J. Jpn. Soc. Soil Phys.
ef¼No. 3/, p. +- ,* ,**- *ῌ*Adsorption of Nitrogen Chemical Fertilizer on Volcanic Ash Soil andElectric Charge Characteristics
Susumu MATSUKAWA* and Hidemasa KATOU** Faculty of Agriculture, Utsunomiya University, Utsunomiya -,+ῌ2/*/, Japan
Abstract
Ammonium sulfate or ammonium nitrate solution was added repetitiously in volcanic ash soil.
The di#erence in amount of anion adsorption or cation desorption, and the change in pH werecompared with the simulated results by the four plane model. pH of soil solution was lowered by
the addition of the ammonium nitrate solution, and pH was increased in the ammonium sulfate
solution. The amount of desorption of the base cation in the ammonium nitrate solution waslarge than that of ammonium sulfate solution addition.
The adsorbed amount of sulfate ion was increased, even if pH rose in the ammonium sulfate
solution addition. The amount of sulfate ion adsorption was depended on concentration, andthat didn’t depend on hydrogen ion concentration by adaptation of regression equation thatcomposed with anion and hydrogen ion concentration. Sulfate and nitrate ion adsorption
calculated by the four plain model were corresponded to the measurements well. Comparing thesimulated charge density at each plain, addition of ammonium sulfate solution was large thanthat of ammonium nitrate solution addition. In the case of ammonium sulfate solution addtion,amount of hydrogen ion adsorption on S plain was large than that of hydroxyl ion compared withammonium nitrate solution addition. These simulated results correspond with the pH measurements.
Key words : nitrogen chemical fertilizer, volcanic ash soil, pH, ion adsorption, electric charge

6A5" z{|;+    5^()*+,- }NH.#, SO.~" $()*+, }NH. NO-~ / ef%Y /?B !" ,**,# $%" &'()*+,-

/L?" ( ῌ ( ῌ )*+,-

. /01" 23 /, 2, ++ '456787

" ef  i" pH . F/YB@ 6+/2, +/3, +.0  t 19:;. <=>7;?@ ABC"YN" A7>P1k3( BCDEF5Q7B{

<" GH1I;J KLM7N?1OPQ7" $ER¡¢3*£¤" Barrow et al. +321#/?N¥¦YB4§F/Y"SῌTFUVKWX1YNZ[Q7\]^1ῌ¨§ i©ªK¢«_`Q7@ aB" bcdDefgh ijk<"¬/­®YB@ ¯°" ()*+,-" ()*+lmneK .1῍ efopqrstpuvwx" +33+#,- /6787± " ± 1²Ya@/yCN?@* ³´µ9 ¶ · ¸-,+ῌ2/*/ ³´µ¹º -/* : "  ef" pH" " »¼

 = P 3/ ¼ R,**-S

14

Jf.- /g-*bh#&ij+34-%OF,   k1,+ ,,   /* mL l0m&no! *./ kg kg*+

p

q-Ar / g 11 s2o -/ mL 3t +2 uvw

      

FxywFx zN wFx{ l0m4b-.*0* cm   , mm*- !"#$ %&'()& NO&"+,-./01 2345678"+,9pH |,ῌGHIJ567}q'(3tF , 58c *.*+ mol L*+~67

RNH.S, SO. :;  <ῌ" = + &>

 NH.NO- *b -/ mL 3t 3t*b56&j   +?&>&';

L,*b3t wFx l9 / 5(@A=BC  , DCa,E F Mg,E @A=GHIJ:  ,HIJ|GHIJ ; f.-r SO.

,*+,9 3t*b- *b{ l0m4<*b-!K"L#M1NO P$= %&'( Q R+331S?

-3t5=&l0mq- R*b>6 + g

T&UVN WXY + &> Y) Z[cm*- FN(;S Nr  %&'( Q R+32+S &?\1NO,]^_*b3t&ON , ?]

:, P$Z['( *b-s2o *.*+ mol L*+ *b3t{ l0mwFd!=!=+e ,HIJ@A-xy +2 uvwFx wFx{l9y9RCECS '(GHIJ@A- RAECS -%L GHIb *../ mm (ON5`apH 0 cJ *b @ON $¡ῌ+ῌ"

A& pH  ( b, GHIJ

=Table + Physical and chemical properties of soil
pH RH, *S
pH RKClS/40//40,H®nH- R¯I}῍S *++41H®nH- R¯7}῍S *+*4+-

