῔
J. Jpn. Soc. Soil Phys.
./A*B'
No. 23, p. ,/῍-- ῎,**,῏  *ῌ **ῌ

**ῌ

**

Ion Concentration Prediction of the E%uent during the Sulfuric
Acid Solution Permeation into Volcanic Ash Soil.
Kouji KAMEYAMA*, Susumu MATSUKAWA**, Tomoyasu ISHIDA**
and Hidemasa KATO*** The United Graduate School of Agricultural Science, Tokyo Universityof Agriculture and Technology, Fuchu, Tokyo +2-ῌ2/*3, Japan** Faculty of Agriculture, Utsunomiya University, Utsunomiya -,+ῌ2/*/, Japan
Abstract
The prediction method of ion concentration in the e%uent during pH - sulfuric acid solution
permeation into the air-dried volcanic ash soil column was examined in this study.

The method

for prediction was composed of chemical reactions between acid solution and soil, and mixing cell
model.
The chemical reactions were composed of aluminum dissolution, cation exchange between
dissolved aluminum and basic cations, bicarbonate formation, sulfate ion adsorption, charge
valance and mass balance of sulfate ion and basic cations. Cation exchange between dissolved
aluminum ion and soil bases were lumped together with the mineral weathering as acid bu#ering
e#ect.

Mixing cell size depends on dispersivity and that value was determined by the break-through curve during KCl and pH - sulfuric acid solution permeation.
Characteristics of the variable charge on volcanic ash soil were considered in the simulation
model by applying the anion adsorption equation (Wada, +32+) in which adsorbed amount of
sulfate ion depends on pH and sulfate ion concentration.
The simulation results agreed well with the measured values of pH, aluminum ion concentration and cumulative release of basic cations in the e%uent.

These represent the most serious

e#ects of the acid deposition on the soil. Therefore, parameters used in this simulation model areuseful for predicting the main e#ect of the acid deposition on the Kanto loam subsoil.
However, it could not estimate basic cations concentration of the e%uent with good accuracy.
This discrepancy may reﬂect the assumptions that cation exchange treated as aluminum-divalent
basic cation exchange, the equilibrium constant was assumed and exchange between hydrogen
ion and cation was not included. Therefore, it is necessary to describe the cation exchange inmore detail.
Key words : acid deposition, volcanic ash soil, chemical equilibrium equation, Mixing Cell model,
simulation*  +2-ῌ2/*3  ! -ῌ/ῌ2** "#$ -,+ῌ2/*/ "# %! -/*ῐῌῒῌῑ : &'()*+ ,-./+ 0123456786+ 9:;<+ 20=>?2@3ΐ  26

ῌ+ µ]  ῌNQ:b+    

 

23 ¼ ,**,

Table +

 pH KCl
pH H,O     Bloom and Grigal, +32/ ; Reuss|rN ῍῎*+
CEC cmolc kg¦+῎*,
cd&'( cmolc kg¦+῎*,
Ca,¶
Mg,¶
K¶
Na¶
cdC&'( cmolc kg¦+῎*Cl¦
NO-¦
SO.,¦
[·

and Johnson, +320 ! "  #$%&'()*+,-./&'(0
Gaston et al. +33,

1 2345  ! 676 8 9:;<= =26 > ?@A BC&'(DE2FGHI J!
K L
 MN6JO P
NQ RS +33.    +333   Ishiguro and Nakajima, ,*** !N B82
T"I ! 8 > ,  0 X+,=-NQ.YZ=/ 01[2
]^9 

*40,
*41*4/1
*4+2

+40+
*401
.4*3

*¸¹(

# * : NC *º&»1*, : Shollenberger #*- : *.*+ M NaOH # , g : +/* ml l&'9 +332 b  ()ῌW* +332 1

!

.43/4-1
,4*2
,,4-0

+

U#V$ %" !

J3\ pH )&'(45!NPhysical and chemical properties of soil!

JK ?@A !<b= 

676  6 pH !N $%&'(J> pH 2&'(45!N1C&'(cdcNG 601 _[2JG27896 `!Nb=0! bP T# 326 aI ! bP \  # pH 2T&'(45!N1 T  6&'(cdJGNQ:

201 _[2=e\821 f>;\:J<g h,J2H9 !

8b=34H > &'(DN2 pH
K&'(452=-Z d* +32+

i= j>@?@k#ABC? D
Elmn FM82OGI ! @B-H
El6

&'(DNO!N82 H9 !

DoIJK=pq2r0=e/6 T&'(DX+,=+N6!

LJ,   1 se65:MtJu=BMvw x?I
 > yz{, Mt! "  D
-D256 |rN OJ P)QRῌ, +  fghRijMQklA3

NOOJ2H9 ! 8 > S T}~

mn@ .*0* cm oI796

JG:X+, )ῌU +33, )cd$D=/ !

