56 J. Hot Spring Sci. /2 2+ῌ32 ,**2ῌ῍  




789+ :;<=+ > ?+ @AB, C<D- ,*

0,0  ,*

2,*

Behavior of Rare Earth Elements in Mixing of Di#erent
Type Hot Spring Waters : Acidic Saline Hot Springsin the Northern Beppu Geothermal Area,
Oita Prefecture, Japan
Tetsuya SANADA+, Nobuki TAKAMATSU+, Hajime YAMASAKI+,
Kazuhiro AMITA, and Shinji OHSAWA-

Abstract
The rare earth elements (REE) concentrations of the hot spring waters in the northern
Beppu geothermal area were determined to clarify their behavior in the hot spring mixing
system. It was clariﬁed that REE was removed from the H-SO. type hot spring waters by
the mixing of them with Na-Cl type hot spring waters. It was conﬁrmed by the experiments using the two type hot spring waters that Fe and Al concentrations decreased withdecrease of REE concentration, and the light REE (LREE : La, Ce, Pr and Nd) was removed selectively from the H-SO. type hot spring waters. The LREE may be substituted
with the elements in alunite and/or co-precipitated with hematite during the mixing
process. The REE is very useful tool for interpretation of the mixing process of the hotspring waters.
Key words : Beppu, rare earth elements, hot spring, geochemistry, ICP-MS+

 ,1.ῌ**1,  ,ῌ,ῌ+ + Department of Chemistry, Faculty of Science, Toho University, Miyama ,ῌ,ῌ+, Funabashi-shi, Chiba ,1.ῌ2/+*, Japan.
, ! *+*ῌ2/*, "#$% +ῌ+ , Department of Earth Science and Technology, Faculty of Engineering and Resource Science, Akita University, +ῌ+Tegata Gakuen-machi, Akita-shi, Akita *+*ῌ2/*,, Japan.
-&'()*+, !-)*./ 21.ῌ*3*- 01234 - Beppu GeophysicalResearch Laboratory, Graduate School of Science, Kyoto University, Noguchibaru, Beppu-shi,
Oita 21.ῌ*3*-, Japan.

81     

ῒ



ῑ


 REE  !"#$ %&'
 REE (# )*+ H-SO. ,- Na-Cl ,."/.01 LREE : La, Ce, Pr 23 Nd 45
6789/.-54.&:# )95
-(#;
 Fe 23
Al - LREE ..<=>"/. 23 LREE -?@AB9/. C,
 D#E!FG0H"(# //.45 I#0 LREE -JK
LMN .$O"4 PDQRSTMN.U%( 6789.V(# REE Q
WX"Y0& &Z'0P@ REE [T\] D^W("/.2@)I#-2@H0_/.-`4:#
a\b\c :    de ICP-MS+ῌ ῏ ῍ ῐ ῎
*+,-Q .SfS45g/,-h0 ῌi12jk 2*Wl&

.&m2@<#589 no *p3iq_s6`. t59^D 7tu vw5 +331 /9B0%)r452:^)r4q8pxy

VQz9,- { +33* ; 5 +33. ; Sturchio et al., +330 ῌ|:};< Matsubaya et al., +31- 5- D59^_# ~= -(x/>2@z9,-&5?@,-CD^<As )95
D5 +33. )0<E0-BC89^@ 7tu

REE  "-F`92&:# ~0Q G REE HIq-JHIK-`9^D 7tu 
5 ,**, - `-L||M

 REE  "NQAsQ&D Kikawada etal., +33/ ; OP5 +333
REE QdeI#0 M]Q+-_sh0"RD 0P@ )

M.S&--9&Z'.(^

D59^@ TU)I#V"Y0< &V&N.&/.-W89
Sanada et al. ,**0 QP( ῌi12jk 2@

X  -* = `# REE 6CD^ !

<#589 REE .L|M].2 54(# "&`¡ SfSo62@ |eL¢£¤-¥5-6e(*^¦L|.&@ /9-§¨|e©Yª2@L|.&@L|M]-Z(^ X i1 «
i .L||M.[\02jk

2@1



LREE : La, Ce, Pr 23

Nd -*p89/.54(# B# 5 ,**0 Q]^_`a¬­

L¢b®45)p"|M¯P)°c REE CD^K( L¢P45def±²)g"B0I#0 REE Q³)¯P)g2X. pH Y´c|eh%ij,2U%k 2@ ¯P456789^D/.54(# /95*+Q|M¯P REE - ῌi12jk 2*W ³)45)g2X h5.U%k &mkµ&I# !"Y0& 0P/.¶(#l0Q % -&/.0m59^DD^

·l& %nª¸59 Na-Cl ,. H-SO. ,-°0( H-Na-Cl-SO. ,|M¹º »,89; REE  REE [T\]0W(( REE - %l&q)I#&m !"Y0& &Z'&@o4m4K:#82

-¼½

 /2  ,**2  ,  
,+  ,++  ,**,  2    ! "#$%&' ()*")+,-  Na-Cl . /0()&123 &456"789 H-SO. .