CEC Rcmolc kg*+S *,Ca,EMg,EKENaE
BCJK6 R῍S,,41,*4-+*4,+*4+1*4+3-4/,@A=GHIJRcmolc kg*+S*Cl*NO-*SO.,**421*4-0+413°!±,41,L6² : ³´ R῍Sµ¶·¶M¶N¸¹ Q&',
56(FNO NH.E 7}s2 ( ,HIJ¢£f¤ GHIJHIJ¥¦&'(-    -+pH 

s2o3t+ 58§0 *.*+ mol L*+ B¨ / 5C©3t ª¨*b

pH "Y , &> B¨*b3t pH /./0 FD pH *./ «-¨*b pH -D *.1 E pH "&¬-2VF­ B!HIJF!HIJf.&Gx OH* F,42,/4*1.,413,34-+Light Clay*+ : CN º» R(no! -3.2῍S*, : Shollenberger *- : *.*+ M NaOH *bR, g : +/* mLSO

ῌ+Fig. +

P$Z[Electric charge characteristics of soil.

£¤ : ¥¦§  ¨©S'%&ª«¬f15



   `a^" IJHAQbcmp!^qxHA yA

!" #$%&'(

fsNOP" , z Ca,w Mg,w +F + z Kw

+, pH /./-0./ . /0123%"

Naw >{Q^qxHA |=^ IJ<X} Mg,w)+332*4567 89 pH :;< =>?@.A-, HA:U /B0CD:EFGHIJHAKLMNOPQRST:U - Naw Q~Dgg:VHA AWH IJ<X + <Y"Z[\H VHA + zfsNOP Naw ", zfsNOP+FH u=:VHvu IJ]Q^_  BNOPQ" . <Y`abc-- ῌIJHA *.*+ mol Ld+eHA fMNOPg"h

MNOPsNOPg"^ HA

VHA+i  CldjNO-d ^_ >kNOPlm

C* : IJHANOPQ )mol Ld+* V* : IJCDg+nQo;:VH IJ.ABNOPdd-Cl  NO+F

"bcmgMNOP>6pAqr.

A)L* Cn : CDIJ n <YNOPQ )mol Ld+*
Vn : n <YCDIJCDg )L* Vrn : n <YCD~[CDg )L* h  n <Y/0CD:I

NOPg" )Cnd+Vrnd+wCoVo*dCn

Q"IJ<X . <Y

Vn ^  =:g^ Hv n¡+ <sNOPQRS tuv" U .
w.

JHAKLT:VHA NH

ῌ,Fig. ,

ῌFig. -B0 /0CDIJ<X pH RS

pH change with repetitious ammonium
sulfate and ammonium nitrate solution
addition.

B0IJ]MNOPQRSAnion concentration change with repetitious ammonium sulfate solution addition.

ῌ.

/0CDIJ]sNOPQRSFig. .

Cation concentration change with repetitious ammonium nitrate solution addition.

ῌ/

B0 /0CDIJ] Mg K ¢gFig. /Ammoniu$ sulfate and Mg, Na accumulation desorption quantity in the ammonium nitrate solution addition.

K-@O A 3/ ¼ W,**-X

16

 n/ 

cmolc kg+ !

"#%& NO-  ' NH.$  7;

 0  + #  H$ pH 78 CEC FGL&l!%&7ῌ !" !"#%&' !"#()  *

(+,ῌ-,.

-,./ , 456 pH 7 *.1
8 9:1 .);5< NO- 7=> AEC ; CEC 87?@A
BC& DE NO-  ;'.
 !"#7FG NH 7;H

C& IJ K. !"#7;L&

MNOPQ7BC1RSBC&IT K.

7'D op pH =>5& CEC ;l!%&=:H

C&  +) 25< !"#  ,. NH.$ H$^_7`BqBCIJ DC ῌ !"# r pH bs7?
@&$g0'1 tuvw&x%yz{5&& r H$ OH|}~3H

L&D

 !"#L&K. !"#%&.  D7 UV W+32*X 5<YZBC1'&!"#%&

7#'D NH.$ 7 , n

SO., D5< -, NH.$/0'123%&$.

m& f",.

.+   0 4+) 2L& H$
 !"#7[\']  H$^_l ,* ' (O)L&.

*L&E #q%+?yz{7,7`B'D7& ,./ pH BC*./ => a pH bc7GI'de8 0Bowden et al.W+311XBolan and Barrow

%&D7fgHC IJ

!"#%&NH.$  3Ihi

b- !"#.j/'C1W+32.X Barrow et al. W+321X Goldberg W+33,X 7%& x%yz{1O0'1# b-!

