J. Jpn. Soc. Soil Phys.
FKNo. 3/, p. --.* ,**- *ῌ **ῌ **ῌ

**Prediction of Ion Concentration in The E%uent during Permeation of AcidSolutions Including Multiple Anionic Species into a Volcanic Ash SoilKouji KAMEYAMA*, Susumu MATSUKAWA**, Tomoyasu ISHIDA** and Hidemasa KATO*** Graduate School of Agriculture, Utsunomiya University, Utsunomiya -,+῎2/*/, Japan** Faculty of Agriculture, Utsunomiya University, Utsunomiya -,+῎2/*/, JapanAbstractThe prediction method of ion concentration in the e%uent during permeation of acid solutions
involving multiple anionic species into volcanic ash soil was examined in this study.

The

method for prediction was composed of chemical reactions between acid solution and soil, andMixing cell model, which approximately describe solute transport in soil. The results weresummarized in the following.
+)

The model could simulate well pH and monovalent anions (NO-Cl) in the e%uentduring permeation of acid solutions involving NO-, Cl and SO., into soil column. This showsthat it is possible to handle sum of NO- and Cl as a monovalent anion.
,)

The simulation results agreed well with the measured values of pH and concentration ofanions and BC, (sum total of Ca,, Mg,, K and Na) in the e%uent.

Therefore, it seemed thatsimulation model used in this study is useful for predicting the main e#ects when acid rainincluding multiple anionic species deposited on the Kanto loam subsoil.
Key words : acid deposition, acid bu#ering capacity, chemical equilibrium equation, Mixing cellmodel, competitive adsorption  $%QKHmnu L7M+      /*῍5NO& ῌ (EF61abcdeQF!"

fuQ H-]

IH #$%& '( )*+#,*- 'n NO  SO.

./0123456789:7;<=#>?@AB op ῌ +322 ;  ῌ +33+t  ῍ 12345CD-./0(EF ,*?+#P# SO., NO sC#?~sn >n$%&GHIJK  L7M5NOP#sW& L7M5 NO+#? ,

CDL7M5NOmn#W

QRSTUVW )XYZ[\<=] QK^Os H P_`1abcdef+#ghKijA<£u NO- Cl ?¤¥` SO., &$%

=#>?klmn`A# op ῌ +322 ; qrsNO¦K§"`ij SO.,  ¨©

+333tB >u" QK^OP#$%vw x+# <& NO- Cl &DNOmnCA>

y+#u" z{ | }?~sn#B?ªmn`A# o« Kamewada +330tB* ¬­®i¯i¯°±¯²³´ µ-,+῎2/*/ ¬­®¶· -/*** ¬­®i¯±¯¸ µ-,+῎2/*/ ¬­®¶· -/*: QK^O QRST ¯¹º Mixing Cell 8»a ¼ NO¡¢Bsj  3/ ¼ >,**-A34      H!  "#$  % &'"#$ ()*+)*+,gth ijy pH ..*  HNO- H, SO. J>NO-B : SO.,B >q A*./* : *./*,
SO.

,BB: Cl>q*.1/ : *.,/,

NO-B :A*..* : *..* : *.,*A 3sD ,/j,2 mL hB+ >dmlr/ +.**j,-. / 0123 (4+.*3+*B- cm sB+ qA /|4, E *+J"#546789':;<= 9 8  HIeos t\ >H>+ +332 a +332 b ; ῌ? +332 ; FumotoIeum +331ῌ,**+A  v and Sverdrup, ,*** ; + ,**+ ; @1+ ,**,A / w'x >NO-B : SO.,B : ClB >q+67/)

D)

:9 SO.,B C8"#:99E9,A*.-. : *.., :*.,.A 3)p4,.Jvrrm >_t + >ZDy +2 mLA /2 kz4, E { ,-¡ ¢£|FEG;+ H >@1+ ,**-A //J:9 , ¤:<, E}¥NO-B SO.,B  8IE J3012

*.. cm  ¦p +0*j,/* mm wv§dm3[KL4 >MNO A J!"#3& D|4J8uvn 3#P Q(J/$R %&E%S'T(3)94,*+$ F~4,;*+4;4 *+   pH ,% Ca,!,

3y +* L (e*_t>@

8y 0** >( (E,  _t +* >

Mg,!, K!, Na! -.#  /UV#

pH _t -* >!"3p4, pH w%S0-W/E' 12 3X4(5654v¨ / / >Al, Ca, Mg, K, NaA ©

7(48Y$ 9&8Z , : *x m ª  «   © © " ¬ >  m n+ "#  //UVE[>NO-B, ClB, SO.,BA rlª~­v§mD

