View
219
Download
0
Category
Preview:
Citation preview
����������� �����������
��������
SPring-8���������������� 5!"(2011. 10. 14)
Cd
CdCd
CdCdCd
Cd
CdCd
CdCd
Cd CdCd
#$%&'()*+,-./�0�
1 23456789:;<=> 1
Cd, Zn, Pb, Cu…
?@A�B.A"CDE&
FGHIJ:;K;
L 95000MJN *
* Phytoremediation�of�toxic�metals,�ed.�by�I.�Raskin,�B.D.�Ensley,�John�Wiley�&�Sons,�Inc.�(2000).
OP:QR<STUV
Arsenic Hyperaccumulator Pteris vittata L.
WXYZ5[\WX�]^[_`;a;H
bcd#$�e&_fgh
Oijk>ilmnTKHopq
Cadmium Hyperaccumulator Arabidopsis halleri ssp.gemmifera
( Matsum.) O'Kane & Al-Shehbaz
23456789:;<=>�r&s23456789:;<=>�r&s
Cd As tu)vwtu)vw300 kg 300 kg UVxyz{UVxyz{270 g270 g
|} �~)2Ql
���U%#$%&'z���
URa����K�<�w�����80��"��y�\���URa�_��f�h����
������23456789:;<=>
S. Dushenkov, et al.: Environ. Sci. Technol., 1997.
U, 137Cs, 90Sr, 3H�����s
URa�%���URa�%���UU����������(1997(1997� ¡¢£¡¤� ¡¢£¡¤))
6¥�¦§y�URa�%&'z¨��
2¥�©\xty'URa��ª\«¬�
pH�®�¯v%°±�
�²n;I³%�´<Zµ4>��¶'·¸¹ºx»(¼½�.
¾¿²H:ÀIl²n>,2345Á�²>,7l²nÃ4>.
�ÄÅ�ÆÇÈÉÊËxÌÍ(ÉÊËÎÏ�
ÐV�Ñ
��¸Ò
ÉÊÓ
Cd
Cd
Cd
ÔÊ
ÉÊÕÖ׿�ØR
cell
PC-Cd
Cd Cys
Gly
Cys
Cys
CysGluGlu
Glu Glu
SS
S
S
Cd CysCys
GlyGly
CysCys
CysCys
CysCysGluGluGluGlu
GluGlu GluGlu
SS
S
S
ÙÚ�Û�%Ü(��xÝÞ
��ß\Ýààà
áâßãwäåæ(��_çèéwêëìí�\îxïðæ(�èñ�<>jÂ5Â>��ß"��\
��
��ß��ß
òó ��ßïð�ôD
S
N
õd�>Àxö�÷íçø��ù!úû%�üõd
��ß�Äý
þb¶®çb'ß�2��jZ
���ç�ÉÈ�����ì�����%Üìí( ���_��wî(
�b'���ç���%�´
�R4jÂ�;q�ïð_����������ç47;Q>À��_��
����ì X�!w�"#':ÃI$;%&%�´�Ä�ÐV�'()*ç��+Ò���XAFS��"
,-.�/ß%\0�1(
�Z2>���/ßx3æ(Û�%&'����4��x5f6�jÀ�p>H�7�
89IZÄ�%�´����:¨�
��ß;< 1��ß;<��=xÝ >?@\'A&B%&'(1
C?@Tb:ÃI$;¨�&xD<÷í�EãFwïðyzy!A
(G0$�HI)��ß%Jðyze&æ(;<(G0$�HI)
K?@T��ß%e&æ(LhwD<÷í�õd�>À%�´;<
�M&�HIw�îNïO) s Photon Factory
P?@TÖ>QQ6;lßR%S�yzD<÷í�;<
�ty'��w�T;<) s SPring-8�ESRF, APS
U?@T6;m;�»AxV"W&%Xyz�¶®��ß%ïðæ(HI
�H24.3ì}&YZ[) \]�Yï�
s X�^_��6;m;�SACLA"ç:ÃI$;!`T�4��j(ERL)
��ß�ab��ßc���Ý1947dxÖ7�K�e(�f�EãFç��<>jÂ5Â>wg�z �
:ÃI$;:ÃI$;bb
:ÃI$;:ÃI$;XX
ß�ñø\$h��î÷
?i���ß;<
19861198719881199419941
19861198819891199419961
19871198919911199719971
jk
D<
e&
dlmÏ
6 GeV56n844 m
7 GeV68n1104 m
8 GeV62n1436 m
:ÃI$;
�;q�4>
ùø
o;Â�918K ÀIp;qI�r"
� :ÃI$;s
ÖIt>u��"
ô�àD�
vw �xyz{
<I|
<Ié}
ESRFEuropean Synchrotron Radiation Facility
APSAdvanced Photon Source
SPringSPring--88
;<~�
P?@��T��ß;<
s��#$��wÝààà
?@A
SEM-EDSçô��ßAçICP-MS�AES��à��h�CDx»0ðî�!!�+Ò_�z�'à���:�_�'à���x»(��S7;Q