  ); <,)=>5?6" H-Na-Cl-SO. .89@A B C: D

Eῌ F +330  ! ,* G2?H>"  IJ  
 N;:OM  PQLR  S  TU 

XY 

:

K  %LM

TU & 

VWR

Z[  A \  ]^S  B \  _`abM  WR   cRd  De fghijklm  nop  C \ q" Na-Cl . rc s3tu:"v wxmkyz{ |M }5~c  *4",)23 Fig. +! ": )(v8?4"xazk# ,$45

>" pH, 8% ORP =;%&' EC   }5H>" REE=;()"

  *../ mm lm3"}5«¬4 *.*+ mol L+k¡¢£¤¥k¦§k¨©ª8*­/=® ¯°4" ±² ³"4"%

LM=;S    ´~8µ =*¶ + , -·.8
 3?6¸¹/º"v 0¶#»/¼  ½~ 0¶4"

Fig. + Sampling sites (arabic ﬁgures) of hot spring waters in the northern Beppu geothermalarea, central Kyushu, Japan. Sample names are shown in Table -.
 + 


83  

 





,+, 

 REE ῌ'"$%(!"#$%&)*+$%,-./0% 1( &'"$%3456 ,**,

2

2 789: ;< REE !6=.!

,, >  :!? " @AB/ # C 

DE " FG $ +!@ !% E & ? " '( 5FG $TAMAPURE-AA- +** 6H! REE )IJ@ ICP-MS 'K*L!)I+J +* mg L+SPEX Industries Inc. $ 6MN:/H! ?",$ MN OPQRS-./@%E01TUVWX$ Milli-Q %E$234 6H!
,,-+ REE  Na K Ca, ;< Mg, 56@YZ[DD&\ HITACHI $ +1*ῌ+* ]
^_`a Cl SO., Br ;< NO- 7&56@_`abcdefPg Dionex $ QIC
Analyzer SFe 56@DD&\ HITACHI $ U--,+* ] Al- 56@ ICP-AES SEIKO $ SPS-*** ] 6$h$H!
,-, REE 
REE 7&56@i,j] ICP-MS ELAN 0+** ] 6H! kPldemn;<o]

pqP_rm@sOPQ$( ?8+J@tUQuvwxybVak6H/pqP_rm
9::! 56z&;<@=)IK*:/ +*-Rh 6H {|56+J Rh 7& +*mg L+ -%} + mol L+ >~6H/MN:! ?@@ ICP-MS 'K*L!)I+J6 *ῌ+ mg L+ -%},$:!
,. 

?8 pH  1 AB ( Fe  Al 6*+-H

@ REE 7&j/CH

&'"$% +! Na-Cl ]DE@ 7&H1" $A%FG
HZ_`a-DHIJ-%! ICP-MS 6H!56(@++56?8
A%1@K(%  me6H!LM7NO#$  REE 6?P#$/H%
" ,**, 1(@ QY

 RS T <AT;<U REE 7&j/CH&'"$%?8%H@ 7&H?8H/@ _TV~me xQb QUm¡¢$ 6H/ +**,/* W7: LdeUybQX£
6=H 56z&C¤Y¥Z¦:! [gcm6 Fig. , §A-; La @¨ybfP©aª\ REE  .!! 56?8 La 7& +* ppt ¤?8H/@«¤¬]¤ ND :!,/ 

?8@­adm6H/) 6® 9  ^H/uafQwa¯m¨_ª$_`6H/a/ mm ¤b°c±:! ²³dc±´ 0e$ AMN-+*** 6H/ ,** µy¶·¤fc±:!?8:! !?86d_bc©¸mq¹34(¹: º° *../ mm µaqPagxvum([»¼½:/?8+J6,$:!
84 /2  ,**2

Fig. ,

 

Pre-concentration procedure of hot spring waters using chelating resin disk.
 , 


,0 REE  !"#$%& H-SO. '  Na-Cl ' 

()* "+,-./* pH 2 0

1 H-Na-Cl-SO. ' 234 536"7%&  *89:;)<=> REE ?@ABCDEF
Na-Cl '

LRSJ

*L

6

M

" H-SO. '