%S0-(12 3X43\$ (Dz ® p4, { y uvn  1];0E"#<^8_=E ()*+3p4\  1 *.1-1j*.11, cm- cmB- />@1+ ,**,A,A



Z,

 >67/ ?@ A3 Q .J!"¬¯3<F°±² >J

J8012*+4.J!"# NO-B, ClB, SO.,B ±!"A 3³o D

:9`B3<, C  H >@1+´,,**-A /)9%S'T((3X43aD0E$ (FG /|_3aῌ gth

Mixing Cell bcd >Appelo and Willemsen, +321A 3ij34y uvnW3 /* mL µt2)9, , zy µt3µ2-43 \CJ3kz4, z4 ¶·v§d,    

m/\CJ3¸4 rlª~­v

 @1+ >,**-A (FG HIeJfKgL$hMi

SNOPQRS .*j0* cm T§m/ NO-B, ClB, SO.,B ±!"3p4,;-    +k45UlmnoV3)9,Wp - cm X+- cm qrsdtuvnYZ-+ wmx3[9y z\ , mm ]3^{4|_.J!"¬¯)9%S'T( 'Tp3}`5" *./+0j*./.- g cmB- / +* cm aῌ4, z@ ²E[E + 4 @1+ >,**-A (FGP4 uvn3MN~\ bc13d :u3)9,  Ca,!, Mg,!, K!, Na! ¬ ,vnYZe* fgth ij3<,^/3¹p4 BC,! (4 (zDºE bc13d :e* MN~\, NO-B ClB P F G  ¬ ¯ 3 »  % $B-Bbc1( gt186k49 $R NO  Cl ¬3 + ^uvn;+MN~\Klm3n o*º,/Z, lm8$R4

(4 (zD

F( Ca,!,E %S'T(3¬¯$ °!"bMg,!, K!, Na! -. p\E["#3e* (d!" >mol LB+A /¬¯4,  BC,! :9µ : ¶'8·¸¹¢©.º»detmn¼-. /

ῌῌ+Table +-.

35`

Chemical equilibrium equations, equilibrium constants and conditions used in ion concentration
prediction of the e%uents+ ,W"Al-!+4-.+*0 H!,4-/0o/ : HNO-!
Al-!+4.+.+*0 H!,4-1+o/ : .!
Al-!+4,/3+*- H!+420o/ : H, SO.!
-Al H, OAlOH,H
logK(/4*, Wolt, +33.!
 Al-,H, OAl OH!, ,H
logK(34-* Wolt, +33.!
, 
 ,HExBCBC,,ExHlogKBC(H )'!
 -HExAlAl--ExHlogKAl(H )'!
  BC,  Ca,, Mg,, K, Na  Ex v  P ExBCExAlExH+- ¡¢£ CO,H, OHHCO-(logK(1.2, Wolt, +33.!
. 89:"¤ 9: SO.,(! cmolcῌkg(+!/,3¥SO.,(¦*.,,/¥H¦*.--/¥NO-(Cl(¦(*.++/o/!
 9: NO-(Cl(! cmolcῌkg(+!.0.1¥NO-(Cl(¦*.-/,¥H¦*.+./¥SO.,(¦(*.*+o/!
 Al-SO.,(AlSO.
logK-4,* Wolt, +33.!
/ + \]^_`c _`c FW cmolcῌkg(+!KW¥H¦*..*KW )'!
0 §¨jE©ª«ῒῌ ῏῍ ῏ῑῒῌ ῐ῍ ῐΐ ῎ ῎
ΐ ῎ ῎

1  }
 BC, mol! : ¬­ .E BC,!9: BC,!!
 SO,(mol! : ¬­ .E SO,(SO,(.
. AlSO. !9:. !!
(((( NO- Clmol! : ¬­ .E NO- Cl !9: NO-(Cl(!!
®¯ª«!

°±²­³mol!(¬¬³mol!

 Ca,, Mg,, K, Na  ,   +     mol!

´*4**+*+,mnop"PqC5"BrO5 s7
KLMN67O[\]^_`F+GHI    ,**-! " #  ³

$%&'*+,mnopt345u3v"BrO5
[w [\]^_`E H

logKBC(H logKAl(H )'" *+,-. pH]^z{ |}451PQ5/01"234523167

+32/! ~sP  89:  +    

Freundlich =9:>?

Mesquita and Vieira e

Silva, ,**,! 3 + 8, 84;<NO-(Cl(! "SO. ! @A9:B,(CD   EF+GHI  ,**-!