��ßàÉÊ6�I����:�àÆÇ4�%�÷�����à�ÐV����_��à�vÐV�����àb:ÃI$;�ßX������SPring-8"
��ß%�Ae�
���%�z�Í(\
��S7;Q
l6Y������+�*ÆÇ�5�4Y;q"
ô��
Ý�î�÷í���
Cl��
���ß
XX�x»()*�x»()*
�x»()*�ßX��ïðôD
X���ßX�"�ïð
$hx��%ez(\ÐVx�5�$hx��%ez(\ÐVx�5�:ÃI$;��ß��_ïðæ(�:ÃI$;��ß��_ïðæ(�
In-vacuum undulator
Sample
XY slit
Si(111) monochromator
Si(Li)-SSDor SDD
Kirkpatrick-Baez (K-B) mirror
XY slit
SR facility: BL37XU, SPring-8 (undulator)The flux of the photons: ca. 108-109 photon s-1 at 37 keV.Focusing optics: K-B mirror (fused silica coated with Pt)Focal length: 250 mm, 100 mm, Average glancing angle: 0.8 mrad.Monochromator stabilization (MOSTAB) systemBeam size: ca. 1 µm x 1 µm with K-B mirror
μ-XRF47;Q>À & μ-XANES<Zµq
Cryogenic N2 gas
ijk>ilmn�in vivo XRF47;Q>À
�;qk4Ø 50 µm�50 µm
XANES EXAFS
s��� ¡�� ¢£¤¥¦§Z¾j5I
8550 9100 9650 10200
Energy /keVN
.I. (a
.u.)
�`¨
©ª©
A = ln(Io/I) = �t
« ¬
Z¾j5IìÜìí(Û�XANESTË®j¯ì�'�úû,6>H°�±²x³´.EXAFSTX�x»�zµ¶�æ��\çù·�ô�x»�z¸¹÷í(��\�º»f�x»�z*�÷í(\¼.
2½ 3½
4½ 7½
Mn�¾�¿_2ç3ç4ç7½we(���XANESZ¾j5I
¾�¿_�îN�(x´íz�`�ÀüÁ_0_b:ÃI$;Âx<25
KMnO4Z¾j5I��`¨»0X:ÃI$;Âxpre-edge 2;j_e(ÃMnO4·Ä_U�ÄÅI%Æ(\îx
Äýh2;j÷Ä�³��%ÇÈwî(
��s\yzÝçÉ�ÊÈË�Êx&'ìí(R>Ì>¾�$�MnxÌÍ(Ë��xÍA¾�¿Î�%ÏA��x&'ìíz'(
Ðj�Ñ$%&'�29�µ9>Àx»0�Ñ$�Ò]Ó%Ô�ìí(
¤¥ÕÖ§:�s
�×�¾�¿�R>Ì>·Ä�XANESZ¾j5I
EXAFSØÙ�*R)*Úô���(Û�Ü)ß��(ß��ñ)\yz��
K®L®
ÝÞ5j¯
4n>�j¯
jÛ�Ü
Û�Ü
E0
E
Energy 1ô�wÝï¸
ßàô�x»0¸¹÷ízá�zN(
ñâìã�¸\äå%:��@(
XANES
EXAFS
X�
X��`ô�
ß��ñ¸¹ô�
äå r
ß��ñ
EXAFS Extended X-ray Absorption Fine Structure
æLô���`¨x³´y�:ÃI$;�X�%ç�
Ä��Ë®��%)*àèå
UÚéÚxêvyçßàô�x»0¸¹
ßàô�x»�z¸¹÷í�����ëxUÚéÚxêv
ìÚ¸¹÷íz�`ô�xí®î�zN(¹��Ò]
��ô��ù·�ô��¿Èc�!w�äå%ï��@(
ðx�&yz'(��ß;<
�SPring-8(Super Photon ring -8 GeV)BL37XU ààà ñ-XRFKlÐ47;Q>À�ñ-XANESçñ-XRD"
�PF(Photon Factory)BL-12C ààà XAFSBL-9A ààà XAFSBL-4A ààà ñ-XRFKlÐ47;Q>À�ñ-XANESçñ-XRD"
�PF-AR(Photon Factory-Advanced Ring for Pulse X-rays)NW10A ààà XAFS
8 GeV
2.5 GeV
6.5 GeV
b:ÃI$;�ßX���_��
21
4Ã��KHopq��4Ã&§òxKHopq�CdSO4"%óEyçHCl%E�zpH%4.7x°±y��ô�õ¼öË��ß÷%&'z�11��øø�ù30ú�û25ú�üýþ"���þw¦§yz�3��ìx`�y��
��%Æ0�yçKHopq��v%�����
5.11.0C3.70.3B1.20.15A0.110���
����Cd�®/ ppm§ò�Cd�®/ ppm��~
� ¦§y����4Ã��Tøn�"�Cd�®
Fig.1��4Ã�×Q5Â>47;Q>À
107Cd×Q5Â>47;Q>À
Cd%��yz20��ì�CdÝ�°²�÷í��w��ìíz'�
23456789:;<=>x3æ(��
����:ô��eye, 2006.S. Fujimaki, et al.: Plant physiol., 2010.