*L

G

"HI&JK

6NOP

Q

TULVWJ

TUE XYZ[\] ^_`abcdae MAC-, Lfg +/* " ,**  hi
VWJ jklmnop NOP Q "S uvwxy

t&g . z{M qL ,* mL rst&

1| 2 z{}S9:L53%~J SJ *../ mm memk-aSg9:LS SJ ῌ3|q"vSJ

REE L

1@53SJ9:v*

 E X  JEOL n SX--,,* Element Analyzer Lf =v E X  cmn MXP-AHF ' Cu-Ka LfJ

- ,-&'(./-+!"#$ REE %&'( REE )*+¡¢£?SJ ¤¥ 3 REE  1|¦m§b Masuda et al., +31- ;Masuda, +31/  REE ¨©ZSJ REE ª amL Table + ,6

1| Fig. -«&¬&­¡¢¤¥E®)Z¯°  /0.,῍  @ ±N¤"²³& ´J REE °

E LREE µG HREE : Er, Tm, Yb

1| Lu

¶g·¸6±N¤ ¡&

¹'ºª am !³» ¼O ,**, ½K&J Fig. -

85      
Table +

The concentrations of major elements in Tsurumidake unaltered rock sample.
 +
SiO,



TiO,

SFe,O-*

Al,O-


MnO

Sample

MgO

CaO

Na,O

K,O

H,O

-4.+

14-/

-4--

+4*0

*4*1

῍

Tsurumidake unaltered rock

/04,

*43/

+14,

041,

*4+.

* The total concentration of iron regarded as Fe,O-.
H,O : adsorption water

Table ,

The concentrations of REE in Tsurumidake unaltered rock sample.
 ,
La Ce





Pr

Tb

Nd Sm Eu

Gd

Sample

Dy

Ho

Er

Tm

Yb

Lu

+

( mg g )Tsurumidake unaltered rockFig. -

+-

,3

-4/

+.

-4, +4- -41 *4/3 -4, *400 ,4* *4,3 +43 *4-*

REE pattern of Tsurumidake unaltered rock sample.
 --,  !" REE 

#$% REE !"#"$%&'()*+, REE ()-./0/ Table - *+, Table . 1
234
5678934 !:;<=>"<?!1@4ABCD" EFGHI4

HJ/A " Na-Cl K<#9 LM N1'OPAQRS" H-SO. K<#T E-UEPAV
W:XY3 H-Na-Cl-SO. K"RSZ["#T\&J/ JH1 ./0/T]^_U>`a-`bUE3bcAd9TLHG1J/bcA ῌef +330 gh i"j k l
86

++-

224-

.42-

 Shibaseki spa

῍,3-

3242

142/

 Heiwaen

.4+1

,42,

1433

-4+-

 Floricultural center Kuroki memorial
hospital

 Private well C

ND : not detected

EC : Electric conductivity

ORP : Oxidation reduction potential

334*

-12

/1

+3.

+/*

.1.

,-+

233

12/

,/+

1,+

.+,

+/+*

+-3*

.*3

++-

-04*

,/-

+22

,04+

/*4+

.*4*

-04,

//4+

2+4*

+*42

+4*-

+,43

,40-

+4,1

-4.1

ND

/4,+

*4,.

*4*0

*4//

*4*+-

*4*1+

*4*2+

*4*+2

322

-+*

,-0*

,+2*

.1+

+/+*

3,2

/3.

2--

+01*

/.3

..-

.-2

-*.

-3-

.+0

-12

/1+

.,2

-0*

+/-

/0,

,+3

ND
ND
ND

,4-+403
,40*
.4-0

+40,

*43/

04,.

/413

ND

ND

ND

ND

ND

ND

/4--

*421

ND
*4/2

+42.

*4.0

ND
,4/,

*4.,

ND

ND

ND

ND

ND

ND

ND

NO-

 

114*

314,

3.43

῍-+1

 Spout of Umi jigoku

3,4,

141/

 Source of Shiraike
jigoku

*4*//

+4-*
/4+.

./40

+./

+*0*

/.*

῍++

+**4*

-420

 Sakaeya hotel

*4*.2

*4**,
*4,/

/+41

1,41

1-*

.+/

῍+3,

3,42

24+0

*4*0/

*4/*

,4/-

 Private well B

*4*12

+4-.

-410

*4*-3

*4*1

,40+

/343
,,43

-./

,+.

3*4*

.4-2

 Kyukouen

+0/

*4,/

-*4+

0/40

/3*

13+

+4.1
ND

-423

+243

0+4.

,.4*

-3-

+.1

3340

.4**

 Private well A

++0*

/.42

+*.

2+4*

00*

33

2.4*

0410

Kannawaen

-0-

//1

+.-

*4//

,4,*

/4+.

+.4.

3.4,

,/.

0/4-

040.

Kamegawa spa

-*4+

/31

.-,

/,2
῍.3

0.4.

,411

Chinoike jigoku

+-2

-12

+*3*

+4/.
-22

../

*4*+

,4*3

++4.

/.4/

0243

/4.1

+*0
+/3*

*4-2

*4**,

*4**,

0/4.

