, Mn Kβ Ca Kα Ca Kβ Ca Kα K Kβ Mn Kα 6.4 kev 6.4 kev Mn Kβ Fe Kα Zn 340 ppm Rb 75 ppm Cu 12 ppm X X Cu Kα X Zn Kα Cu Kα, Ta Lα Cu Kβ, Ta Lβ Zn Fig.1a X Rb Rh Kα Rb Kα X X Rb Co 23 ppm Ni 8.7 ppm Cd 6.7 ppm

7 X X X Fig.2 pond sediment X a b X X X Ta L 8~11 kev Cu Kα 8 kev 8 kev X Ta Lα, Cu Kα 700 counts X X Rh Kα kev kev 2100 counts, 2700 counts X Fe Kα X X 7000 counts counts Ar 2.96 kev 1500 a) Fe Kα Fe Kβ Intensity (counts) Ti Kα Mn Kα Ca Kα K Kα Ar Kα Ta Lα Cu Kα Ta Lβ Cu Kβ Ta Lγ Fe Kα Energy (kev) b) Intensity (counts) Fe Kβ Ti Kα K Kα Ca Kα Ar Kα Rh Lα Mn Kα Ti Kβ Cu Kα Zn Kα Pb Lα Fe Kα SUM Rb Kα Energy (kev) Fig.2 XRF spectra of pond sediment measured with (a) the dry battery XRF spectrometer and (b) a commercial XRF spectrometer

8 Fe 6.53 wt% K 0.68 wt % Ca 0.81 wt% Ti 0.64 wt% Mn 770 ppm Cu Kα, Zn Kα, Pb Lα 10.5 kev Rb Kα X Cu 210 ppm Zn 343 ppm Pb 105 ppm Lα Rh K Rh L 2.70 kev, 2.84 kev Pb Mα 2.35 kev M L X Pb Lα 10.5 kev Ta Lγ 10.9 kev Si 21 wt% Si Kα 1.74 ev Si Kα Al 10.6 wt % Al Kα Fig.3 X X 8 kev X 800 counts X Rh Kα kev kev 1700 counts, 4700 counts X Fe Kα X X 1200 counts counts Fe Zn wt% Ca 0.53 % Ti, S K wt% Zn X Zn Kα Pb 219 ppm Mn Kα Cu Kα 67 ppm Br Kα 56 ppm X Mn Kα X Br Kα 11.9 kev Pb Lα 10.6 kev Pb Lβ 12.6 kev X Pb Pb Mα 2.35 kev S Kα 2.31 kev 200 ev X X Pb Lα,β Pb S Fig.2 Pb Lα Pb Mα 3 Pb Lα 2.3 kev 1/2 2.3 kev S Kα

9 1000 a) Fe Kα Ta Lα Cu Kα Intensity (counts) 500 Ca Kα Fe Kβ Ta Lβ Cu Kβ Zn Kα Ta Lγ Ar Kα S Kα Ca Kβ Ti Kα Fe Kα Energy (kev) b) Intensity (counts) Ca Kα Fe Kβ Zn Kα S Kα Ar Kα Ca Kβ Rh Lα Mn Kα Ti Kα Zn Kβ Cu Kα Pb Lα Pb Lβ As KαBr Kα Energy (kev) Fig.3 XRF spectra of vehicle exhaust particles measured with (a) the dry battery XRF spectrometer and (b) a commercial XRF spectrometer. S Pb L Pb Lα,β Pb Lβ 1:1.1 Pb Lα Pb Lα As Kα 10.5 kev X S X Zn Pb Lα, β Table 1~3 X He * X X

10 Table 1 Summary of dry battery and commercial XRF measurements for pepperbush and the abundance of elements. Elements Dry Battery XRF Commercial XRF (air) XRF Measurements (He) Certified Values (ref. 10) K 1.51 (wt%) 1.38 (wt%) Ca 1.0 (wt%) 1.51 (wt%) Mn 0.25 (wt%) 0.2 (wt%) S (wt%) Si 390 (ppm) Fe 310 (ppm) 205 (ppm) Zn 320 (ppm) 340 (ppm) Cu 110 (ppm) 12 (ppm) Rb 44 (ppm) 75 (ppm) Sr 31 (ppm) 36 (ppm) Table 2 Summary of dry battery and commercial XRF measurements for pond sediment and the abundance of elements. Elements Dry Battery XRF Commercial XRF (air) XRF Measurements (He) Certified Values (ref. 10) (*Reference Values) Si 6.0 (wt%) 21* (wt%) Fe 6.6 (wt%) 6.5 (wt%) Al 3.7 (wt%) 10.3 (wt%) Ca 0.84 (wt%) 0.81 (wt%) K 0.66 (wt%) 0.68 (wt%) Ti 0.59 (wt%) 0.64*(wt%) S 0.3 (wt%) Mn 980 (ppm) 770* (ppm) V 500 (ppm) 250* (ppm) Zn 470 (ppm) 343 (ppm) Sc 250 (ppm) 28* (ppm) Cu 210 (ppm) Pb 105 (ppm) Zr 90 (ppm) Rb 45* (ppm) X X X Rb, Br X X

11 Table 3 Summary of dry battery and commercial XRF measurements for vehicle exhaust particles and the abundance of elements. Elements Dry Battery XRF Commercial XRF (air) XRF Measurements (He) Certified Values (ref. 10) (*Reference Values) S 0.60 (wt%) Ca 0.52 (wt%) 0.53 (wt%) Fe 0.51 (wt%) Si 0.18 (wt%) Zn 0.15 (wt%) (wt%) K 0.10 (wt%) (wt%) P 340 (ppm) 510* (ppm) Ti 420 (ppm) Al 380 (ppm) 3300 (ppm) Sc 220 (ppm) 0.55* (ppm) Pb 250 (ppm) 219 (ppm) Cu 150 (ppm) 67 (ppm) Mn 130 (ppm) Sr 95 (ppm) 89 (ppm) Br 110 (ppm) 56* (ppm) As X Fig.3 Rb Kα, Br Kα Ti Kα Ti Kα X X X X X X 6.7 ppm Cd Cd Cd Lα 3.1 kev Rh L X X 5 Zr Zr Cd K X

12 4. X Si PIN X X 3 X X K, Ca, Ti, Mn, Fe, Zn, Pb X Cu, Br, Rb 100 ppm X X X 100 ppm X ( ) 1 M. Terasawa: J. Phys. Soc. Jpn., 25, 1199 (1968). 2,, : X 29, 203 (1998). 3 J. D. Brownridge: Nature, 352, 287 (1992). 4 J. D. Brownridge, S. Raboy: J. Appl. Phys., 86, 640 (1999). 5,, : (Bunseki Kagaku), 53, 183 (2004). 6, : X 35, 81 (2004). 7 H. Ida, J. Kawai: Anal. Bioanal. Chem., 379, 735 (2004). 8, : (Bunseki Kagaku), 53, 753 (2004). 9 H. Ida, J. Kawai: Anal. Sci., 20, 1211 (2004) H. Ida, J. Kawai: X-ray Spectrom., in press (2005)

% 1% SEM-EDX - X Si Ca SEM-EDX SIMS ppm % M M T 100 % 100 % Ba 1 % 91 % 9 % 9 % 1 % 87 % 13 % 13 % 1 % 64 % 36 % 36 % 1 % 34 46

% 1% SEM-EDX - X Si Ca SEM-EDX SIMS ppm % M M T 100 % 100 % Ba 1 % 91 % 9 % 9 % 1 % 87 % 13 % 13 % 1 % 64 % 36 % 36 % 1 % 34 46 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