%X+, VI 
2H9 !
26 @BX>?@A  J ῌNQ:b=- -+ 6 ! JK  #-ῌ+ p¡=#P !

8   6 3\
Y/

W /*῍ =Y/D =Z6 !

<¢q Schoﬁeld =# rs +300 ¡£¤B ! J¥ HCl "  NH. OH  pH = -3
tu6*., mol L¦+ ¦NH. Cl # /* mL =]o -U#  2#2vB [JNQ.Y

g vP §w¨©xyª§z1{6 |}^#=

Z 2  _ [ 2 =   :  -  Mixing Cell   +«~¬= +* ­®16 +* ­|}^# pH

Appelo and Willemsen, +321 =/ ! "  \= 6 =.Y# pH 2^J6 ! ¯1 B°T#=oIJK=G6 ]o±^] *., mol L¦+ ¦KNO- #= /* mL ©

 /I #&'(45 2 7t²³79§z1{6 |}^#=´>

34579

~¬=®1! ´> |}^#=c26 86

U#2^_`=a6

 : 89:X016./5(6)%

27

 + ,Sst_.vE )%   !

(6#[T;5/. SO.,,, NO-,, Cl, )%UV$W.P5 O)%   ! pH #~f Al- Ca, Mg, K Na #=
Cl, NO-, SO.,, #./&   ! Mw $tXY[.K    Z[ \# *.03.j*.1*, cm- cm, + h^# .1.*3j.3.0+ cm- %- !


, -

7 ./51]^ _;5 O ``Z7-FG5'(  )cmolc kg,+*5a ; b.4GF7 C%
O ! c )+323* ./0 7 C%

ῌ+ ns 
Fig. +#

Electric charge of soil.



af )molc g  aC%7 d\e.M-

ῌ+ 

  !

,+ ,+

s *

E5!


B

(6 )% f  gA  h[FO h[a7 \PQ.iFj W.
! ;5Q DC7 C% O !

"# pH 0./ $%& pH 1 '( )CEC* +'( )AEC* #  /.0
cmolc kg,+ -.2 cmolc kg,+ %- !

, . 

01k # 016 ¡&lm¢£/&O !

, , 

Hd /* mL ¤n_ - ,.

Ishiguro and Nakajima ),**** ./0 123

 |U.

-/ mL

7V / gmUVo ! 

  + 4%516789:.

m[ p ¥ +2 PQp  ¤qr[ s;5< =7> ?@ .! 7

t¦6 vE ! st¦6vE[§¤n_.# pH"A5B 7#CD.EFG5! H  $I2J

 , - . .uv016-* mL m

1%.&';5 pH 167;5<# +2 PQp  ¤qr st¦6vE w {Q(6 pH ! @KL)%! MN¡&l ! st¦6# R{ -* mL ;5 O.*PQ7+ M5! B O¨ / mL,RS# 6 F T-UC )+33/*©&vE6# *../ mm ª«Kg 9

./

vE

xG j¨.~f  pH



  !

y= z¬ [ ./pH- 016 1  !

V234 5W XYZ 6 O 7V [ , mm 89\ :] - cm *E +- cm
^K_`.V2;% *./, g cm,-  +* cm aE.<ῌ Liu et al. )+33**#bcd. pH- 016

&01)%   !
H P01k#­3{DC®

a ! C* : m01)% )mol L,+* V* : m./ =_>?@A016 )L* CN : N {Sm[|¯01)e^fghi./& /*% )mol L,+* VN : N {Sm[`6 )L* VrN

j0* m h,+ )kKlBC ,.*,m+*,-j,.--m+*,- cm: N {Sst¦6vE[©  )L*s,+ .&'* no !

S01°}# )CN,+mVrN,+C*mV** ,CNF (6 lp

qrg )st_ + ,' &D ,* mL* uvE! Mw $t# ,-x yzF , {b- ! GH.#aE *.. cm |I}] +0*j,/* mm ~fKg J hi./&no 0167`K .;5/.LM !
N

3,,**j+*,*** mLO.PmVN OC B
)molc g,+*G;! N {V~ )g* zFk

F®a !

BFOCpH 01)%k±². k³ )? +32+*

01

%F#O !

, / 

Os[T;5 Mixing

Cell ´Kµ¶.IF

t_,Q7 .2*j/3* , OI M- ! B O s

·.4GF>*7¸¹%5!

t_ +* ,R.(6 pH st_ -* ,R.(6 >*

;5 O.# Qº|BC »¼

v*b » 23 ¼ ,**,

28<+ ij1*klmKῌ,Table ,

Chemical equilibrium equation, equilibrium constants and conditions used in ion
concentration prediction of the e%uents+¥  ¡ ¦§ L ¨©L Al-_..,30ª+*-H+. 3,+1
 Al-H, O_AlOH,H Al-,H, O_AlOH
, ,H

-
logK_9/.*, Wolt, +33.
logK_93.-* Wolt, +33.