4Ã_4Ã_CdCd%�`æ(ë�%ðî�!!���%�`æ(ë�%ðî�!!���
×Q5Â>����"%��æ(×Q5Â>����"%��æ(����¯Ä����¯Ä107107CdCd%#$°��%#$°��
áâ�ÖIl4qw�m���áâ�ÖIl4qw�m������:����:� 2.4 mm2.4 mm
2�mm
K Ca�K� Mn
Zn Fe CuCu CdCd
Imaging�area:4.0�(V)�mm�4.4�(H)�mm(��ÐV) PF�BL�4A3.8�(V)�mm�2.56�(H)�mm�(Cd) SPring�8 BL37XU
mm
mFig.�����ò
(m:��� ,b:!Õ,r:"ù�� )
b
r
���:����:� 4040 -- 5050 µµmm
øn���§#Ô�Cd�® 1 ppm���Cd�® 5 ppm
0
20
40
Cou
nts
Fe
Zn
0
36.5
73
Cou
nts
Cd
0
24
48
Cou
nts
Mn
0
68.5
137
Cou
nts
Rb
0
26.5
53C
ount
s
Beam size : 50 �m � 50 �m
Measurement points : 101 � 41 points
Exposure time : 2 s/point
)*+$õd��YÁ
1.�%>P>QtÁ (Scopelophila cataractae)�1)
2.�U=pl>tÁ (Funaria hygrometrica)�2)
•É&hve�0112%�'%().•SEM�EDS�*��'ÝÉÊÕxõd÷íz'�.•¾�+Ôw'_��x,�÷í(.
•-%b�®xõdyz'�.•.�0���°�´&_/0÷í(.•*%óEì�YÁ_�x12y�.
1)�K.�Satake,�et�al., J.�Bryol,�15,�353�376�(1988).2)�M.�Itouga,�et�al.,�Bryological Research,�7,�84�85�(1997).
YÁ�ð3YÁ�ð3
ï4
Ê�Ä��Ä
Ê�ô5Ä
67
�v§#�8A_9À÷í�
Samples• %>P>QtÁ (Scopelophila cataractae):�w;Æy���Ä(a) �w<0 (control)(b) -%óE (+ Pb)(c) ¾<0wCu%Æ0�'�ì�-%óE
(- Cu, + Pb)
• U=pl>tÁ (Funaria hygrometrica):�w;Æy���Ä-!�Ý*%óE
ô5Ä-!�Ý*%óE ô5ÄÉÊ
��Ä
1mm
��Ä
=>?@�@A��Ä�µ-XRF£B�?@C@
2mm
0.5mm
10 mm
Cu
Pb
(a)�control���������������������������(b)�+�Pb (c)�–Cu,�+�Pb
Low HighXRF�intensity
•CuÝ:�ì;Æ÷í���Ä��xb�®xõd÷íz'�.•Pb%óEy�\���Cu\�ëx�xõd÷í�.•¾CDì����Cuݯ�.���v�CuÝ���DxE�z'�.