Hxy' deBloom and Grigal,+331! B"_`xy'KLMN67O1 _`' KW )'" *+,mnop
D5-. pH /01 BC,

-

/0

1 234523167H

;5 BC,  !
CD P _`c  + ;J KLMN67OPQJ   1

R0&'ST*.3.+ *.23. "UV KLM/0W

BCX"3YPQZ

P [\]^_` ;5.t BC, abB[\]^_` ;5 BC, abc _`c!
 de"."fghij kl45KLM",O_` }

 !  r5s"
 + ^_l ¼ 3/ ( ,**-

36-,Mixing Cell          

Mixing Cell

Appelo and Willemsen, +321  Mixing Cell 



C "fC !*./+#fC !C ῌ,af"+#$x

῍$xv

῎ji!+$t"

j#+i

j#+i#+j#+i!+

ῌ%῎ &'() *  C : + ,-. mol#+

L  i : + /( j : 01/( f : 234567 *8f8+ a : 9 cm $x : +  cm $t : :;0<9 s v : <=>? cm s#+ @AB CD 9 a + $x EBFGH ,**, IJ KL*.// , cm  M NOPQRST
<=>? v I+

9$x  ῎ UVW

ῌ+pH ..*  HNO-, H, SO., 45,QRA
5, pH qr r

Fig. +Measured and predicted pH in the e%uentduring permeation of pH ..* HNO-, H, SO.
and mixed solution.

ῌ,pH ..*  HNO-, H, SO., 45,QRA
5 BC,!  qr r

Fig. ,Measured and predicted accumulative
release of BC, during permeation of pH ..*HNO-, H,SO. and mixed solution.

IXY $t  +,.**%+,/** s IZ[H -- \]

XYZ[H#-^_,& SO.,# +#`abcd NO !Cl  ef-.)*,g+*#0 -.2/g+*#. mol L#+ hi M efjklmn op^_jklmnqr FGH ,**- s h-.

*.22 cmolc kg#+ eftuIAB v

Mw eftuIxyz{H SO.,# + `abcd NO-#!Cl# |}~+ efz-.)AB $t 0<K+ ,-. ῌ 45A 45z-.xyz &ltu SO.,# + `abcd NO-#!Cl# I BC,! tuI

YAXYZ[ W0<MYA..+ pH ..*  HNO- H, SO. 45, NO-# : SO.,#"*./* : *./* QRA5, pH qrIr + BC,!  qrIr r ) I«¬JrA , A CD & KW IAK,QRA5DB , pH  ­*.-x23r logKBC#H logKAl#H |®¯°qrIr±A M BC,! IAbcdjk23r) * AB °±A bcdjkIxX ²³CD H ,**+ ¡¢^ £G¤^_ qrIr¦­*.+ cmolc kg#+ |®¯´ µ¶q B I·vH EB¥¦i , `bcd Ca,! Mg,! I H!

| ¸  ¹ º { H W W     KW, logKBC#H,Al-! I H! bcdjk§r )logKAl#H r3¶I·vH [ W Hr*  +*.*1%+*./. +,.+-%+-.00 hY ¨©{HªB|®»irs : tuv lwxk yz{]^|.,  pH  -

NO- : SO.,  *./* : *./* *.1/ : *.,/ 
-6$%&%'SO.

( )* BC

Ca,, Mg,, K, Na#+,-. /012

3- , 4 -537(

89*.- :;<=8.>?  pH @;ABCDCl SO.,  ! " - . #,

6 ' pH . 7 pH BC  +  NO,}

!EFG>?
,( H. 7.FI)>? ' BC, + 8(J# NO- : SO., : Cl  *..* : *..* : *.,*  pH BC, + 
-/ #'(NO Cl  SO.,  ! " pH . 9*.- :;<=8( H  BC, +  NO-Cl.>?
SO.

,6FI)>? ':KLMNO Cl 

PQRAB(S# NO- +  -HS-T2UVWXY8ZBW'[% (.-  pH  
NO- : SO., : Cl  *..* : *..* : *.,*  7
ῌ-Fig. - pH, BC,, +  NO-
Cl SO.,   NO- : SO.,q*./* : *./*
Measured and predicted pH and concentration of BC,, monovalent anions (NO-Cl) and SO., in the e%uent (NO- : SO.,
*./* : *./*).

\]^ +  NO- CDCl  SO.

#', SO., _`abcde " 0( )* SO., _`abc. ]^#ab[%SO.

,c ' -*2

\#/NO]^fg -, hij5k SO., .lH%-,),(+* +/ m\ + . 3n#*,-op + 8ZB *.*0 mmol L+ ῌ.

 pH, BC,, +  NO-
Cl SO.,   NO- : SO.,q*.1/ : *.,/ῌ/ pH, BC,, +  NO-
Cl SO.,   NO- : SO., :Clq*..* : *..* : *.,*

Fig. .