1-40

ND

+13
/4*-

ND

,4++

.4,/

-,43

-4*1

+*43

ND

.//
-4*0

+34/

+.40

+*4.

-141

+-41

,-4-

ND

,3+*

--4,

+-2

+-41

*43,4-3

Br

+2.

0/4,

/402

-043

SO.

ND

Cl

ND

/.3

Al

,10

*4,2

124-

+.4,

+-4*

῍+

0.0*

+3+

mg L

Fe

,4//

Mg

+4++

Ca

+3+

.-4,

K

,400

234,

Na

0.0

+*1

,+3

/,4/

-400

Lower reaches of
Shibaseki spa

,0/

ῌ

/,

῍.+

-04/

-4,0

 Konya jigoku

+*/

῍33

/34+

,433

 Ebisuya hotel

0-2

῍3

0,4-

,4*.

.041
-1

 Yamadaya hotel

῍+

mS m

EC

++*0

..42

mV

ORP

.2/

-4/.

῎

Tw

῍+0-

+412

 Myoban jizou

pH

The concentrations of major dissolved components of hot spring waters in the northern Beppu geothermal area.
 - 


 Tsukahara spa

Sampling location

Table -

 /2  ,**2

87 
Table .

   





REE concentrations of hot spring waters in the northern Beppu geothermal area.

Sampling location

La

 .



Ce

Pr

Nd

Sm


Eu

Gd

Tb

Dy

Ho

Er

Tm

Yb

Lu

+14/
141
+,40

-41
+4/
,42

++4.4/
243

+41
*40
+4.

+*41
.4+
342

+41
*40
+4/

mg L+
 Tsukahara spa
 Yamadaya hotel
 Ebisuya hotel/+4- +,+/40+-4. ..4- 042+,4, -,4+ .41

034*
-.4+
,.42

+04.
24,
14+

/41
,4.
-4.

+043
24+
341

,41
+4+42

ng L+
 Myoban jizou--,
0,1014- ,--/4, ++41-+4+ -43,-41 .40 +.4+ ,4.
++4/ ND
 Konya jigoku,-4, 204+ +043
3*4. --40 +-4+
.14. 24*/+41 ++42 -/4* /42-24. 042
 Heiwaen
ND-42 *4+4.
*4- *4,*4. *4+*4. *4+*4, *4*.
*4, *4*.
 Shibaseki spa
ND,4+ *4+4*4. *4.
/4- +42+34* /4+ +-4- +4/4. *42
Lower reaches of
ND
,43
*4/
-4.
++4.
+-4,
+*+
,24.
,-0
/,4/
+/+
,*4.
+,+
+040
Shibaseki spa
Chinoike jigoku
2,4+ ,,.
-14, ,,0+/32-4+ .,- +-*++*- ,-3
1+*3341 /10
1+41
Kamegawa spa
ND,4* *4+4,*4- *4+*4/ *4+*41 *4,*4/ *4+*4. *4+
Kannawaen
ND
14- *41,40*4. +4*4/ *4+*40 *4,*40 *4+*42 *4,
 Private well A
ND+4/ *4,4.
143 ++4/ +++-,4. ,*.
-,42 034, 14*--4, -42
 Kyukouen
ND+40 *4+40-43 /40/,43 +14. +,*,*4. ..41 .40,+43 ,4/
 Private well B
ND*4- *4*/*4, ND*4*.
*4+ ND*4, *4*. *4+ *4*,
*4+ *4* Sakaeya hotel.*4- 004/ 24/-341 +/4. ++4034* ,,40 +2,-.4+ 2+41 340/+4+ 04.
 Source of Shiraike
ND+4* *4+*40*4, *4+*4. *4+*40 *4+*4/ *4+*40 *4+
jigoku Spout of Umi jigoku +,4/ -14+ 14*.-4, ,-40 +,40.043 340-4- +,40 --41 .4,.4, -4,
 Floricultural center
ND+-4- +43
340
04, /4,.*42 +-4+ ++*,/4, 134/ +,40
2043 +,4/
 Kuroki memorial
ND*41 *4+*40*4, *4+*4- *4*/*4- *4+*4- *4*.
*4, *4*.
hospital
 Private well C+1.*,..4/ +3+
014+ .,4- ,0+
2*4/ 0/- +,1-+,-14- ,*+,14Marine Palace
ND+4* *40-4+*41 *4,+4, *4,+42 *4/+42 *4+41 *4(Aquarium)
ND : not detected  !" #$% &'()*+, pH -./012 Na, Cl 345 SO. 67-./
089: ;<=9$>, Na-Cl ?345 H-SO. ?@-ABCD8E$>:FE GH$I
9JK GH$LM!"9@, NOPQ38DR H-SO. ?9S:FE;T-U