,¥ $ 
 ,Al--ExCa_-Ca,,ExAl« Ca 2' Ex 2( ExCaExAl_+-¥ ¬ m CO,H, O_HHCO-9

logK H

logK_91.2, Wolt, +33.

.¥   FG  ­ FG SO.,9 _*.**2 ®SO.,9¯*.,0- ®H¯*.,/1
Al-SO.,9_AlSO.
/¥-
logK_-.,* Wolt, +33.

+ &kY
&kY Fw_3.2..ª+*9+, molc g9+ s9+-0¥ =>°bno

9 9
SC
i Zi _SCi Zi
1¥ I)±,9SO,9+°SO,9. mol : ²;³_²;´. AlSO. FGSO.  Camol : ²;³_²;´ +°CaFGCa²;´ ¹mol9²;³ ¹molµ¶no·¸_º*.**+²;³ ¹mol BreakthroughCurve BTC : - 

    !"# $%&'()#*

+, -./ BTC 0 12)34506 7
8 *.+ mol L9+ 9KCl

- + 

ij1*klmK m no3p0q+0, :; <+BC, 1r 3` s- btu1@v=>? 1@/ BTC 0AB 7

wx f y45, -.U z{C DEFG0H

|3*u}0*B ~1@~ !"IJ

KLML van

Genuchten and Wierenga +320 1DENOP

0QC R0AB ST@UAB/V5
WXYR1  K0C2B R

Z0[ Mixing Cell \]^1Q

88 D : R cm, s9+ a : RZ cmv : 5WXY cm s9+ 06 3` KClb Ca, Mg, { + f6

b K Na {0 b Ca, Mg, {!"+.2 # )#* 8B $ 2 %1 ,

D_av

2 3h

+,

$


0Hb$Mg  K  Na ;i
,

Al-

 Ca,

pH u 1 6 Ch 1 %B CEC 

pH b2$ 12  CEC 2

-./AB/VRZQab0c6

CUh q &k1@ !"

B pH - 2 b0T 0r6b$ +,

1d*C( KCl; 1 
CR0AB KCl+0*:

e0*+0, :;5WX

Y R f0gh

&kY molc g9+ s9+ ;ie0ij1*q /AB ¡LK¢£, -.1`¤ <+ ¡  BC : ¹º».¼+*'  *

Gaston et al.



29

 

+33,

   !
"# $%&'()  *+ !
+

Schnabel et al.

+33+

Khanna et al. +320 ,- 

+ ./+012

34 Gaston et al., +33,  52678&+9# 
 !"#: *+ !

;

Mixing Cell - ,<=:>?@ ABC=# ;; C=#B !+DEF#  GH+ !:IJ?@BKL, M NOPQ:RS ῌ,

pH- *'!8¤4

Fig. ,

E%uent pH and cumulative release ofbasic cations.

TU V3 W <=:XYZIJ Mixing Cell 012:;
B

Mixing Cell +[\+]! "^#_,Appelo and Willemsen+`:

+321

Mixing Cell +[\Ba#!bM ῍ #!C' a +- ῑ #:je+je+Cjic+dfCije+c*./ +ef Cie+
cCic+

ftd

῎

,a
fx

῏

fx
v

ῐ

fd+e

῎gῐ #+hiBWj

C : k2*mol

Le+

i : k2$i j : lm$i f : no@pq *rfr+

fx : k2% cm

ft : &slm' sv:

 k2%fx +':]!> W; ῏ # no@pq f
k2+(*

PostmaB+33-

Appeloand

a#+ J,y!PQ:|F:῎ #}o@; o@+(ῑ}~ fx +'B ῑ #:R>-;!
> 

!+<45/+wx:PQ>6;  + ¡:¢!+lmM6;

.B/"
.*+Z
NO-e CleUNO0,- ~ + SO.,e+PQB * + 12+)Z*+
SO.

Cl

e

!

:XY33

+PQBWj /+*e0-+*e- /+*e- mol Le+ ~ M O4B)ῒ+ +O Ca,c Mg,c Kc Nac +@-,.+* cmolc kge+ :PQ;33
- .





. + 

 *+O* !

74:£{T+:8¤;8¤4 pH +¥¦:§ῒ, ¨O Kc

Nac +4:93 /* lm©B!

ª,« ¬ }~ :Aa­;+<  Kc Nac
A- - 

e
-

:

(# NOPQ  !O*; Kc Nac 8¤4B /* lm )ῒ+ ¨;

a
+
r
fx
-

,e

:> ft lm+k2+.῎ #B AH+*9 fx +' W+ῐ # &slm'ft :]!>

PQ(# SO.,e NO-e Cle +mt(uv cm se+ :);
wxy!++, z{ pH O*O Ca

;V3, ®+O* ! Ca,c
Mg

,c

,c



K



+4:93 ¬,~,.- ¯°§ῒ, +!c

Mg,c Bc<v :

Na +<v BWj /.,3.

