Citation
Leaching of cations during displacement by acid solutions through columns of cecil soil

Material Information

Title:
Leaching of cations during displacement by acid solutions through columns of cecil soil
Creator:
Liu, Ko-Hui, 1951-
Publisher:
[s.n.]
Publication Date:
Language:
English
Physical Description:
xvi, 221 leaves : ill. ; 28 cm.

Subjects

Subjects / Keywords:
Dissertations, Academic -- Soil Science -- UF
Ion exchange ( lcsh )
Soil Science thesis Ph. D
Soils -- Effect of acid rain on ( lcsh )
Soils -- Leaching ( lcsh )
pH ( jstor )
Subsoil ( jstor )
Topsoil ( jstor )
Genre:
bibliography ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis (Ph. D.)--University of Florida, 1987.
Bibliography:
Bibliography: leaves 215-220.
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Ko-Hui Liu.

Record Information

Source Institution:
University of Florida
Holding Location:
University of Florida
Rights Management:
Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
Resource Identifier:
030574320 ( ALEPH )
17625202 ( OCLC )
AEW2000 ( NOTIS )
AA00004842_00001 ( sobekcm )

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Full Text
130
Concentrations of exchangeable cations in all of the treated
soils were determined by extraction with 1 M neutral NH^OAc
(Thomas, 1982).
Soil Column Preparation and Procedure for Displacing HC1
Solution Through Columns
Each soil column consisted of a stack of 1-cm thick
_2
acrylic plastic (plexiglass) rings with 3.72 x 10 m
inside-diameter. Water-proof, acid-resistant electrical
tape was tightly wrapped around the outside of the rings to
insure that lateral leakage of water did not occur during
runs. Each column had dimensions of 0.2 m length and 0.0375
m inside diameter, giving a total internal volume of 2.21 x
-4 3
10 m The soil was held in the columns by a fine nylon
mesh and a piece of Whatman no.42 filter paper placed over a
thin plastic disc with small holes distributed over its
surface in each of the inflow and outflow endplates. A
check for water leaks was made prior to packing the soil
into a given column. Each column was then placed in a
vertical position and sequentially packed by slowly adding
incremental quantities of soil and tapping the side of the
column until a desired soil bulk density was obtained.
After packing, the entire soil column was mounted between
two wooden boards for support and fastened with four
threaded steel rods to hold the soil and rings in place.
Duplicate soil columns were constructed for each chemically
pretreated and mixed soil. Columns included Ca-saturated
topsoil, Mg-saturated topsoil, K-saturated topsoil,


203
proportional to the H+ concentration of the applied solution
for the mixed soil, but the application of pH 3.9 acid
solution did increase the quantities of cations leached
compared to the case where pH 4.9 solution was applied.
Base saturation of cations was apparently decreased by acid
application to the soil columns.
Conclusions
The clay content of treated subsoil was 2.7-fold
greater than for treated topsoil, but organic matter content
was 1.6-fold greater for the topsoil than for the subsoil.
Exchange sites of pretreated Cecil subsoil gave
equivalent fractions of 95 and 99 % saturation with respect
+ + 2+
to the major cation of saturation (K Ca or Mg ) in the
cases of where exchangeable Al^+ was considered or not in
the calculation of cation exchange capacity. For pretreated
Cecil topsoil, however, equivalent fractions totalled 85 and
95% saturation with respect to the major cation of
+ 2+ 2+
saturation (K Ca or Mg ). Leaching of Cecil soil with
unbuffered salt solution resulted in an increase in the
cation exchange capacity of the soil.
All of the first few samples of effluent from soil
columns that received HCl solutions were observed to have
low pH but high concentrations of cations. This observation
could be explained by the replacement efficiency of H+ for
the cation-saturated sites as well as by a salt effect.
Soil chemically pretreated with a given cation was observed
to be more sensitive to the pH effect of the input solution


Concentration (mmole (+) /l)
Figure 3-9 The effect of input solution pH upon the breakthrough curves of summed
concentrations of Ca^+, Mg K+ and Na+ in effluent from subsoil
columns.
V£>
00


183
Table 4-16 Concentrations of cations in solution
and exchange phases for Mg-topsoil after
leaching with pH 3.9 HCl solution
Depth
Ca
Mg
K
Na
A1
Sum
(cm)
mmole
(+) l'1
1.0
0.587
0.115
0.142
1.340
0.213
2.397
2.0
0.322
0.584
0.161
0.164
0.024
1.256
3.0
0.067
0.387
0.106
0.848
7.860
9.268
4.0
0.569
0.370
0.215
0.861
0.078
2.093
5.0
0.192
0.704
0.115
1.410
0.053
2.474
6.0
0.215
0.629
0.299
1.280
0.367
2.790
7.0
0.657
0.398
0.197
2.260
0.178
3.690
8.0
0.354
0.432
0.141
1.680
1.350
3.957
9.0
0.399
0.388
0.186
1.890
1.860
4.723
10.0
0.491
0.372
0.075
1.660
0.173
2.771
11.0
0.595
0.652
0.179
4.050
0.053
5.529
12.0
0.539
0.559
0.197
2.300
1.630
5.225
13.0
0.437
0.580
0.230
2.490
4.170
7.907
14.0
0.503
0.991
0.321
3.310
21.200
26.325
15.0
0.439
0.457
0.127
1.530
0.058
2.611
16.0
0.255
0.431
0.117
1.570
0.138
2.511
17.0
0.403
0.536
0.216
1.620
10.900
13.675
18.0
0.411
0.497
0.106
1.640
3.750
6.404
19.0
0.527
0.454
0.157
1.730
5.570
8.438
20.0
0.517
0.872
0.199
1.870
21.000
24.458
Depth
Ca
Mg
K
Na
A1
Sum
(cm)
phase
Kg 1
1.0
1.320
0.473
0.230
0.391
6.772
9.186
2.0
2.880
4.110
0.281
0.478
1.001
8.750
3.0
2.060
7.200
0.153
0.435
0.767
10.615
5.0
2.540
8.640
0.326
0.467
0.890
12.863
7.0
1.950
9.260
0.166
0.348
0.801
12.525
10.0
1.850
9.460
0.198
0.304
0.767
12.579
13.0
1.920
9.460
0.185
0.348
0.745
12.658
16.0
2.160
8.840
0.166
0.283
0.645
12.094
18.0
1.980
10.100
0.205
0.337
0.601
13.223
20.0
2.210
10.700
0.230
0.500
0.556
14.196


181
Table 4-15 Concentrations of cations in solution
and exchange phases for K-topsoil after
leaching with pH 4.9 HC1 solution
Depth
(cm)
Ca
Mg
K
Solution
Na
A1
Sum
ise
mmole(+)
L
1.0
0.407
1.330
0.426
2.050
0.006
4.219
2.0
0.292
1.620
0.463
0.761
0.012
3.148
3.0
0.182
1.420
0.478
0.946
0.016
3.042
4.0
0.139
0.259
0.511
0.528
0.016
1.453
5.0
0.135
2.120
0.744
1.150
0.014
4.163
6.0
0.212
2.710
0.700
1.230
0.018
4.870
7.0
0.355
1.050
0.565
0.487
0.016
2.473
8.0
0.208
0.449
1.140
1.580
0.019
3.396
9.0
0.164
2.420
0.770
0.661
0.009
4.024
10.0
1.150
1.460
0.919
1.500
0.018
5.047
11.0
1.380
0.518
1.170
1.720
0.012
4.800
12.0
0.436
0.992
1.080
0.763
0.012
3.283
13.0
0.120
0.062
0.721
0.380
0.011
1.294
14.0
0.092
0.045
0.733
0.283
0.012
1.166
15.0
0.144
0.089
1.040
0.430
0.014
1.717
16.0
0.103
0.037
0.967
0.274
0.023
1.404
17.0
0.045
0.052
1.040
0.215
0.022
1.374
18.0
0.076
0.059
1.110
0.215
0.076
1.536
19.0
0.112
0.089
1.170
0.313
0.020
1.704
20.0
0.501
2.100
0.944
1.050
0.039
4.634
)epth
cm)
Ca
Mg
K
Na
A1
Sum
mmole (+) Kg
1.0
0.561
0.041
0.582
0.217
2.891
4.292
3.0
0.599
0.062
1.300
0.239
1.768
3.968
5.0
0.674
0.082
1.920
0.261
1.568
4.505
7.0
0.699
0.082
2.620
0.207
1.423
5.031
9.0
0.561
0.062
2.290
0.196
1.579
4.688
11.0
0.649
0.103
2.650
0.239
1.501
5.142
13.0
0.674
0.082
3.200
0.217
1.390
5.563
15.0
0.836
0.082
3.010
0.239
1.446
5.613
17.0
0.836
0.103
3.480
0.217
1.357
5.993
20.0
1.500
0.391
6.270
0.087
1.201
9.449


Concentration mmole (+)/Kg soil
miscible displacement with 3.6 pore volumes.