-, !"#%& NO-   pH 8j1;  SO., )k pH
7=> AEC 7FGL&l!%&3( a ;

"# 01 Barrow et al. W+321X 5<!"# 2q&D74BC1'&$I3 4 W+32,X -.  5C # !y ¡!¢J5p{£¤¥¦, -,./ pH  NH.$(+ !"# 0 4 -,.]5b-%< .%.j%+yz{
5<&3HC&  x%yz{
J§&¨%!"#67 Barrow et al. W+321X
5C H$ OH  S % # ῌ !"# ῌb-!"#r©ª8 a % f9 ῌ !"#b %67BC&  d %«:!"#;7

 ¬­ , ©®¯&7<L&DE ,ῌ-,.de83 ῌ-!"# a %   $ I!"#

WNH.$X  b % L&  , |/'4  ,  aiani aicat «C°C i %!"# !"#±=  y  WmVX g ¨%  !"#  Wm molc m,X s ¨%&Wm molc m,X C ¨%²> WFm,XL  KH, KOH, Kani, Kcat «C°C H$ OHῌ0Fig. 0

ῌ !"#pH (+*!"#Adsorption of anion and cation in relation
to equilibrium concentration and pH.

!"#!"#}) Z ³)41'& B F : ´¡zµ ) R : ²+ ) T : ¶·  e : ²¸ k : {¹º# ) NS : S %»?!"#  NT : a b %»? «C°C

GH : IJKLMNO PQRSTUVWXY%Z[   1  Bowden et al. +32* !"#$ %&'()*+ ,-.
 /01  23456 Barrow N. J.

 Nernst  S  yS ῍ῌ,
Table ,+321 78 pp. +,/9+-, :; <= a 01

Equations used for the Four-plane model+ῌ+> ai?ani@Concῌ
i Zῌ
i exp ῌZῌi FyῌRT+ῌ,> ai?cat@ConcῌῌZῌ
i Zῌ
i exp ?
i FyῌRT,> PZC@Alog KHB +.?log KOH Cῌ,-> yS@ KTῌe ,4-*- PZC?pH.> gS?H@NS aS?Hῌ +BKH aS?HBKOH aS?OH/> gS?OH@NS aS?OH +BKH aS?HBKOH aS?OH
0> sS@gS?H?gS?OH
1> ya@yS?sSῌCa b
2> ga?ani@NT Kani aa?aniῌ+BKani aa?ani
3> sa@ga?ani Zani+*> yb@ya? sSBsa ῌCa b++> gb?ani@NTZaniAKani ab?aniῌ +BKani ab?aniBKcat ab?cat C+,> gb?cat@NTZcatAKcat ab?catῌ +BKani ab?aniBKcat ab?cat C+-> sb@gb?catgb?ani+.> yd@yb? sSBsaBsb ῌCa b+/> sd@?+4,,D+*+*ECF*./sin h *4*+3/Zcat yd+0> sSBsaBsbBsd@*

ῌῌ1Fig. 1

17. 

Bowden et al. +32*

Schematic representation of Four-plane model (Bowden et al. +32*).

bc*W » 3/ ¼ ,**-18

  , : ga anijiklm,DS !" jiklm3A 3   , : NS, NT, CSa, Cab, Cbd, KH, KOH,UVPA pH Lm $ iklm

KCat, Kan   !" !#$ %3A pH LUVP+m& '( +33+ $ %)*( +33/ +,!-.D$  UVPA$ iklm+~,

/01 + 234$ 56 Marquardt 789

+Z" b:;<=!" >?$ 789@9ABC F-D," hUVPAi$ jiklm

UV34!#$ ! NH. +g
N(=" NH. AUVP~Z($ iBASIC Ver 0.- ,DEF!"

NO$ Bowden etklm+jikLῌ"#al. +311 $ Barrow et al. +321 $ Kamewada +33/+4N" Alva et al. +33* A$ P$[bc3G H IJKLM $3A$  PQ  $ pH <N!R

M ST$ UVW 

X+EY=D,"Z $  P+Q 3$pH <[\]A^_`abc3Adef>,gN(=" h3$ i$ jiklmnop pH$  P mol Lm

 - J

,+$  m molc

 D Mq<!"eL$ Ca, +m¡¢D," !$ dA£¤ , ¥¦§¨3$ iῌjik6©V D?$ ª% D,N"
$ S?« pH  H$ OH +*  !" H Aiῌjiklm pH &FDm$ OH A

iῌjiklm pH Lm !" h>?$ rqb sA$ btuW^vwxyz{| +32-  / }~ 0* cm : --* m g,

,D$ + m molc m , D$ iklm pH [A,  !L¬$pH /.2­0., jiklmL,'®34!

#$ OH Ailm+M=!"Z $ H AiklmRA$ jik!"lmL +­, ¯=$ iklm

.ῌ, ῎ῐ῏῍HIJK3!aMm molc m , i$ jiklm

,D2 !"AM0 n3$kg

 SO., +SQ! cmolc

3 3 pH  UVPi$ ,

²³ !">?$  - (M3´#!  !" b­dVµ) Cbd A¶ ·S ~$ Barrow +321 L=O$ b>!"!$Abck pH +°±dA¸¹ D, D," !$ H  o KH Ailm+ . ¯ºP~$ H +ῑῌ2Fig. 2

i$ jiklm aM S3

Comparison of the experimental anion adsorption with calculated valuesin the aplane by four plane model for each solution addition.