Measured and predicted pH and concentration of BC,, monovalent anions (NO-Cl) and SO., in the e%uent (NO- : SO.,
*.1/ : *.,/).

Fig. /

Measured and predicted pH and concentration of BC,, monovalent anions (NO-Cl) and SO., in the e%uent (NO- : SO., :Cl*..* : *..* : *.,*).

+jkJ l 3/ m e,**-f38

῏ῌ0

WcdXY + +  eNO-&\Cl&fSO.,& : Cl&i*..* : *..* : *.,*f

WcdXYFig. 1+ pH BC,\ BCgh]^J_`*BC+' eNO-& : SO.,& : Cl&i*..* : *..* : *.,*fProﬁles of predicted pH, concentration of BC,ῌ and exchangeable bases at several elapsed times(NO-῍ : SO.,῍ : Cl῍῎*..* : *..* : *.,*).

+*
$%+/ +  !

"#SO.,& ' SO.,& ()*'+BC.DE6FG +  SO.,& ++HIJ+KLMNO
6P+QR/ "#012" SO.,& +345

S NO-& : SO.,& : Cl&  *..* : *..* : *.,* +TU=

6"7 89:+; <45=>+=?

>VWXYZ[2" +=>+ pH BC,\  ],-./
gh SO.,& ()*BC+' eNO-& :Proﬁles of predicted concentration of monovalent anions (NO-῍ῌCl῍) and SO.,῍ and accumulativeSO.,῍ adsorption at several elapsed times (NO-῍ : SO.,῍ : Cl῍῎*..* : *..* : *.,*).

Fig. 0῏ῌ1SO.,& BCSO.,& @ !

"# A"+ +^J_`*BC+'Va 1 b2"#_` : + ,-./0#12#456 E F):; pH BC,     BC,  pH   !"# $%&'()*ῌi++ ,-./0#123456 78/0#12456 BCDE F):; #G$)* H IJKL89%*-./45 ^%#456 E6F):;

pH P%K + Q,-./ RNO-N ClNM  SKT89)A NO-N  ClN#US@%; # + Q,-./FVA

WXY &Z'P%&[89)*,M pH \,-./ BC, RCa,, Mg,, K,; M ]FKT^_#[F `a')>+ ,-./0#
123456  R]bcD

 3% 3- : -ῌ ^M  F):; <= d'P%&e89)*ῑ ῔ ΐ ῒpH  3%

 2* : -ῌ+*.
i+ ῌ01ῌ7-89ῌ:;  R+332 bM :#X<F6F)
pH

NO-N, SO.,N, ClN #12O;# F):;

BCD

ῌ,-./ῌ01 R,**-M : ,i+ ῌ01 R+332 aM : qbrs/ E 29):; <=>#?@%)A + ,-.

Na 3% 23 : ,/ῌ--.
5++.

/ῌ ῍ ῐ ῏ ῎+M39

 3% 11 : ++ῌ+2.

Mesquita, M.E. and Vieira e Silva, J.M. (,**,) : Preliminary study of pH e#ect in the application ofLangmuir and Freundlich isotherms to Cu-Zn
competitive adsorption. Geoderma, +*0 : ,+3ῌ,-..

0ῌ-= R+332M : >?%SS -{tz%tz S E @%AQ ()* 03 : .11ῌ.21.
0ῌ¡iB¢9ῌC

DE R,**+M : >?% SS -{tz%
F£G¤IJE @%¥¦§w]@%¨H ( )* 1, : -3.ῌ.*,.

Appelo, C.A. J. and Willemsen, A. (+321) : Geochem-IF Jῌ©ªKῌL«ῌ5¬­kῌM-N9ῌical calculations and observation on salt water

OPQ! R+331M :S®Rx¯%

intrusions, I. A combined geochemical/mixingSSTS _° ±²³´ +* : ,21ῌ

cell model. Journal of Hydrology, 3. : -+-ῌ--*.

,33.

Bloom, P.R. and Grigal, D.F. (+32/) : Modelling soil

U;µV¶±²·/¸cW¹±²X R+331M : 85 2 Y

response to acidic deposition in nonsulfate ad-º3G¤ U;µV¶±²·/¸cYsorbing soils. Journal of Environmental Quality,Z , : +.+ῌ+./.
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Fumoto, T. and Sverdrup, H. (,***) : Modeling of sulfate adsorption on andisols for implementationin the SAFE model. Journal of EnvironmentalQuality, ,3 : +,2.ῌ+,3*.

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model’ to the adsorption of K, NO-N and SO.,Nº3G¤ U;µV¶±²·/¸cY

from a mixed solution of KNO- and K, SO. on

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40

John Wiley & Sons Inc., New York.

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