SR�facility:�BL�4A,�Photon�Factory,�KEKBeam�size:�3.5�μm�x�5.5�μmMeasurement�time:�1�s/point�
��ÄLeaf
Cu Pb(a)�control���������������������������(b)�+�Pb (c)�–Cu,�+�Pb
•Cu\Pb_ÉÊÕxõd÷íz'(ë�_�Fx���÷í�.•�DxÌ'z�b�®xõd.
Cu Pb Cu Pb
GÉ�ÐV�Ñ
�Cu 295
0control 4532
0
X�ray�energy:�10�keVMeasurement�areaControl:�138��μm�x�246�μm��Cu:�302��μm�x�392��μmMeasurement�time:��������0.1�s/pointSPring�8�BL37XU
����m
����m
��ÄÈ��µ-XRF£B�?@C@
�����
��� ���
���
���
���
�����������
Nor
mal
ized
Inte
nsity
(a.u
.)
Energy (eV)8970 90309000
��Ä�CuCu K-XANESZ¾j5ICuS
CuO(CH3COO)2Cu
control+�Pb
� Cu,�+�Pb
HI¾'�Z¾j5IxJz'(K
C
O
O
O
O
CCuH3C CH3C
O
O
O
O
CCuH3C CH3
YÁ��
Lç$h
������
�����������
Cu�O Cu�Cu
���
FT�m
agnitude��(a.u.)
R��(Å)0 1 2 3 4 5
���
���
�����
CuCu K-EXAFS:�ìÜìí�ÙM4�3¿
•YÁìÜìí�2;jÝCu-O*Ñ\CN.
YÁ��
Lç$h
Cu�CuCu�O
�Cu�+Pb
13000 13050 13100Enegy(eV)
Nor
mal
ized
Int
ensi
ty (a
.u.)
PbCl2
Pb acetatePb stearate
+Pb
PbS
PbO
PbSO4
Pb(NO3)2
��Ä�PbPb L3-XANESZ¾j5I
•YÁ���Z¾j5IÝZµÖ�>¾-xJz'�.•PbÝKIO`<I³\*Ñ.
YÁ��
Lç$h
-È*%õdæ(U=pl>tÁ
U=pl>tÁx-%óEæ(\�b�®xõd
*�b�®xõd2_ÎP(��x12"
)*+%Q�(#$�Yï
à ./���0�
)*+%Q��'#$�Yï
à ����RW$
ÐV��k4jI
ÐVSR�9�
z{TU�3&
��ß3Û�LVòW�<>jÂ5Â>��ß ãñXY $D�?i
ÁNZû ãñW[�¨&<>jÂ5Â>��ß
b\]^ ø_�`taf���ß �öb
c"dàefg �h���i��X��`�ßAjXAFS \c�´&j
klm�n Ö42;<;
���ßw:î�æop��p?iøn��ß��n XqfqI;6�jZ
�http://pfwww.kek.jp/indexj.html�http://www.spring8.or.jp/ja/
�Arsenic distribution and speciation in an arsenic hyperaccumulator fern by X-ray Spectrometry utilizing a synchrotron radiation source, J. Anal. At. Spectrom. 21, 321 (2006), A. Hokura et al.
�Micro X-ray fluorescence imaging and micro X-ray absorption spectroscopy of cadmium hyper-accumulating plant, Arabidopsis hallerissp. gemmifera, using high-energy synchrotron radiation, J. Anal. At. Spectrom. 23, 1068 (2008), N. Fukuda , et al.
� In vivo micro X-ray analysis utilizing synchrotron radiation of the gametophytes of three arsenic accumulating ferns, Pteris vittata L., Pteriscretica L. and Athyrium yokoscense, in different growth stages: Metallomics, 2, 261-270 (2010), T. Kashiwabara, et al.
���ßR4jÂ�;q�ßX���\XAFS:�x»(%>P>QtÁ�Scopelophil acataractae"ÄËxÌÍ('\-�õdx3æ(��T�����år, 42, 347-358 (2011), stì.
�����Tuv1î, 2009(9), 476-480 (2009).�����T��\�`,��\�`�2009(11), 1185-1187 (2009).�����ìT��ß, 23(2), 69-80 (2010).
)*+õd#$x3æ(��¹�à:w
xly��JASRI SPring-8"hz���2Ql"
{|��D�} ��~��"
tf��ç�ô��D�PSC"�Á ��DOWA:Y<Zµq�"ìf��çsôeC����"
�t�
����ç�U��ç�lä�ç�ô��çP����çbl�ÇçU�]��çst�C
���D ��D�"
©��e0_\A©�'!y�
Recommended