165
exchange sites, but was not as effective in enhancing
+ s 2+
competition of H ions with divalent cations such as Mg
_ 2+
and Ca
3+
Concentrations of Al in Effluent from Mixed Soil Columns
3+
Concentrations of Al in effluent from mixed
topsoil and subsoil columns that received HC1 solutions, are
presented in Figs. 4-21 and 4-22, respectively. Initial
3+ -1
concentrations of Al were approximately 2.80 mmole(+) L ,
for effluent from mixed topsoil that received pH 3.9 HCl
solution, and 0.47 mmole(+) L 1 from subsoil columns that
received pH 4.9 HCl solution. In general, concentrations of
eluted Al3+ in the effluent from columns of mixed subsoil
were quite low after the first few samples of effluent, and
no differences in these values were observed for applied HCl
solutions with different pH. For mixed topsoil columns,
3+
concentrations of Al decreased gradually and the pH of
3+
input HCl solution did effect the concentration of Al in
the effluent. Higher concentrations of Al3+ occurred
in initial effluent from columns receiving pH 3.9 solution
3+
than at pH 4.9. Total quantities of Al in the effluent
from columns receiving pH 3.9 solution were not reasonably
greater than for pH 4.9, however. The reason for this
observation was uncertain.
Concentrations of Cations in Solution and Exchange Phases
for Treated and Mixed Soil Columns after Application of 25
Pore Volumes of HCl Solution
Treated Subsoil. Concentrations of cations in solution
and exchange phases are presented in Tables 4-6 and 4-7 for


ion (mmole ( + ) /l)
-p
(0
L
-P
C
0
u
c
G
U
10
'O
B-+
] 1 1 1 r
O Ca2+
* = Mg2+
+ = K +
X = Na +
2
%
' + +
OQ
^X-XIxgff a%^
++ +
X
Pore Volume (V/V ) of Effluent
a
Figure 4-15 Breakthrough curves of cations in the effluent from a mixed-cation
topsoil column which received pH 3.9 input HCl solution.
25
158


(mmo le ( + ) / 1)
30
145


15
sites (Helfferich, 1962; Cho, 1985). The value of CT is
assumed to be constant for a given soil material. For
numerical simulations in this work the magnitude of K
s was
assumed to be constant (Valocchi et al., 1981) during the
ion exchange transport process.
Transport with Ion Exchange
For the case of binary cation exchange and steady water
flow, the convective-dispersive mass-transport equation
[2-1] can be explicitly written as
3Cn a 3C. 32C1 3C..
+ = D v [2-15]
3t 0 3t 3x 3x
and
3C9 a 3C9 32C9 3C9
+ = D 1- v [2-16]
3t 0 3t 3x2 3x
Equations [2-14] and [2-15] are coupled through additional
equations for the time rate of change of adsorbed-phase
terms (the second terms on the left-hand sides of equations
[2-15] and [2-16]) to specifically describe the cation-
exchange process. If one assumes the soil cation exchange
capacity CT to be time invariant at any given location in
the soil, it can be expressed as the local sum of the
concentrations of cations in the exchange phase as
CT
c + c
ul c2
[2-17]


178
Table 4-13 Concentrations of cations in solution
and exchange phases for Ca-topsoil
after leaching with pH 4.9 HC1 solution
Depth Ca Mg K Na Al Sum
(cm)
Solution
phase
T 1
1.0
1.330
0.204
0.565
0.268
0.006
2.373
2.0
0.913
0.103
0.453
1.090
0.012
2.571
3.0
0.606
0.086
0.413
0.891
0.016
2.012
4.0
0.718
0.174
0.632
1.020
0.016
2.560
5.0
0.731
0.197
0.577
0.939
0.014
2.459
6.0
0.521
0.089
0.445
0.646
0.018
1.719
7.0
0.687
0.215
0.465
1.100
0.016
2.483
8.0
0.599
0.148
0.256
0.630
0.019
1.652
9.0
0.695
0.109
0.200
0.522
0.009
1.535
10.0
0.692
0.207
0.387
0.770
0.018
2.074
11.0
0.674
0.070
0.224
0.500
0.012
1.480
12.0
0.958
0.074
0.216
0.600
0.012
1.860
13.0
0.852
0.194
0.401
0.852
0.011
2.310
14.0
0.888
0.140
0.380
0.826
0.012
2.246
15.0
0.946
0.156
0.299
0.750
0.014
2.166
16.0
0.727
0.046
0.176
0.496
0.023
1.469
17.0
0.862
0.099
0.259
0.665
0.022
1.907
18.0
1.080
0.155
0.186
0.565
0.076
2.062
19.0
1.230
0.270
0.265
0.609
0.020
2.394
20.0
1.010
0.165
0.164
0.435
0.039
1.813
Depth
i Ca
Mg
K
Na
Al
Sum
t \
phase
l cm)
Kg 1
1.0
6.610
0.082
0.249
0.130
6.249
13.320
3.0
10.500
0.082
0.288
0.174
5.393
16.437
6.0
9.480
0.062
0.160
0.272
5.526
15.500
8.0
10.100
0.062
0.205
0.217
5.582
16.166
10.0
10.900
0.062
0.275
0.283
5.582
17.102
12.0
11.100
0.021
0.230
0.261
5.315
16.927
14.0
10.500
0.021
0.179
0.283
5.404
16.387
16.0
11.500
0.000
0.217
0.304
5.010
17.031
18.0
13.000
0.103
0.294
0.326
4.759
18.482
20.0
11.400
0.103
0.480
0.370
6.416
18.769


168
Table 4-6 Concentrations of cations in solution
and exchange phases for K-subsoil
after leaching with pH 3.9 HC1 solution
Depth Ca Mg K Na A1 Sum
(cm) Solution phaje
mmole ( + ) L
1.0
0.354
0.058
0.215
1.130
0.014
1.771
2.0
0.287
0.054
0.413
1.230
0.009
1.992
3.0
0.619
0.107
0.640
2.420
0.014
3.801
4.0
0.372
0.062
0.454
1.480
0.007
2.374
5.0
0.344
0.049
0.370
1.310
0.046
2.119
6.0
0.489
0.099
0.570
3.700
0.008
4.865
7.0
0.564
0.115
0.532
2.680
0.009
3.900
8.0
0.531
0.099
0.350
1.930
0.021
2.931
9.0
0.473
0.064
0.390
1.530
0.008
2.465
10.0
0.459
0.066
0.384
1.220
0.110
2.239
11.0
0.297
0.078
0.480
1.720
0.024
2.600
12.0
0.437
0.084
0.502
2.210
0.009
3.242
13.0
0.312
0.058
0.434
1.200
0.029
2.033
14.0
0.374
0.064
0.454
2.180
0.011
3.083
15.0
0.803
0.140
0.734
2.960
0.009
4.646
16.0
0.713
0.104
0.962
2.680
0.009
4.468
17.0
0.342
0.058
0.315
1.340
0.014
2.069
18.0
0.332
0.069
0.465
1.580
0.028
2.474
19.0
0.743
0.118
0.622
2.990
0.019
4.492
20.0
0.813
0.111
0.458
2.320
0.006
3.708
Depth
Ca
Mg
K
Na
A1
Sum
(cm)
Hjau i id i ly l
-'lid C.
Kg'1 i
1.0
0.661
0.041
1.820
0.652
9.885
13.059
3.0
1.070
0.041
13.400
0.685
0.512
15.708
5.0
1.100
0.123
14.100
0.674
0.701
16.698
7.0
1.520
0.103
14.800
0.739
0.467
17.629
9.0
1.250
0.041
15.100
0.652
0.789
17.832
11.0
1.380
0.082
13.000
0.674
0.556
15.692
13.0
1.330
0.062
14.300
0.652
0.441
16.785
16.0
1.470
0.062
14.100
0.685
0.311
16.628
18.0
1.170
0.062
14.400
0.652
0.523
16.807
20.0
1.160
0.062
14.100
0.696
0.478
16.496


4-15
Breakthrough curves of cations in the effluent
from a mixed-cation topsoil column which received
pH 3.9 input HCl solution 158
4-16 Breakthrough curves of cations in the effluent
from a mixed-cation subsoil column which received
pH 3.9 input HCl solution 159
4-17 Breakthrough curves of K+ from mixed-cation topsoil
columns which received input HCl solutions with two
different pH values 161
2+
4-18 Breakthrough curves of Ca from mixed-cation topsoil
columns which received input HCl solutions with two
different pH values 162
4-19 Breakthrough curves of K+ from mixed-cation subsoil
columns which received input HCl solutions with two
different pH values 163
2+
4-20 Breakthrough curves of Mg from mixed-cation subsoil
columns which received input HCl solutions with two
different pH values 164
3+
4-21 Breakthrough curves of A1 from mixed-cation topsoil
columns which received input HCl solutions with two
different pH values 166
3+
4-22 Breakthrough curves of Al from mixed-cation subsoil
columns which received input HCl solutions with two
different pH values 167
xiv


29
Clemson, South Carolina. The exact location of the site was
reported earlier by Dr. V. L. Quisenberry (Cassel, 1985)
from the Agronomy Department of Clemson University.
Reported texture of the Cecil soil profile varied from site
to site, with the clay content of the Ap horizon ranging
from 6 to 38 percent depending upon the amount of subsoil
mixing which had occurred subsequent to soil erosion. Clay
content in the B horizon ranged from 42 to 72 percent
(Cassel, 1985). In situ values of unsaturated hydraulic
conductivity reported (Cassel, 1985) for the 0-30 cm depth
-4 -2 -1
ranged from 1.70 x 10 to 4.51 x 10 cm h whereas those
for the 30-60 cm depth ranged from 4.32 x 10 4 to 4.6 x 10 1
cm h 1, respectively. In situ values of soil water content
3 -3
for the 0-30 cm depth ranged from 0.275 to 0.495 cm cm ,
3 -3
whereas values ranged from 0.409 to 0.560 cm cm for the
30-60 cm depth (Cassel, 1985). Typic Hapludult soils are
freely drained with great or moderate depth to hard rock,
have an ochric epipedon that is not both thick and sandy,
and have a loamy or clayey particle-size class in an
argillic horizon.
Cecil topsoil and subsoil bulk samples for this
research were obtained from the 0-30 and 30-60 cm depths,
respectively, of the profile. The soil was air-dried,
passed through a 2-mm sieve, and stored in covered plastic
buckets.
Values of pH for the soil samples were determined in a
soilrwater suspension (1:1 soil:water) using a glass