VW<XM!"9@, pH - ,.*. :YZ7- 0,.- Fe, Al, SO. [9\]^_`a=_b
ppm 9c+d+:efg?0h H-SO. ?9@:FiX j REE 67R ppb c+d+:ek<D3l mnopq9@rstuvwQ4lxra=@yQzZCXR9T{|=<E}9@, pH - 1.2/ :YZ7- 32.2 :Fl Na 345 Cl ^~2e Fe  Al ^
Tekh8g?0h Na-Cl ?9@:FiX kX REE 67, D12 . ng L+ 
q:FiX ;<, $qa=RX=W<Eyn9 Na-Cl ?@yQ, REE ,ek<D3= $YZEk:9Q38D@rstuvwQ4l @yQaQRX=W<D
8ET{|=<E-- 

REE 

$>9@9 REE *+)^ Fig. . Q ;9$>9@9 REE *+),
 :67.-./08*+)  LREE - HREE T./CD12hE*+) 88 /2  ,**2 

Fig. .ῌ+ REE patterns of hot spring waters in the northern Beppu geothermal area.
 .ῌ+ 
 REE 89    Fig. .ῌ, REE patterns of hot spring waters in the northern Beppu geothermal area (continued).
 .ῌ, 
 REE  90

 /2  ,**2 

Fig. .῎- REE patterns of hot spring waters in the northern Beppu geothermal area (continued).
 .ῌ- 
 REE   !"#$%&'()*+, -.)
/012. !3#$%&' ῌ 456 789: ;<=>? @ABC>?
DE=9FGHI H-SO. JKLB .M NOP

4 LREE Q HREE

-R*STI U Q IV3.M W XY pH "#564 Z[\]I^ _. REE XY3* `a.MbcdaeQfg La hP Lu i.jChklBmnKoIV# NO4 REE pqrst.aehPuvwxyz {|VY^
P}OV#NQKo~IV  H-SO. J WQPO῍ $%&'KoB 4#.Meet 

9F A   >? 9F '%& C GHI 4V
H-Na-Cl-SO. J.M N$%&'W4 HREE Q IV LREE "* -R
91





     Fig. / REE patterns of the solutions prepared by mixing Yamadaya hotel
hot spring water (,* mL) with Heiwaen hot spring water (,* mL).
 /   REE : +/*  ,** :  ,* mL !"# ,* mL$

Table / The concentrations of major dissolved components in the solutions prepared by mixing Yamadaya
hotel hot spring water with Heiwaen hot spring water (before and after heating).
% /&'()*+,-./0
pH

Na

K

Ca

Mg

Fe

mg L

Al

Cl

SO.

23*
3*1
3+1
3,/

+/1+.,*
+.**
+-3*

+

Yamadaya hotel (,* mL)Heiwaen (,* mL)
Before heating/0Heated at +/* for . hr
+43/,.
Heated at +/* for 2 hr
+43/,1Heated at ,** for . hr
+41
/,2

.-41
--4-+42
-/40

+*,
+*.
+*1
+*-

+040
,*4*
+343
,*4*

-,40
+-4,
*4/3
*4/0

2141
-*42
+143
14*

Yamadaya hotel (.* mL)
Before heating
Heated at +/* for . hr
Heated at +/* for 2 hr
Heated at ,** for . hr

+-41
24,
-43
*4/-

+-2
+.,
+.+
+-/

--4,
.*4.*40
.*4+

0/4,
14-43
/4,

+1/
+/*
+,3
-04-


+41
+41
+40

-043
-241
-040
,/41

,4.
,4,
,4.
,4/

-*.*
-*+0
,300
,1**

 : not measured

 !"#$% LREE &'()*+,-./01-$2 !34560 78*9%:;<=>?
ῌ @ABC&CD)EFGHI@% JK LM NO B P QRSTUVWXYZ[&\]5

$% Na-Cl ^@+"# CD_`@2a*bc52deHIFf

g+hi"j/52k+@ REE FGHI%k+*lm)n Ce @o@pqHdeH34560
92

 /2  ,**2  ῑ  !"# $%&'()*+ *+,-. /01 Na-Cl 2  34
567 89.:;<=>?

@ABCD#"E+  DFῒG H>I J

K" +33-  LΐM5NOΐP Q;.