+*e+, molc ge+ se+ ~ }~..//*

+@- 3.2..+*e+, molc ge+ se+ )ῒ, ῌ # :<v
;
A 1±².³ =´#µ:<v :!;¶· +332 a  4 =´#µ>+ pH? ../ ,~l@Aa­;+<  ¸A W B k2

¸¹ºῐ » 23 ¼ ,**,#

30ῌ- ῒ'89῔·89"I῍
Fig. -

Empirical isotherm applied to sulfate
ion adsorption in batch experiments.

 ῌ/

pH - ῒ'ῌST+
BCD7PQD

Fig. /¡Jῌ¢ pH

Measured and predicted pH in the
e%uent from soil column.

_`<ῒ. =+ & a

pH - ῒ'ῌST1

Lῒ' BTC UV23 WXYZῑ7\];^:;bcdefg.h+ & i ῌjk"lmlnῌST1L BTC I῍+ _` op;^DA KCl ῌ@ +.,-+q+.,23 pH - ῒ'ῌ@+/+.0*-q+/0.*0, @r &῎ "I῍1) \]s a A *.// cm 723Vt?D Mixing Cell uvwC῍R & a,

xyz+ ῒ'ῌSTy{1)|Vt DA }~xfg.ht & e KCl ῌSTy{
UV23 \]sI῍A 7t &. . 

ῌ. WXYZῑ7\];^:;Fig. .

Relationship between average ﬂow
velocity and dispersion coe$cient.

\]s a  *.// cm @rLUV ῑ "1)x+.0/cm +tVR& a

x As+* cm Z\L῎rL@x, cm 7

C+ & e IJA x, cm a*.//ῌ pH  ../ 

 ῏ῌ῔

ῌ῏

῍ "# $% &῔ !ῒ, ῌ

cm ῍R ῏ "1) f*../ 7+ & i <ῒ. =+

1 ῒ'ῌSTy{WXYZῑ v A ,.3q-.-+*[- cm s[+ @r

& PQI῍LnSTy{

WXYZῑ v ttῐ" +. , 

ῒ'ῌ()*+,$+ -./01)23 45& t sA 0*0q03* s @r &6 ῒ'67ῒ'89῔:;. / 

<ῒ- =+ &>+ ?<@Aῒ'67

pH - ῒ'ῌST+t 23¡Jῌ¢ pH PQD

ῒ'89῔:; ῕=+ & BCDAEF

7BCDEF<ῒ/ =+ & PQA !ῒ, @£¤GΐH89"IJ+ <K"ῒ'891¥¦^@rL῏§¨Y©C^ logK# ªQG

L'MNOPQ῍R &«%KCl ῌST1L BTC UV23

ῌ¢ pH BCD7PQDIJbΐR

D¬­®01 & logK2 7+ ¡J pH. -WXYZῑ v

cm s[+# 7\];^ D cm, s[+# :;῎ "I῍+

PQDA

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calculations and observation on salt water intru-+TUV Mixing Cell WX+Y/<ZH@

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Rotterdam.
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response to acidic deposition in nonsulfate adsorbing soils. J. Environ. Qual., +. : .23῍.3/.
Gaston, L.A. Mansell, R.S. and Selim, H.M. (+33,) :Predicting removal of major soil cations andLM=> ?@ ME +{1anions during acid inﬁltration : Model evalua-

230e-3 3 NOPQ0 Mixing Cell Wtion. Soil Sci. Soc. Am. J., /0 : 3..῍3/*.

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Reuss, J.O. and Johnson, D.W. (+320) : Acid deposition

dilute acid solutions. Soil Sci. Soc. Am. J., 0. : 2+-

and the acidiﬁcation of soils and waters.,

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Springer-Verlag., New York.

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E#ects of Sulfate on ionic transport and balance

Schnabel, R.R., Potter, R.M. and Richie, E.B. (+33+) :in a slightly acidic forest soil. Soil Sci. Soc. Am.

Applying batch-determined retension properties

J., /* : 11*ῌ110.

to predict sulfate transport through soil col-ῌ

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Liu, K.H., Mansell, R.S. and Rhue, R.A. (+33*) : Cation
removal during application of acid solutions into
air-dry soil column. Soil Sci. Soc. Am. J., /. : +1.1
ῌ+1/-.

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van Genuchten, M.Th. and Wierenga, P. J. (+320) :Methods of soil analysys. Part +, p. +*--, Klute, A.
(ed.), Agronomy, USA.

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Wolt, J.D. (+33.) : Soil solution chemistry, pp. +/2ῌ+0+,John Wiley&Sons Inc., New York.
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