192
Table 4-23 Charge balance of cations for columns of
K-topsoil
K-
topsoil
pH 3.9 (mmole(+))
2+
.. 2+
+
3 +
H
Ca
Mg
K
Na
A1
Initial cations
0.219
0.030
6.272
0.109
2.115
Total input 0.348
Final #
0.036
0.117
0.075
0.121
0.009
solution phase
Final #
0.335
0.048
0.893
0.081
2.210
exchange phase
Total 0.009
0.001
0.001
5.144
0.042
2.910
output in effluent
K-topsoil pH
4.9 (mmole(+))
2 +
, 3 +
H
Ca
Mg
K
Na
A1
Initial cations
0.217
0.029
6.233
0.108
2.102
Total input 0.029
Final #
0.026
0.078
0.069
0.068
0.002
solution phase
Final #
0.275
0.040
0.990
0.077
0.584
exchange phase
Total 0.008
0.233
0.044
5.167
0.098
2.518
outputin effluent
#: undetermined


Exchange Phases for Treated and Mixed
Soil Columns after Application of 25 Pore
Volumes of HCl Solution 165
Charge Balance Using All Major Cations
for Treated and Mixed Soil Columns 190
Conclusions 203
V SUMMARY AND CONCLUSIONS 206
Summary 206
Conclusions 212
REFERENCES 215
BIOGRAPHICAL SKETCH 221
vi


pH of Effluent
7 O
6.4
5 e
5.2
4.6
4.0
,8?*
*
oOOcJt)
***** *%
*o
**>
o
o
L
o
L o
-o
14
o
t * OO" o o
^> o 000 eo
o o O o
H o o
Oo
*
* O
8 -
o o
O pH 3.9
* pH 4.9
^ lO 15 20
Pore Volume (V/V ) of Effluent

25
Figure 4-2 Breakthrough curves for pH in the effluent from Ca-subsoil columns which
received input HCl solutions with two different pH values.
141


solutions with two different pH values
140
4-2 Breakthrough curves for pH in the effluent from
Ca-subsoil columns which received input HC1
solutions with two different pH values 141
4-3 Breakthrough curves of K+ from K-topsoil columns
which received input HC1 solutions with two
different pH values 144
2+
4-4 Breakthrough curves of Ca from Ca-topsoil
columns which received input HCl solutions with
two different pH values 145
2+
4-5 Breakthrough curves of Mg from Mg-topsoil columns
which received input HCl solutions with two
different pH values 146
4-6 Breakthrough curves of K+ from K-subsoil columns
which received input HCl solutions with two
different pH values 147
2+
4-7 Breakthrough curves of Ca from Ca-subsoil columns
which received input HCl solutions with two
different pH values 148
2+
4-8 Breakthrough curves of Mg from Mg-subsoil columns
which received input HCl solutions with two
different pH values 149
3+
4-9 Breakthrough curves of Al from K-subsoil columns
which received input HCl solutions with two
different pH values 151
3+
4-10 Breakthrough curves of Al from Ca-subsoil columns
which received input HCl solutions with two
different pH values 152
3+
4-11 Breakthrough curves of Al from Mg-subsoil columns
which received input HCl solutions with two
different pH values 153
3+
4-12 Breakthrough curves of Al from K-topsoil columns
which received input HCl solutions with two
different pH values 155
3+
4-13 Breakthrough curves of Al from Ca-topsoil columns
which received input HCl solutions with two
different pH values 156
3+
4-14 Breakthrough curves of Al from Mg-topsoil columns
which received input HCl solutions with two
different pH values 157
xiii


58
respectively. The CEC for each section was obtained by
extraction with buffered 1 M NH^OAc plus unbuffered 1 M KCl,
2+
and then summing exchange-phase concentrations for Ca ,
Mg^+, K+, Na+ and Al^+. The CEC for the last set of
sections obtained from the soil column were used to
represent the CEC for experimental columns of subsoil and
topsoil, respectively. Column effluent pH values were below
pH 4.5 for both columns (Fig. 2-23). This acidity could be
3+ 2+
coming from A1 which underwent exchange with Ca and
2+
Mg The pH values of the input solutions were 5.5 for
CaC^ and 5.7 for MgC^.
Figures 2-13 and 2-14 demonstrate the dramatic model
sensitivity to the cation exchange capacity parameter.
The cation exchange capacity values used were 10.6 and 54.0
mmole(+) Kg 1 soil for topsoil, and 17.0 and 70.0 mmole(+)
Kg ^ soil for subsoil, respectively. A large increase in
2+
CEC value the simulated movement of the Mg
front to be retarded during miscible displacement relative
to the experimental data. This effect was greatest for the
finer-textured Cecil subsoil.
Calculated and observed data did not coincide exactly
for either the topsoil or subsoil columns. Overall,
model-simulated curves for distributions of solution-phase
2+
concentrations of Mg with depth best described
experimental data when the smaller of the cation exchange
capacity values were used. This result was as expected,


129
1.10 cm h 1 ( 3%) Darcy velocity to each column. A check
for concentrations of cations in the column effluent was
made periodically. A conventional way to estimate if the
soil exchange sites are saturated with a specific cation is
by monitoring concentrations of the specific cation in the
effluent with time. If the cation concentration in the
effluent becomes equal to that of the input solution then
the soil exchange sites are commonly considered to be
saturated with that cation species. Such a technique,
however, is not without difficulties, particularly if the
exchange sites initially contained highly-preferred species
of cations. In this investigation concentrations of a
specific cation in the effluent reached 99% of the input
solution concentration after about 3-4.5 pore volumes of
elution, but very small concentrations of other ion species
remained even after leaching of the column for a month or
more. After the flow was terminated, the columns were
leached with 1.5 liters of 95% ethanol to remove all soluble
salts. Soil was then removed from each column, air-dried,
ground, passed through a 2-mm sieve and stored in large
plastic bottles for future use. Three columns of subsoil
were prepared similarly to the aformentioned procedure for
topsoil columns. Therefore, Ca-saturated, Mg-saturated,
K-saturated topsoil and subsoil materials were obtained.
Pretreated mixed-topsoil and mixed-subsoil were obtained by
carefully mixing equal weight ratios (1:1:1 for Ca:Mg:K) of
Ca-saturated, Mg-saturated, and K-saturated soil materials.


191
Table 4-22
Charge balance
Ca-topsoil
of cations for columns of
Ca
-topsoil
pH 3.9
(mmole(+) )
2+
.. 2+
, 3 +
H
Ca
Mg
K
Na
Al
Initial cations
4.163
0.007
0.036
0.000
0.783
Total input
0.284
Final
#
0.075
0.060
0.017
0.169
0.004
solution
phase
Final
#
3.682
0.017
0.103
0.116
0.518
exchange
phase
Total
0.004
4.060
0.016
0.024
0.100
0.116
output in
effluent
Ca
-topsoil
pH 4.9
(mmole(+))
2+
, 3 +
H
Ca
Mg
K
Na
Al
Initial cations
4.240
0.007
0.036
0.000
0.800
Total input
0.029
Final
#
0.070
0.012
0.029
0.059
0.002
solution
phase
Final
#
3.810
0.022
0.093
0.095
2.000
exchange
phase
Total
0.003
2.120
0.042
0.019
0.023
0.193
output in
effluent
#: undetermined


22
and { S } = [ -C1 ,0,
'' Cn+1 ]
Consequently, one has
{ C'^ } = [ A ]_1 [ B ] { } + [ A ]_1 { S } [2-35]
Alternatively, in component form
ti n+1 i i
Ci <*>>=) (t> + 6Biin+1Cn+1 (t) .
where [ a. ] = [A]-1 [B] [2-36]
f J
and [ p. ] = [A]"1
Substituting equation (2-35) into equation (2-29), the cubic
polynomial approximating function g(z,t) for C(x,t) in the
ith element, in polynomial of degree three in z, is given by
the following formula:
n+1 ,
9i(2't)=+1ai,j(ZlCj(t) + bi,l(z)C l(t) + bi,n+lC n+l(t)
where
z3-3z2+2zh.2
+ ai+l,j
3 2
z -zh.
l
6hi
[2-37]
z-h.
6i,j
+ 6i+l/j
[2-38]
3 2 2
z -3z n.+2zh.z
t>i ! -*- / J- -L / J- V,
3 2
z -zh^
i+1,1
^ z3-3z2hi+2zh.2 z3-zh2
bi,n+l(z) _Pi,n+l + Pi+l,n+l ~
in which 6 is the Kronecker's delta. Therefore the cubic


Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
LEACHING OF CATIONS DURING DISPLACEMENT BY ACID
SOLUTIONS THROUGH COLUMNS OF CECIL SOIL
By
KO-HUI LIU
August, 1987
Chairman: R.S. Mansell
Major Department: Soil Science
Cation transport under conditions of steady liquid flow
was investigated, using columns filled with water-saturated
Cecil (Typic Hapludult) topsoil and subsoil. Initially the
2+
soils were saturated with Ca using CaC^ solution, which
was then miscibly displaced by MgC^ solution.
A Galerkin finite-element method with cubic-spline
shape functions was used to numerically solve the equation
for one-dimensional transport and binary exchange of cations
in the Cecil soil columns. The numerical model was verified
by assuming that the solute was non-reactive solute or that
paired cations had no preference for soil exchange sites.
Cation exchange capacity (CEC) was shown to be the most
sensitive input parameter when the model was used to
simulate cation transport in the soil columns. Increase of
CEC increased retardation of cation movement. Relatively
xv


18
superscript notation for C was only used for formulation
purposes in the finite-element method.
A Galerkin Finite-Element Numerical Method
Finite-Element Method
Finite-element methods typically incorporate an
approximating integral equation to replace the original
governing partial differential equation (Pinder and Gray,
1977). Variational and weighted-residual techniques are two
methods most commonly used to obtain the approximate
integral equation. The Galerkin finite-element weighted-
residual method has been widely used for the mass-transport
equation (Price et al., 1968; Pinder, 1973) and is the
method used here. In the finite-element method, the domain
of interest is discretized into a number of subdomains
called elements. In this study, a line-segment element was
used and a cubic-spline function was chosen as the
interpolation function. For the Galerkin approximation,
consider a linear differential operator of the form
L (u) =0 on domain D (2-24]
To solve u, a trial function u(x,t) is assumed which is
composed of a linear combination of approximation functions
containing time-dependent, undetermined coefficients G^(t)
and specified-shape functions N^(x) that satisfy the given
boundary condition of the problem. The trial function can
be expressed as
* u(x,t) = 2 G.(t) N.(x) .
j=l 3 3
u(x,t)
[2-24]


Concentration (mmole ( + ) /l)


III CATION LEACHING DURING CONTINUOUS DISPLACEMENT
BY AQUEOUS HYDROCHLORIC ACID SOLUTION THROUGH
COLUMNS OF CECIL SOIL 75
Introduction 75
Basic Theory 77
Surfaces of Soil Particles 77
Cation Exchange Equilibria 78
Effects of Acidification 79
Materials and Methods 80
Physical and Chemical Properties of Soil... 80
X-Ray Diffraction 81
Column Preparation and Displacement
Procedure 82
Dissection of Soil Columns, Extraction, and
Chemical Analysis 83
Results and Discussion 85
Concentrations and pH of Column Effluent .. 87
Concentrations of Cations in Solution
and Exchange Phases 101
Estimated Selectivity Coefficients of
Ion Pairs 106
Charge Balance of Major Cations for
Topsoil and Subsoil 114
Conclusions 119
IV CATION LEACHING DURING CONTINUOUS DISPLACEMENT BY
HYDROCHLORIC ACID SOLUTION THROUGH COLUMNS OF
CHEMICALLY-PRETREATED CECIL SOIL 123
Introduction 123
Cation Exchange Reaction 124
Saturation Mechanisms for Soil Exchange Sites
with a Single+Cation Species 124
Mechanisms of H Replacement of
Exchangeable Cations on Soil Exchange
Sites 126
Materials and Methods 128
Preparation of Pretreated Soil 128
Soil Column Preparation and Procedure for
Displacing HC1 Solutions through Columns. 130
Method for Dissection, Extraction and Chemical
Analysis of Soil Columns 132
Results and Discussion 133
Exchange Sites for Chemically Pretreated
Soil 138
Effluent pH for Treated Soil Columns 138
Cation Concentrations in Effluent from
Treated Soil Columns 139
Cation Concentrations in Effluent from
Chemically Pretreated Mixed Soil Columns. 154
Concentrations of AlJ in Effluent from Mixed
Soil Columns 165
Concentrations of Cations in Solution and
v


H
N
+
w
Q>
ri
0
E
E
c
0
-H
0
c.
c
0
u
c
o

Depth (M)
Figure 2-8 Experimental distributions of Mg + concentrations in the solution phase
of the subsoil column after miscible displacement with 3.6 pore volumes,
along with calculated results obtained using three values for the
volumetric water content.
tn


193
Table 4-24 Charge balance
Mg-topsoil
of cations for columns of
Mg-
topsoil
pH 3.9 (mmole(+))
2+
2 +
, 3 +
H
Ca
Mg
K
Na
A1
Initial cations
0.326
4.241
0.072
0.109
0.181
Total input 0.277
Final #
0.030
0.043
0.016
0.145
0.330
solution phase
Final #
0.756
2.836
0.776
0.141
0.491
exchange phase
Total 0.001
0.033
9.840
0.022
0.021
0.739
output in effluent
Mg-
topsoil
pH 4.9 (mmole(+))
2+
3 +
H
Ca
Mg
K
Na
A1
Initial cations
0.326
4.241
0.072
0.109
0.181
Total input 0.025
Final #
0.033
0.044
0.020
0.146
1.341
solution phase
Final #
0.656
0.320
0.082
0.141
0.330
exchange phase
Total 0.001
0.035
4.128
0.040
0.017
0.849
output in effluent
# : undetermined


109
Table 3-8 Topsoil selectivity coeffients as determined
after leaching with pH 4.9 HC1 solution
Mg-->Ca
K-->Ca
Na-->Ca
Na-->K
K-->Ca
1
0.15043
0.10667E-01
0.13705E-01
1.1335
0.70911E-01
2
0.12198
0.89593E-02
0.27394E-02
0.55296
0.73449E-01
3
0.09647
0.76123E-02
0.18604E-02
0.49436
0.78906E-01
4
0.08007
0.48023E-02
0.19921E-02
0.64407
0.59975E-01
5
0.11313
0.60545E-02
0.25930E-02
0.65443
0.53520E-01
6
0.12076
0.58130E-02
0.23563E-02
0.63668
0.48137E-01
7
0.03417
0.62203E-02
0.45791E-03
0.27132
0.18206
8
0.05909
0.59719E-02
0.27082E-02
0.67341
0.10106
9
0.17471
0.45946E-02
0.57266E-03
0.35304
0.26298E-01
10
0.17483
0.10347E-01
0.84928E-02
0.90598
0.59182E-01
Average selectivity values
0.11256 0.71042E-02 0.37478E-02 0.63197 0.75350E-01
Na-->Mg
Al-->Ca
Mg-->A1
K-->A1
Na-->A1
1
0.91103E-01
0.88631
0.38408E-02
0.11703E-02
0.17042E-02
2
0.22458E-01
0.01999
0.90790E-01
0.59979E-02
0.10141E-02
3
0.19284E-01
0.00557
0.16127
0.89009E-02
0.10754E-02
4
0.24879E-01
0.00323
0.15917
0.58600E-02
0.15657E-02
5
0.22922E-01
0.02439
0.59357E-01
0.30165E-02
0.84548E-03
6
0.19513E-01
0.00837
0.21037
0.48441E-02
0.12502E-02
7
0.13402E-01
0.00089
0.44839E-01
0.16450E-01
0.32855E-03
8
0.45829E-01
0.00121
0.17083
0.13278E-01
0.40550E-02
9
0.32777E-02
0.02230
0.23916
0.20856E-02
0.91769E-04
10
0.48577E-01
0.04832
0.11060
0.47880E-02
0.35605E-02
Average selectivity values
0.31125E-01
0.10206
0.12502
0.66392E-02
0.15491E-02


160
efficiency of H+ for basic cations described in the
aforementioned paragraph. After the first collected sample
of effluent, concentrations of cations were observed to
decrease drastically in the second or third samples, and
then afterwards concentrations gradually decreased with
time. The initially larger concentrations for mixed subsoil
than for mixed topsoil are attributed to the fact that the
CEC of the pretreated mixed subsoil was three-fold greater
than for mixed topsoil. For mixed topsoil and subsoil,
concentrations of K+ were the greatest, concentrations of
2+ 2+ +
Mg and Ca were less than for K and concentrations of
2+ 2+
Mg and Ca were difficult to distinguish from each other.
The same concentration behavior was also found when pH 4.9
HCl was applied to columns of mixed topsoil and subsoil,
2+ 2+
respectively. This occurred because divalent Ca and Mg
cations are more preferred than monovalent K+ and Na+
cations for the Cecil soil exchange sites.
The effect of pH of the input HCl solutions upon
+ 2+
elution of K and Ca from mixed topsoil columns is shown
. 2+ +
in Figs 4-17 and 4-18, and the effect on Mg and K from
mixed subsoil is shown in Figs 4-19 and 4-20. The pH of
input HCl solution had a greater effect upon concentrations
+ 2+ 2+
of K in column effluent than on Ca or Mg This
observation implies that a lower pH (higher H+
concentration) of input solution enhanced competition of H+
ions with monovalent cations such as K+ and Na+ for soil


ion (mmole (-+-) /l)