Eu RST&UV&,W9"X+-&. 
H-SO. 2 YZ[῎\  Na-Cl 2 LΐM (*+]^( _`*;a_`b +/* 5N ,** >_`*+a c dX"]^ REE $%&'( Fig. /*+ e+ fῌDcgh( Table /))i_` h 5j REE $%&' k?lmn* oLREE;.dmn pq>Ij _` h,r;st LREE ,k?lu:*+ /X  r stvῐwxy,zD* dwxy
LREE ,{j|eX ]^}#"~X+>I"X "  K, Fe, Al 5

N SO. fῌDca@
 +* c +u:*.j _`*.;;a*. Fe

 0* c + Al

u:*.;+_`z+wxy X c c >  +/* >_`*zD*+wxy
Fe, S 5N Si &, e+ ,** >_`*+῏+ //#" zD*+wx

Al,

Al, Fe 5N S &,W9"X

Al 5N Fe wxy>I/,)X+  wxy X ( Fig. 0)i /#" S KAl- SO., OH0

5NU% Fe,O- &,W9"X&¡¢',£¢¤>¥¦§y¨©

:;ª«>?/#" wxy f*./X"§y#"¬DX.;/,­WX+S®¯°

AB- XO., OH0 *.±"X.j A

Ag, NH., Pb, Ca, Ba, Sr 5N REE , B¶ "  XO.y

῍²' Na, U, K,

Al Fe Cu 5N Zn ³´µA²',

SO., PO.- AsO.- CrO., ³²',¶/,·"X.;

Dill, ,*** ®¯ ,§yt/ ¶#  ²'¸¹,k?lº±i¦¬»¼µ½

Fig. 0 X-ray di#raction pattern of deposit produced from heating of the solutions prepared bymixing Yamadaya hotel hot spring water with Heiwaen hot spring water.
 0 
 X  !"#$%

93    ῍  

  !"#$%&'()*+,-./01 A 2,-34 K 567 Na 8,9:;< K : +-2
pm, Na : +*, pm ; ,9:;<8=4>? Shannon and Prewitt, +303, +31* 3@A LREE (BCDEFGHI0E J$ KL3 B 2,-34 Fe J$4 Al ( XO.y 34 SO., (MEFG
HI0E J$ NOPQ8RSTU35A?VWX3YJ0EYZ([\#$]^4 Table / 6_ Na, K, Fe 567 Al ./E`FaIb `0I8]^aIcE)*+,-(!"#$FDE`
F4de./E
fQWX8gZ"h3iA?bKL3jk.lE Dcmn LREE F,9:;<8ῌoDE Sr,9:;< : ++- pm 567 Ba ,9:;< : +-0 pm 8RSU8pq([\#?5_ Table0 `0I8]^b LREE FKL3rstuv3BC#?AEFwx.lE c5 Rb ,9:;< : +/, pm 567 Cs ,9:;< : +1* pm 4RSTU.pq4[\#cay$ `04 `0I8]^4 K 6_,9:;<(lz uv3BC.lcA${FGHI0E
-/LREE  Fe  Al  !

NOPQ35|ERSTU8}X8 REE F Fe 567 Al pqF~8[\ ῌ  Table
1 567 2 3D `8aI Al 567 Fe pq8[\F LREE 8[\3 (I0 

3 Al F La F83A

({I0$ `8`F4 LREE 4 Al FFb3%&'3_J0 RS8 Al Y%&' )*+,- (!"# ~8 LREE (}aI
0$( A`F#?AE 8O"PQ35A?b)*+,-X3 LREE (t3z_J0E(0?5_ I ,**. )*+,-(!"DE`F36_h(! E`F(z¡0$
¢8£¤¥4 .X8 Na-Cl ¦8S}F rst§. Fe zY¨©©8S}8N
O36_ª"0?AE«¬­2,- KFe- SO., OH0 F®¯°,- Fe,O- (%&'F#?
!"#?AE£./E ±I +332 ;I +332 `8£4²8³cE}(NO#?A

E`FaI £}4 LREE (t3§A REE ´°µ:DFGHI0$( A ¶·¸¹º8
63»¼3§A´°µ:.4cay$ `04 ½Y«¬­2,-J$4®¯°,-.4

Table 0 The concentrations of minor elements in the solutions prepared by mixing Yamadaya hotel hot
spring water with Heiwaen hot spring water (before and after heating).
 0
V

Mn


Co

As

Rb
mg L

Sr

Cs

Ba

+,0
+,+,+,.

2042
+42
+43
+43

+

Yamadaya hotel (,* mL)Heiwaen (,* mL)
Before heating
2*4/
+02*
Heated at +/* for . hr
,+4+
+1,*
Heated at +/* for 2 hr
+-4,
+/3*
Heated at ,** for . hr
,14.
+10*

.40
.43
.42
/4,

3+*
./42
+143
/,4-

,03
,2.
,21
,33

1/3
+0+
+*1
+/*

Yamadaya hotel (.* mL)
Before heating
Heated at +/* for . hr
Heated at +/* for 2 hr
Heated at ,** for . hr

34,+*4343
+*42

ND
ND
ND
ND

3,4.
3040
304234++02++22.424-ND : not detected

94

+0+
,43
+*4*
-+40

--/*
-/0*
--**
-1-*

.4.
.40
.40
.4/

-*4/
ND
ND
ND

 /2  ,**2   

Table 1 The concentrations of REE in the solutions prepared by mixing Yamadaya hotel hot spring waterwith Heiwaen hot spring water (before and after heating).
 1
La

Ce

Pr

Nd

Sm Eu

Gd

Tb

Dy

Ho

Er

Tm

Yb

Lu

mg L+
Yamadaya hotel (,* mL)Heiwaen (,* mL)
Before heating
14* ,-4, -41
Heated at +/* for . hr ,4/ +,4+ ,4/Heated at +/* for 2 hr ,4* ++4. ,4/Heated at ,** for . hr *40. .42 +4.