ῑῌ3

i$ jiklmM pH­UVPFig. 3

Caluculated charge density on four planes
in relation to pH.

ΐ¼ :  #$%&'(ῌ89 :;-c19*+01g SO.,n ῐ>89῎_" pH efopjq1 D.c 7ῌ345689῎456rs t$456

rsuvwx " *+ NH.k" SO.,n 8
9῎_ Hk rsyz/c

OPQRST{|}ZYD)[\D a P SO.,n"NO-n89῎_" BC~ ῍ D
0cpHP s FUV " *+01g s" *+01_" 3456ῌ<=ῑ῏ Dῌ+**+" ,+01g S P H"OH 89῎

Fig. +*

Calculated H , OH adsorption on S
plane in relation to pH.
ῌ-Table -1cS P Hk" OHn 89῎[\~G." *+01g Hk 89῎,+G." *+01_ pH efBC]^D" <&6Q" i _#$%(ῌ²³´µ¶·¸~

Most suitable value for each parameter

²³´µ¶

,+*+

NS ¹mmolc mn,ºNT ¹mmo+c mn,ºCsa ¹F mn,ºCab ¹F mn,ºCbd ¹F mn,ºKH ¹L moln+ºKOH ¹L moln+ºKCat ¹L moln+ºKani ¹L moln+º*420.
-43+3+4-2**4/,.
+»+*0+4*-*,4,3»+*+4**»+*n0-410*,4/,3.4*+0.4++0*4+**2410»+*/,401»+*.
340,»+*/
34-0»+*n3.41-»+*, )j BC [\ "   )" #$%&'(ῌ89:;G. Mi
ED" ¡¢ (ῌ£¤¥¦B§¨©" ª¡Ht«¬­®¯M °±ZY  Alva et al. (+33*) : Reactions of gypsum or phosphogypsum in highly weathered acid subsoil, Soil
Sci Soc. Am. J., /. : 33-ῌ332.
Barrow et al. (+321) : A comparison of models fordescribing the adsorption of anions on variable pH charge mineral surface, J. Colloid Interface Sci.,++3 : ,-0ῌ,/*.
Barrow, N. J. (+321) : Reactions with Variable-Charge/    Soils. Martinus Nijho# Publishers. pp. +,/ῌ+-,, !" #$%&'(ῌ)*+" ,+-./USA.

01 " pH

Bolan and Barrow (+32.) : Modeling the e#ect of2&" 3456ῌ745689:;" <=ῑῐ>?

phosphate and other anions on the surface@῎ABC D ED" F01G34568

charge of variable charge oxides. J. Soil Sci., -/ :9῎H pH 2&AIJKLMN" OPQRST )UVWX DGaMb

YZBC" [\]^_`

+c ,+ῒd01,1-ῌ,2+.
Bowden et al. (+32*) : Describing the adsorption ofphosphate, citrate and selenate on a variable-

pH  " *+

charge mineral surface. Aust. J. Soil Res., +2 : .3ῌ

,c <=ῑῐ>?@῎_" ,+01gh*+

Bowden et al. (+311) : Ionic adsorption on variable

_ pH ef D01gi." F

0*.

jῐ>?@῎_ Nak hMg,k " + lh, limD

charge mineral surfaces, Aust. J. Sol. Sci., +/ :+,+ῌ+-0.

 [ 2 3/ ¥ ,**-20

+33+ :  pp. -0ῌ-1  Goldberg (+33,) : Use of surface complexation models
in soil chemical systems, Adv, Agron, .1 : ,--ῌoI +33+ : pqrst,^/uvXWwx

yz{|} SALS pp. 33ῌ++* ~D  mI +33/ :  eft pp. +0/ῌ+03

-,3.

!"#ῌ$%&' +32* : ()*+,-.
/01 2 , 3 ()*,45/6789:;
<=>?@A BCD E /+ : 3/ῌ+*+.
Kamewada (+33/) : Increase in Cation Adsorption
Induced by Surface Complexation of Surfate on
Andisols and Prediction by “Four-Plane Model”,
Soil Sci. Plant Nutr., ., (.) : 12/ῌ133.

FG&HIfjkl : pp. 0,ῌ01 
mn+32, : JKLMNOPQRS?

BCD E /- : .11ῌ.1/.
TU01V9WX ,**, : YZ[\],^/_`abcd efg`efh_`ῌie

~D  BCD+32+ : :; pp. 2/ῌ

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