36
The two different CEC values for the Cecil soil
resulted from the two extraction methods used for
exchangeable acidity. Exchangeable acidity as determined by
BaC^-TEA extraction has more practical utility for
calcareous than for acid soils (Thomas and Hargrove, 1984),
and KCl extraction is reflects the immediate need for lime
(Thomas, 1982). Thomas (1982) suggests that the best method
for determining exchangeable acidity for acid soils is to
use a neutral, unbuffered salt to remove the acidity at the
pH of the salt solution-soil mixture.
Clay content of the Cecil subsoil was 2.7 times greater
than that for the topsoil, but organic matter content of the
topsoil was only 1.6 times greater than that for the
subsoil. The ratio of subsoil to topsoil CEC values was
somewhat less (1.3 to 1.6) than the 2.7 ratio for clay
contents. The higher clay content in the subsoil did,
however, result in a higher CEC and volumetric water content
for the subsoil. The texture of the topsoil was sandy loam
as compared to sandy clay loam for the subsoil. The type of
clay minerals in the topsoil and subsoil indicates that both
soils were highly weathered and had electrostatic charge
sites which were predominately pH-dependent charge surfaces.
Verification of the Numerical Model
Predictive accuracy of the computer program for the
numerical solution to the convective-dispersive ion-
transport equation was evaluated for a simple problem of
transport of a conservative solute (i.e. where Ks = 0) for


74
soil-to-solution ratio a/0. The exact magnitude of R could
not be obtained, since R involved unknown concentration
variables. The cation exchange capacity is the most
critical input parameter to the simulation. This is a
result of the cation retardation function R = (l+(a/0)F),
where the function F in equation [2-20] is a function of CT.
Therefore, cation movement undergoes greater retardation in
soil with a larger value of CEC (and thus a larger value of
R) than in soil with a small CEC.


143
is called a "salt effect" (Wiklander, 1975). As mass flow
occurred, the acid displacing solution mixed with the native
soil solution by hydrodynamic dispersion. Acidity caused by
the salt effect was gradually leached, resulting in
increased pH of the soil solution and effluent once more.
From about 5 to 25 pore volumes of effluent the pH ranged
from about 6.0 to 6.6, indicating strong buffering by the
soil. The buffering reflects that H+ ions which were
partially removed from the solution phase either by ion
exchange, dissolution of clay minerals, reactions involving
aluminum species, or a combination of the three. The
2+
initial effluent concentrations of Mg from Mg-topsoil or
2+
Mg-subsoil were relatively higher than Ca from Ca-topsoil
or Ca-subsoil and than K+ from K-topsoil and K-subsoil. The
cause of these differences was uncertain.
The effect of input solution pH upon concentrations of
eluted cations in column effluent showed that the lower pH
of input acid solution resulted in approximately the same
quantities of cations being leached as obtained at the
higher pH. This phenomenon was found for all pretreated
topsoil and subsoil columns, but was most obvious for the
topsoil (Figs. 4-3, 4-4, and 4-5). Concentrations of
cations in the effluent from pretreated subsoil columns are
given in Figs. 4-6, 4-7, 4-8 for K-subsoil, Ca-subsoil, and
Mg-subsoil columns, respectively. A greater effect of input
solution pH upon cation elution was found for pretreated
topsoil than for subsoil. This can be explained by the


138
Exchange Sites for Chemically Pretreated Soil
Treating the Cecil soil with a specific cation tended
to increase the base saturation and CEC (Tables 4-1 and 4-5)
of the soil, with the largest effect being found for the
subsoil. The pretreated topsoil and subsoil materials were
non-homoionic with respect to cations in the exchange phase,
indicating that the soil exchange sites were not completely
saturated initially with any one specific ion. For example,
equivalent fractions of K+ in K-topsoil were 95 and 72% for
cases in which Al was excluded from and included in the CEC
2+
calculation, respectively. Equivalet fractions of Mg in
Mg-topsoil were 89 and 86% for similar cases, with
2+
corresponding values of Ca for Ca-topsoil 99 and 84%, 96
and 95% for K-subsoil, 99 and 98% for Mg-subsoil, and 99 and
95% for Ca-subsoil. Quantities of other basic cations in
the exchange phase were small compared with the dominant ion
for each of the pretreated soils.
3+
The subsoil had very little exchangeable Al following
the cation-saturation procedures. Saturation of topsoil
exchange sites was not as complete as it was for the
subsoil.
Effluent pH for Treated Soil Columns
Regardless of pH of the applied HC1 solution, effluent
pH of all columns of pretreated Cecil topsoil, subsoil, and
mixed-cation columns started at about 4.0-4.4 and then
quickly increased to about pH 6.7 within two pore volumes of
elution. Thereafter, readings fluctuated around pH 6.1-6.8


UNIVERSITY OF FLORIDA
3 1262 08554 1612


133
obtained extraction with neutral 1 M NH^OAc (Thomas, 1982).
Unbuffered 1 M KCl (Thomas, 1982) was used to obtain
3+
exchangeable Al Concentrations were corrected for
entrapped equilibrium solution near the exchange sites.
2+ 2+ ^
Concentrations of Ca Mg K and Na in the column
effluent, solution and exchange phases of each soil column
were analyzed by an atomic absorption spectrometer as
3+
described in previous chapters. The Al was determined by
optical emission spectroscopy (inductively coupled argon
plasma, ICAP) on a unit located in the Soil Testing
Laboratory, Soil Science Department, University of Florida.
Results and Discussion
Initial exchangeable cations in nontreated topsoil and
subsoil are presented in Table 4-1. The soil parameters
used for the miscible displacement experiments are presented
in Tables 4-2, 4-3 and 4-4 for chemically-pretreated
topsoil, pretreated subsoil, and mixed topsoil and subsoil,
respectively.
From Tables 4-2 through 4-4, the deviation of the bulk
density, volumetric water content and pore-water velocity of
hand-packed treated topsoil and subsoil columns were within
3 %, respectively. Similar deviations for the bulk
density, volumetric water content and pore water velocity
were also found for hand-packed mixed subsoil and topsoil
columns.


CHAPTER I
INTRODUCTION
Description of Problem
During recent decades, the environmental impact of acid
precipitation has become a major concern in many
industrialized countries. Concerns about possible harmful
effects on soil, vegetation and surface-water supplies have
resulted in intensive research in this area. The most
serious effects of acid deposition upon forest soils are
commonly thought to be the potentials for accelerating
cation leaching, for increasing soil acidity, and hence for
decreasing forest productivity. Acidification of surface
waters resulting in the release of toxic aluminum ions
3+
(Al ) from sediments in lakes and streams is harmful to
aquatic ecology (Hutchinson and Havas, 1980).
During rain events, rainwater which does not run off
the surface or undergo evapotranspiration infiltrates into
the soil profile. As the soil water moves by mass flow,
hydrodynamic dispersion mixes the native soil solution with
the incoming rainwater. Ion species moving with the soil
solution may undergo ion-exchange with counter ions
initially present on the soil exchange phase. In addition
to ion exchange phenomena, the presence of H+ in the
rainwater results in secondary reactions such as acid
1


Effluent pH
6 o


137
Table 4-5 Concentrations of exchangeable cations for
pretreated and mixed topsoil and subsoil
Soil
Concentrations of exchangeable cations
(mmole(+) kg soil)
K
Na
Mg
Ca Al
K-topsoi
17.20
0.30
0.08
0.60 5.80
Mg-topsoil
0.20
0.30
11.70
0.90 0.50
Ca-topsoil
0.10
0.00
0.02
11.70 2.20
K-subsoil
50.20
0.40
0.10
1.40 0.70
Mg-subsoil
0.30
0.20
96.80
0.30 1.40
Ca-subsoil
0.20
0.00
0.10
54.40 0.20
Mixed-topsoil
6.10
0.60
6.50
5.10 3.00
Mixed-subsoil
16.10
0.50
31.50
26.30 0.80
CEC
. 1
Dominant cation %
mmole(+) kg
soil
for this specific
Al included
CEC with A1J
included
K-topsoil
23.68
(K) 72
Mg-topsoil
13.60
(Mg) 86
Ca-topsoil
14.02
(Ca) 84
K-subsoil
52.80
(K) 95
Mg-subsoil
99.00
(Mg) 98
Ca-subsoil
54.90
(Ca) 95
Mixed-topsoil
21.30
*
Mixed-subsoil
75.20
*
CEC
1
Dominant cation %
mmole(+) kg
soil
for this specific
Al not included
CEC with Al"3 not
included
K-topsoil
18.18
(K) 95
Mg-topsoil
13.10
(Mg) 89
Ca-topsoil
11.82
(Ca) 99
K-subsoil
52.11
(K) 96
Mg-subsoil
97.60
(Mg) 99
Ca-subsoil
54.70
(Ca) 99.1
Mixed-topsoil
18.30
*
Mixed-subsoil
74.40
*


ion (mmole ( + ) /l)
148


6
then resulting in mixing of displacing and displaced
solutions in the porous media. In some investigations (Lai
and Jurinak, 1971; Reiniger and Bolt, 1972; Persaud and
Wierenga, 1982), empirical equations have been fitted to
measured adsorption data in order to obtain adsorption
isotherms for incorporation into the transport equation.
Ion chromatography theory is based upon differences of ionic
migration rates for different ions in a packed bed. In
modeling, the movement of these ionic species is based upon
the principle of conservation of mass. In multicomponent
chromatography theory (Bolt 1967; Helfferich and Klein,
1970), where the local equilibrium condition is also
assumed, the exchange relationship between any two given ion
species in the system can be described by a Vanselow
selectivity coefficient. This coefficient is valid when
ionic strength and ion-pair corrections are made for cation
activities in the solution phase (Babcock and Schulz 1963;
van Beek and Bolt, 1973). Therefore, quantitative
relationships between the equilibrium constants for ion
exchange, concentrations, and valences of each pair of ions
can be obtained. Using multicomponent chromatography, Rubin
and James (1973) proposed a general mathematical form for
transport and exchange for each of several ion species by
using a generalized Vanselow selectivity function. The
model was later used successfully to describe the processes
2+
of exchange and transport for three major cations (Ca ,
2+ +
Mg Na ) in an aquifer system (Valocchi et al., 1981). In