+14/
+.41
+/4+*4/

.4+
.4+
.4,
-40

+4,
+4,
+4,
+4+

.4,
.4+
.4-41

*402
*40.
*401
*4/3

-40
-43
.4+
-40

*41.
*413
*42*41-

,4,
,4,4.
,4+

*4,3
*4-,
*4-.
*4-*

+43
,4+
,4,
+43

*4,2
*4-+
*4-*4,3

Yamadaya hotel (.* mL)
Before heating+.4* .04- 14. -.43 24Heated at +/* for . hr +*43 -343 040 --4. 24Heated at +/* for 2 hr 242 -/40 04- -,43 24Heated at ,** for . hr *4-0 .42 ,4+ +34, 14+

,4.
,4.
,4.
,4+

24.
24+
24,
140

+4.
+4+4+4,

14140
142
14-

+4/
+4/
+40
+4/

.4.4/
.40
.4-

*4/2
*40*40/
*40+

-42
.4*
.4,
-43

*4/0
*40*
*40,
*40*

Table 2 The decrease rate of concentrations of LREE, Al and Fe in the solutions
prepared by mixing Yamadaya hotel hot spring water with Heiwaen hot springwater (before and after heating).
 2

 Al  Fe 
La

Ce

Pr

Nd

Al

Fe

!

῍

REE 

Yamadaya hotel (,* mL)Heiwaen (,* mL)
0.4/
.142
Heated at +/* for . hr
1+4/*43
Heated at +/* for 2 hr
3*43
134.
Heated at ,** for . hr

-+4/
-*42
0+4/

+/41
+,4.
-340

0.43
1340
3,4*

/34/
324,
324-

Yamadaya hotel (.* mL)Heated at +/* for . hr
Heated at +/* for 2 hr
Heated at ,** for . hr

343
+.43
1+4+

.4/42
./4*

+.4,04134-

2242
3.4*
3,4*

,,40
-141
314.

+-42
,-42340!"#$% &'(#)*+, LREE -./01234,567 89:;<=- >?@*+& A(BCD7 -"0 #$%&'()*+,EFG,$H*I123JK X LMN#O&IPQ!R(ST X LUVG W
3XYP ZD12$H[\  ]^_ῌ`aH!bPG, 9:;<=-$H*
REE #cd=ef:*IghQ-i&'(-)Z7I

j'k

EF&+9:;<=-12*I'(# lm[\9:;<=nopq#mrs0tu*+vw*I tuxy8z{|,k} ῌ ~]sXqD<d q#u ¤῍ '<d q(X<d Z#B*vw I Extended Debye-Huckel
95

    Table 3 Saturation index for alunite of the solutions prepared bymixing Yamadaya hotel hot spring water with Heiwaen hot
spring water (before and after heating).
 3



Temperature

Heating period

Saturation index+/*

Before heating
Heated for . hr
Heated for 2 hr

04+/
-43*
,422

,**

Before heating
Heating for . hr

34/.4+.

Mixture ratio : Yamadaya hotel (,* mL)Heiwaen (,* mL) !"#$%&'(ῌ )*+&,-."#$/012345678 9:
KAl- SO., OH00Hῌ῍K-Al-,SO.,0H,O;<" => Q &,'(῍ 2345678=> Ksp Reed and Spycher, +33, ? ῌ +&,-." => !

@$ SI %&'(AA+ SI+ 7?B

 SI+ 7?B  SI+ 7?BC D'

@$7%&EF Table 3 GD' +/* ,** 7 HIG/ !J K L723456
7 @$MK )?N-!BOPQ-.A?RDSI!/T 23456RU;<V,.A?WX'(EFR<I.

.   
Y7 Z[\+]^-.Z_7 REE = REE `abc8V-.EF d
G0e! REE `abcGfg Rh<I. 'fij klm70nf pH,
op7 H-SO. q7ZM REE =R O r s r 7 REE `abcD-. tuv
w56mxya56;<f(zd{|7}<I( pH- ~77[7Z H-Na-Cl-SO.
q+M LREE RQf

REE `abcD- S<G pH R

qZ+M G LREE R

-. pH. ~7 H-Na-Cl-SO.