120
basic cations in the exchange phase were decreased and
3+
significant hydrolysis of Al in the soil occurred during
leaching with HCl. This effect was more pronounced for
topsoil that received pK 3.9 solution. For the subsoil,
only the end of the column that received acid input solution
showed significant losses of cations and dissolution of
3+
Al Generally, exchange-phase concentrations of basic
cations as determined with NH^OAc extraction before and
after leaching with HCl solutions were decreased for both
soils. The percent of base saturation before HCl
application was 52%, for the topsoil. After HCl
application, base saturation wass 0.1% and 1.5% for pH 3.9
and 4.9 treatments, respectively. For the subsoil, base
saturation was initially 68%. After acid application, base
saturation was 5.4% and 4.4% for the pH 3.9 and 4.9
treatments, respectively.
The distribution of cations in the exchange phase
followed the order Al3+ > Ca2+ > Mg2+ > K+ = Na+ for both
3+
soils. Al was the preferred ion on the exchange sites, as
expected due to its large valence and large equivalent
fraction initially on the exchanger. In the solution phase,
the distribution of cation concentrations followed the order
K+ ~ Na = Al3+ > Ca2+ > Mg2+ for topsoil and Na+ > K+ = Ca2+
2+3+ . .
>Mg > Al for subsoil. The exchange selectivity
coefficients for each pair of cations as estimated from
distributions of ion concentrations in solution and on
exchange phases at specific column depths varied with depth


17
o 3C. 9 2C, 3C1
( 1 + F ) = D = v [2-22]
31 3 3 x
The term R= l+(a/)F is referred to as the retardation
function for transport of ion 1 through the soil. For
binary nonpreferential (Kg = 1) homovaient exchange
F = Crj,/ CT and R = 1 + (a/0) (C^/C^) so that, for constant
cation exchange capacity, retardation of cation transport
tends to increase as CT decreases towards small values such
as those that normally occur in rain water. Also, for this
case, cation retardation can be expected to be greatest in
soils with highest values for CT and with highest
soil-to-solution ratios (a/0). Appropriate initial and
boundary conditions for equation [2-22] are
t = 0 x > 0 ci = c [2-23a]
9 C1
t > 0 x = 0 v = D + v C. and
3 x
9C1 [2-23b]
t > 0 x = L = 0 .
9 x
Partial differential equations given as [2-22] and
[2-23] constitute a mathematical description of cation
transport and exchange in a soil column of finite length L
during steady water flow, they were solved in this research
by use of a Galerkin finite-element method. For simplicity,
concentration for ion species 1 is denoted by C
throughout the remainder of the dissertation. Subscript or


169
Table 4-7 Concentrations of cations in solution
and exchange phases for K-subsoil after
leaching with pH 4.9 HCl solution
Depth Ca Mg K Na Al Sum
(cm) Solution pha^e
mmole (+) L
1.0
0.027
0.008
0.318
0.448
0.007
0.808
2.0
0.027
0.010
0.441
0.368
0.000
0.846
3.0
0.207
0.030
0.187
0.921
0.021
1.366
4.0
0.267
0.029
0.161
1.150
0.000
1.607
5.0
0.031
0.012
0.496
0.965
0.004
1.508
6.0
0.257
0.040
0.344
1.300
0.003
1.944
7.0
0.437
0.049
0.424
1.600
0.000
2.510
8.0
0.398
0.046
0.365
1.410
0.004
2.224
9.0
0.317
0.049
0.394
1.530
0.037
2.327
10.0
0.308
0.054
0.408
1.750
0.000
2.520
11.0
0.428
0.059
0.464
1.790
0.004
2.746
12.0
0.459
0.082
0.496
2.400
0.000
3.437
13.0
0.424
0.054
0.403
1.690
0.002
2.573
14.0
0.608
0.079
0.465
2.250
0.011
3.413
15.0
0.828
0.099
0.454
2.790
0.000
4.171
16.0
0.571
0.062
0.263
1.690
0.000
2.586
17.0
0.689
0.079
0.427
2.420
0.000
3.615
18.0
0.889
0.099
0.562
2.880
0.000
4.430
19.0
0.629
0.079
0.546
2.030
0.000
3.284
20.0
0.790
0.118
0.556
2.680
0.000
4.144
Depth
Ca
Mg
K
Na
Al
Sum
(cm)
pilu L
Kg x so
A 1
1.0
1.280
0.226
9.790
0.739
3.614
15.649
3.0
1.200
0.165
13.900
0.772
0.901
16.938
5.0
1.150
0.062
13.700
0.652
0.678
16.242
7.0
1.410
0.062
15.500
0.696
0.812
18.480
9.0
1.330
0.041
14.100
0.685
0.756
16.912
11.0
1.360
0.062
13.600
0.707
0.645
16.374
14.0
1.270
0.062
14.500
0.652
0.623
17.107
16.0
1.410
0.062
15.100
0.696
0.645
17.913
18.0
1.240
0.062
14.000
0.717
0.689
16.708
20.0
1.330
0.062
14.800
0.739
0.645
17.576


Concentrat ion (mmole (+) /l)
from Cecil topsoil columns.


2-10
2-11
2-12
2-13
2-14
2-15
2-16
2-17
2-18
2-19
2-20
2 +
Experimental and simulated distributions of Mg
concentrations for three values of bulk density for
the subsoil column after miscible displacement with
3.6 pore volumes 54
2+
Experimental distributions of Mg concentrations for
the topsoil column after miscible displacement with
4.5 pore volumes, along with simulation results for
three values of the selectivity coefficient 56
2+
Experimental distributions of Mg concentrations for
the subsoil column after miscible displacement with
3.6 pore volumes, along with simulated results for
three values of the selectivity coefficient 57
2+
Experimental distributions of Mg concentrations for
the topsoil column after miscible displacement with
4.5 pore volumes, along with simulation results for
two values of the cation exchange capacity 59
2+
Experimental distributions of Mg concentrations for
the subsoil column after miscible displacement with
3.6 pore volumes, along with simulation results for
two values of the cation exchange capacity 60
2+
Calculated and experimental distributions of Mg
concentrations in the solution phase for the subsoil
column after miscible displacement with 3.6
pore volumes 63
2+
Calculated and experimental distributions of Mg
concentrations in the exchange phase for the subsoil
column after miscible displacement with 3.6
pore volumes 64
2+
Calculated and experimental distributions of Mg
concentrations in the solution phase for the topsoil
column after miscible displacement with 4.5
pore volumes 65
Calculated and experimental distributions of Mg
concentrations in the exchange phase for the
topsoil column after miscible displacement with
4.5 pore volumes
2+
66
2+
Calculated and experimental distributions of Mg'
concentrations in the solution phase for the topsoil
column after miscible displacement with 4.5
pore volumes 68
2+
Calculated and experimental distributions of Mg
concentrations in the exchange phase for the topsoil
column after miscible displacement with 4.5
pore volumes 69
xi


10
3C. o 3C. 3 2C. 3C.
+ = D = v - i=l,2,. ..n [2-1]
3t 3t 3X^ 3X
where C^(x,t) (mmole(+) L 1) is the aqueous-phase
concentration of species i, (mmole(+) Kg 1) is the
2 -1
adsorbed-phase (exchange) concentration, D (m h ) is the
dispersion coefficient, v (m h ^) is the average pore-water
velocity, a (Mg m 3) is the dry-soil bulk density,
3 -3
(mm ) is the volumetric water content, x (m) is distance
(downward) in the soil, and t (h) is time. The second term
on the left-hand side of equation [2-1] describes the time
rate of change of the exchange-phase concentration for ion
species i. If n cation species are considered, n equations
having the form of equation [2-1] must be solved
simultaneously subject to the following initial and boundary
conditions:
t = 0 and x > 0
t > 0 and x = 0
t > 0 and x = L
+ v Ci
[2-2]
where C^^(mmole(+) L ^) is the initial concentration of each
species i in the porous medium and is the input solution
concentration for ion species i. Before solving equation
[2-1] subject to auxiliary equations [2-2], the time rate of
change of the adsorbed concentration (C^) in equation [2-1]
with respect to should be obtained as a functional