REE `abcD-. pH0 o7 Na-Cl qZM REE

=RO REE `abcR6+e.
Z

.+7Z

;< Na-Cl q

Z? H-SO. q

ZR-! H-Na-Cl-

SO. q77ZR'( LREE MV,-.23456 KAl- SO., OH0

G^TI Z;<GSI(A? - LREE ?5¡c¢7~  {|_7 K R LREE ?£¤-! (?¥¦<I( §7 H-Na-Cl-SO. qZ7¨©+B(
A?D-.
o7EF;< REE Md7ªf( Z7«¬m­7

C®f¯¥°'(+!

f@"+(A?R<;?fe.
±LM tuvw56 KFe- SO., OH0 +M LREE RG

REE `abcDSf#$<;G'(%&R( . {|G LREE R^TI(C®8'(.hGM
SEM-EDS ²³q´µ¶'·῎¸¹3ºb»q X ¼V½£ ( .8VR!+(?¥96 /2  ,**2 

   REE  !"#$%&' ( ) LREE * HREE +,-./"012*34567 *8῏῎ 9: ;%<= >?@ 0*@A"B&CB& D%<EFG"%H1
ῌῑῐ῍
Dill, H.G. (,***) : The geology of aluminum phosphates and sulfates of the alunite group minerals : a view, Earth-Science Reviews, /-, -/ῌ3-.

IJ IKL M ,**. :NOPQRST!URVWX  /+ YZ$[\\]^_` ,0..
a b! cdef "ghL #e$ i%j +33. : Rb kl Cs m&no&'()pqr* s[ .. +2-ῌ+32.
Kikawada, Y., Oi, T., Ossaka, T., Kakihana, H. and Honda, T. (+33/) : Leaching of lanthanoids
from andesitic rocks by acidic aqueous solutions, Geochemical Journal, ,3, 01ῌ2..

IKL M >tu +333 : +,v ,T!URVwx& s[.3 2ῌ+1.

"ghL i%j yz{| #e$ Stewart, M.K., }-~ +33- :p0n&'

*./()pqr* } [\ -/ ,21ῌ-*/.

Masuda, A., Nakamura, N. and Tanaka, T. (+31-) : Fine structures of mutually normalized rareearth patterns of chondrites. Geochimica et Cosmochimica Acta, -1, ,-3ῌ,.2.
Masuda, A. (+31/) : Abundance of monoisotopic REE consistent with the Leedey chondrite
values. Geochemical Journal, 3, +2-ῌ+2..
Matsubaya, O., Sakai, H., Kusachi, I. and Satake, H. (+31-) : Hydrogen and oxygen isotopic
ratios and major element chemistry of Japanese thermal water systems. Geochemical
Journal, 1, +,-ῌ+/+.

#e$ i%j "ghL +33. : '1- ) 2 s[.. +33ῌ,*2.

#e$ i%j +330 :  $[Nn.'"-} )
2 5673 */./,*12 ()p)r**} 156 4N 1 5s[5667 L856 B 56N9 +*-ῌ++..
:; #e$ ,I  cdef i%j +332 : '<=$ >?@@Nῌ $[N=$ s[ .1 +/1ῌ+0/.
A B 4CL M  D E ¡ IKL zEFG HM¢ I£¤¥ +331 : ¦J§¨KL©zª«¬ M­  =$*ªz® Z$[-+ ++3ῌ+,2.
Reed, M.H. and Spycher, N. (+33,) : SOLTHERM : Data base of equilibrium constants for aqueous gas equilibria, Department of Geological Science, University of Oregon.

¯NO cdef |<P° ±²³´ Q«¤P ,**, : µ§¶I

 ,

REE  =$*Z$[R S [· 0- +-/ῌ+./.

¯NO ,¸{ z¹ L cdef ,**0 : IT§UVWº» ¼

v½I ,
97    REE   !" 01 +-ῌ,+.
Sanada, T., Takamatsu, N. and Yoshiike, Y. (,**0) : Geothermal interpretation of long-term
variations in rare earth element concentrations in acidic hot spring waters from theTamagawa geothermal area, Japan. Geothermics, -/, +.+ῌ+//.
Shannon, R.O. and Prewitt, C.T. (+303) : E#ective ionic radii in oxides and ﬂuorides. Acta
Crystallography, B,/, 3,/ῌ3.0.
Shannon, R.O. and Prewitt, C.T. (+31*) : Revised values of e#ective ionic radii. Acta Crystallography, B,0, +*.0ῌ+*.2.
Sturchio, N.C., Ohsawa, S., Sano, Y., Arehart, G., Kitaoka, K., Yusa, Y. (+330) : Geochemical characteristics of the Yufuin outﬂow plume, Beppu hydrothermal system, Japan. Geothermics, ,/, ,+/ῌ,-*.

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