2-21 Simulation results a^d experimental data for
distributions of Mg concentrations in the solution
phase for the subsoil column after miscible
displacement with 3.6 pore volumes 70
2-22 Simulation results a^d experimental data for
distributions of Mg^ concentrations in the exchange
phase for the subsoil column after miscible
displacement with 3.6 pore volumes 71
2-23 Effluent pH values for the topsoil and subsoil
columns 72
3-1 Breakthrough curves for pH in the effluent from
Cecil topsoil columns which had received two input
HCl solutions with different values of pH 88
3-2 Breakthrough curves for cation concentrations in the
effluent from Cecil topsoil columns which had
received pH 3.9 input HCl solution 89
3-3 The effect of input+solution pH upon the break
through curves of K from Cecil topsoil columns.... 91
3-4 The effect of input solution pH upon the break-
thr^ugh+curves o| summed concentrations of Ca^ ,
Mg^ K and Na in effluent from topsoil columns. 92
3-5 The effect of input ^lution pH upon the break
through curves of AlJ from Cecil topsoil
columns 93
3-6 Breakthrough curves for pH in the effluent from
Cecil subsoil columns which received two input HCl
solutions with different values of pH 94
3-7 Breakthrough curves for cations in the effluent
from Cecil subsoil columns which received pH 4.9
input HCl solution 96
3-8 The effect of input ^olution pH upon the break
through curves of Ca from Cecil subsoil columns 97
3-9 The effect of input solution pH upon the brea£-
th^ugh+curves o£ summed concentrations of Caz ,
Mgz K and Na in effluent from subsoil columns. 98
3-10 The effect of input ^lution pH upon the break
through curves of AlJ from Cecil subsoil columns 99
4-1 Breakthrough curves for pH in the effluent from
Ca-topsoil columns which received input HCl
Xll


CHAPTER II
MODEL SIMULATION OF BINARY CATION EXCHANGE
AND TRANSPORT IN COLUMNS OF CECIL SOIL
Introduction
The exchange of cations between exchange and solution
phases in a soil system is an important phenomenon which
greatly influences nutrient movement in soil, leaching of
cations by acid-rain infiltration, reclamation of
salt-affected soil, contaminant migration, and other
processes. Ion transport in packed exchanger beds and in
soil columns has been investigated for many decades and
several approaches have been used to model the ion-exchange
process. Thomas (1944) developed an equation applicable to
cation transport in columns of synthetic ion exchanger,
assuming that the exchange mechanism obeyed reversible,
second-order, reaction kinetics. Rible and Davis (1955)
used chromatographic theory of ion exchange to investigate
cation exchange and transport in soil columns, but neglected
the effect of hydrodynamic dispersion during transport.
Assuming chemical equilibrium between cations in solution
and on the exchange phase, Lapidus and Amundson (1952)
proposed a model for ion transport such that exchange
followed a linear isotherm, with hydrodynamic dispersion
5


198
initial quantities for Mg-topsoil. For all of the
pretreated topsoil, quantities of all cations leached were
not directly proportional to the H+ concentration of the
applied solution, but larger quantities of major cations
were leached from columns receiving pH 3.9 HC1 than for pH
4.9 HC1. For example, for Ca-topsoil that received pH 3.9
HCl, 4.06 mole(+) of Ca^+ were leached but only 2.12
mmole(+) were leached when pH 4.9 HCl was applied. Mineral
dissolution was implied from concentrations of cations in
the leachate and on exchange sites. For example for
Ca-topsoil, K+ and Na+ were initially 0.036 and 0.0 mmole(+)
in the exchange phase but became 0.103 and 0.116 mmole(+)
after leaching with pH 3.9 HCl. Similar results were
observed for all treated topsoil columns of all cations
species examined. The increase of exchangeable-cation
3+
concentration was most dramatic for A1 Output from the
treated topsoil was observed to be greater than input, and
the resulting positive-charge-balance errors can be
attributed to the dissolution or decomposition of
interlayer-hydroxy vermiculite, as well as to other mineral
weathering processes in this soil.
Treated subsoil. Tables 4-25 through 4-27 present the
charge balance for Ca-subsoil, K-subsoil and Mg-subsoil,
respectively. Inputs were 18.336 and 18.089 mmole(+) and
outputs were 19.473 and 18.418 mmole(+) for Ca-subsoil that
received pH 3.9 and 4.9 HCl solutions, respectively.
Ca-subsoil gave charge-balance errors of + 6 and + 2 % for


CHAPTER IV
CATION LEACHING DURING CONTINUOUS DISPLACEMENT
BY HYDROCHLORIC ACID SOLUTION THROUGH COLUMNS OF
CHEMICALLY-PRETREATED CECIL SOIL
Introduction
Leaching of cations and movement of organic and
inorganic anions in response to acid rain deposition in
forest soils has been investigated by Mollitor and Raynal
(1982) and Ulrich et al. (1980). Cation exchange is
recognized as one of the important soil processes which
control detrimental effects of acid rain upon the nutrient
status of forest soils (Wiklander, 1975; Reuss, 1983; Cosby
et al., 1985a, 1985b). Experimental results have shown that
neutral salts added to soil-water suspensions or to dilute
solutions percolating through soil columns tend to decrease
acidification of the soil (Wiklander, 1975).
Very few published papers report investigations of the
leaching of soil cations during the displacement of aqueous
acid solutions through columns of soil where the exchange
sites have initially been saturated with a single specific
. + 2+ 2+
cation species such as K Ca or Mg Such an
investigation was performed during the research reported in
this chapter. The advantage of using chemically-pretreated
soil is that the soil system involves fewer species of
cations and thus the data are more easily interpreted.
123


exchange phases for K-topsoil after leaching
with pH 3.9 HCl solution 180
4-15 Concentrations of cations in solution and
exchange phases for K-topsoil after leaching
with pH 4.9 HCl solution 181
4-16 Concentrations of cations in solution and
exchange phases for Mg-topsoil after leaching
with pH 3.9 HCl solution 183
4-17 Concentrations of cations in solution and
exchange phases for Mg-topsoil after leaching
with pH 4.9 HCl solution 184
4-18 Concentrations of cations in solution and
exchange phases for mixed-cation subsoil after
leaching with pH 3.9 HCl solution 186
4-19 Concentrations of cations in solution and
exchange phases for mixed-cation subsoil after
leaching with pH 4.9 HCl solution 187
4-20 Concentrations of cations in solution and
exchange phases for mixed-cation topsoil after
leaching with pH 3.9 HCl solution 188
4-21 Concentrations of cations in solution and
exchange phases for mixed-cation topsoil after
leaching with pH 4.9 HCl solution 189
4-22 Charge balance of cations for columns of
Ca-topsoil 191
4-23 Charge balance of cations for columns of
K-topsoil 192
4-24 Charge balance of cations for columns of
Mg-topsoil 193
4-25 Charge balance of cations for columns of
Ca-subsoil 194
4-26 Charge balance of cations for columns of
K-subsoil 195
4-27 Charge balance of cations for columns of
Mg-subsoil 196
4-28 Charge balance of cations for columns of
mixed-cation subsoil 201
4-29 Charge balance of cations for columns of
mixed-cation topsoil 202
ix


Concentration (mmole ( + ) /l)
column after miscible displacement with 4.5 pore volumes, along with
simulation results for two values of the cation exchange capacity.




3
as acid solution infiltrates soil is central to evaluating
acid-rain effects upon forest soils. Predictions based upon
established soil physical-chemical methods would be the most
reliable method of evaluating long-term effects of acid rain
on soil (Reuss, 1983).
Objectives
The ion-exchange process is one of the most important
soil chemical processes which influences cation leaching
during infiltration of acid rain into soil. Thus, a
computer model solely based on binary ion-exchange
equilibrium and saturated steady water flow was developed
for predicting the movement of cation species in soil. The
response of cation leaching to input acid solution at two
different pH values was determined using columns of Cecil
soil (Typic Hapludult).
There are three objectives in this study. The first
objective was to evaluate a numerical model by simulating
binary cation exchange and transport during miscible
displacement of electrolyte solutions through columns of
Cecil soil. The second objective was to experimentally
determine effects upon cation leaching of applying
artificial acid-rain solutions (hydrochloric acid) to
columns of Cecil soil The third objective was to
determine the leaching effect of applied artificial acid-
rain solutions (hydrochloric acid) to columns of Cecil soil
pretreated to saturate exchange sites with specific cation


12
M
B
and
M.
B
[2-5]
M,
T
where represents the sum of Mft and Mfi (mole per kg)
of the soil. The relationship between activities and mole
fractions for ion species in the exchange phase is given by
Sposito (1981) as
*
[A] = UA Ma
[2-6]
tBl = MB ;
where uA and u0 are activity coefficients for cations A and

B on the exchange phase, and and Mfi are mole fractions
for cations A and B on the exchange phase, respectively.
The relationship between activities and concentrations
for the solution phase is given by Sposito (1981) as
[A] = rA Ma
[2-7]
[B] rB Mg ;
where rA and rg are ion activity coefficients for cations A
and B in the solution phase and and Mg are molar
concentrations for cations A and B in the solution phase.
Substitution of equations [2-6] and [2-7] into equation
[2-8] yields
K
[2-8]


172
Table 4-9 Concentratons of cations in solution and
exchange phases for Ca-subsoil after
leaching with pH 4.9 HCl solution
Depth
Ca
Mg
K
Na
A1
Sum
(cm)
r -L
1.0
0.503
0.066
0.178
1.910
0.129
2.786
2.0
0.826
0.092
0.257
2.440
0.018
3.633
3.0
0.479
0.046
0.137
1.140
0.765
2.567
4.0
0.523
0.056
0.192
1.310
0.369
2.450
5.0
0.575
0.053
0.192
1.610
0.080
2.510
6.0
0.659
0.066
0.235
2.310
0.167
3.437
7.0
0.665
0.069
0.135
1.660
0.013
2.542
8.0
0.555
0.056
0.108
1.250
0.129
2.098
9.0
0.645
0.072
0.143
1.660
0.125
2.645
10.0
0.659
0.053
0.171
1.380
0.156
2.419
11.0
0.681
0.066
0.221
1.650
0.040
2.658
12.0
1.220
0.094
0.327
3.900
0.040
5.581
13.0
0.840
0.072
0.193
1.940
0.031
3.077
14.0
0.831
0.082
0.132
2.200
0.067
3.312
15.0
0.495
0.049
0.085
1.380
0.018
2.027
16.0
0.575
0.049
0.151
1.230
0.031
2.036
17.0
0.816
0.095
0.204
2.030
0.027
3.172
18.0
0.551
0.076
0.171
1.570
0.142
2.510
19.0
0.591
0.072
0.153
1.460
0.169
2.445
20.0
0.399
0.059
0.099
1.060
3.180
4.798
Depth
(cm)
Ca
Mg
K
Na
A1
Sum
IUUWJ.G v t i\.y
1.0
8.980
0.123
0.205
0.261
0.979
10.548
3.0
10.400
0.041
0.173
0.304
0.289
11.207
5.0
11.600
0.041
0.256
0.283
0.300
12.480
7.0
10.500
0.041
0.198
0.326
0.289
11.354
9.0
11.000
0.041
0.147
0.370
0.322
11.880
11.0
11.500
0.041
0.160
0.391
0.334
12.426
12.0
9.610
0.041
0.192
0.348
0.311
10.502
15.0
10.500
0.021
0.179
0.174
0.311
11.185
17.0
10.500
0.041
0.166
0.196
0.300
11.203
19.0
11.600
0.041
0.179
0.380
0.322
12.522


79
*
The equivalent fractions (C^ ) for cations 1 and 2 in the
exchange phase are given by
where i and j refers to cations 1 or 2, (or C^) is the
concentration of exchangeable cation 1 or 2 in moles of
positive charge (equivalents per Kg of soil), and is the
solution-phase concentration (mmole(+) L of cation 1 or
2. The magnitude of Ks indicates the relative preference of
exchange sites for cation 2 over cation 1. If and
Ks = 1 the exchange sites show no preference for either of
two ions, whereas Ks < 1 indicates that cation 1 is adsorbed
preferentially, and Ks > 1 indicates that cation 2 is
preferred by the exchange sites.
Effects of Acidification
Continuous addition of acid solution to a soil tends to
increase total acidity of the soil and to decrease pH. The
extent to which soil pH is decreased by addition of acid is
greatly determined by the buffering capacity of a given
soil. A number of associated effects are also observed upon
addition of acid to soil. One of the more important effects
2+ 2+ 4"
is the loss of basic cations such as Ca Mg K and
Na+. Basic cations are leached with co-anions, such as
bicarbonate, chloride, nitrate, sulphate, or organic anions.
A second effect is the displacement of cations from
weak-acid exchange sites such as occur on humus and on


196
Table 4-27 Charge balance of cations for columns of
Mg-subsoil
Mg
f-subsoil
pH 3.9
(mmole(+))
2+
2+
, 3 +
H
Ca
Mg
K
Na
Al
Initial cations
0.093
30.164
0.093
0.006
0.436
Total input 0.125
Final #
0.044
0.013
0.015
0.148
0.001
solution phase
Final #
0.237
2.518
0.077
0.099
0.725
exchange phase
Total 0.021
0.041
22.959
0.043
0.041
0.062
output in effluent
Mg
-subsoil
pH 4.9
(mmole(+))
2+
. 3 +
H
Ca
Mg
K
Na
Al
Initial cations
0.094
30.380
0.094
0.063
0.044
Total input 0.026
Final #
0.037
0.010
0.020
0.108
0.029
solution phase
Final #
0.263
2.956
0.075
0.111
0.602
exchange phase
Total 0.01
0.154
22.438
0.035
0.039
0.035
output in effluent
#: undetermined


c
o
-H
-p
ra
L
-p
c
0
u
c

u
25
161


173
2 +
Ca occur in nonexchangeable forms such as between lattices
or interlayers of interlayer-hydroxy vermiculite
(M+(Mg,Fe)3(Si,Al)4O10(OH)2)/ where M+ denotes cation
species located between lattices or interlayers (Dixon and
Weed, 1977; Bohn et al., 1985). A long period of leaching
with acid solutions will result in weathering of the
minerals, releasing nonexchangeable cations from within the
lattices or interlayers.
Tables 4-10 and 4-11 present concentrations of cations
in solution and exchange phases for Mg-subsoil columns after
application of pH 3.9 and 4.9 HC1 solutions, respectively.
In the solution phase, concentrations of cations were of the
order Na+ > Ca^+ > K+ = Mg^+ > Al"^+ but, for the exchanger
2+ 3+ 2+
phase, concentrations of cations were Mg > Al > Ca >
Na+ > K+ for both pH treatments. If we compare
concentrations of cations in the exchange phase in Tables
4-10 and 4-11 with values in Table 4-4 for initial
2+
Mg-subsoil, the concentrations of Mg were greatly
3+
decreased by leaching but Al concentrations were changed
2+ +
only slightly, Ca and Na concentrations were increased
and K+ was decreased. This change in cation concentrations
was found both for pH treatments 3.9 and 4.9. Usually,
cation species with the higher valence have a higher
affinity for exchange sites. Therefore, high concentrations
of divalent and trivalent species were observed in the
exchange phase compared to Na+ and K+. Cations with low
valence demonstrated lower affinity for exchange sites, such


84
the whole system was of equilibrium. The next day, with the
column still in the vertical position, the tape was removed
carefully. After removing the outflow endplate, a piece of
parafilm was placed over the end of the column and a fine
steel thread was forced between consecutive rings in order
to slice the column into sections. Resulting sections of
soil were carefully removed and placed on a piece of
parafilm. Each whole section of soil was then packed into
a prenumbered small centrifuge tube which had a predrilled
small hole on the closed end. A Whatman number 42 filter
paper was place on top of the hole, inside the tube. Each
small centrifuge tube was then placed into a corresponding
large-size centrifuge tube along with a glass bead to
separate the extracted solution from soil in the small
centrifuge tube. Paired tubes were carefully placed in the
centrifuge and spun at 4000 rpm for 30 min. Soil samples
were then removed from the small centrifuge tubes and placed
into a weighing boat, and wet soil weights were recorded.
Soil in each weighing boat was air-dried and the soil weight
2+ 2+ +
recorded. Exchange-phase concentrations of Ca Mg K ,
and Na+ were obtained using a neutral 1 M NH^OAc extraction
method (Thomas, 1982). Correction was made for entrapped
equilibrium solution remaining in the exchange phase after
centrifuging, by taking differences in equivalents per L for
the extractant and the residual solution. Unbuffered 1 M
KC1 (Thomas, 1982) was used in order to obtain exchangeable
3+ 2+ 2+ +
A1 concentrations. Concentrations of Ca Mg K and


185
for mixed subsoil columns that received input HCl solutions
of pH 3.9 and 4.9, respectively. Concentrations of cations
throughout the column for the solution phase were generally
in the order K+ > Na+ > Ca2+ > Mg2+ > Al3 + but, for the
+ 2+ 2+ 3+ +
exchange phase the order was K > Ca > Mg > Al > Na .
If one only examines the shallowest depth for the column
receiving the pH 3.9 input acid solution, the exchange-phase
3+ 2+ 2+ +
concentrations were in the order A1 > Ca > Mg > K >
Na+ and for pH treatment 4.9 in the order Ca2+ > Mg2 + > Al3 +
+ + 2+ 2+
> K > Na Concentrations of the basic cations Ca Mg ,
*4" 3
K and Na were much less than the A1 concentration for
the pH 3.9 case. The pH 4.9 treatment had a reverse effect.
A comparison of concentrations on the exchange phase in
Tables 4-18 and 4-19 with values in Table 4-4 for the
original exchangeable cations in mixed subsoil showed that
2+ 2+ + +
concentrations of the basic cation Mg Ca K and Na
3+
were decreased but those Al remained fairly stable. The
base-cation saturation was remarkedly decreased by leaching.
Mixed topsoil. Tables 4-20 and 4-21 present
concentrations of cations in the solution and exchange
phases for mixed topsoil columns after receiving pH 3.9 and
4.9 input HCl solutions, respectively. Concentrations of
cations through the soil columns for the solution phase were
generally in the order Al3 + > Ca2+ > Mg2+ > K+ > Na+ for pH
treatment 3.9 and in the order Al3+ > Mg2+ > K+ > Ca2+ > Na+
for pH treatment 4.9. The exchange phase was in the order
Ca2+ > Al3+ > Mg2+ > K+ > Na+ for both treatments.


26
m, 3 3 t
n+1
hi
n
j£2J0 Vi (z> 11 + -
( CT + W)
n+1
E a. dz
i=l
3 Cj(t)
3 t
[2-48]
where n = CT Kg CT,
n+1 n+1 *
and W = CT + (K 1) ( E 6. E a. C,
1 s i=l 1 i=l 1/J 3
n+1
+ E 6. b. 1(-Cf q/D))
i=l 1 1,1 1
For the right-hand side of equation [2-46], the matrix
coefficients are
given as:
n+1
n+1
R =
m, 3
(
j-2
(
A J
hi a]
0
n+1
n+1
V,
U = v
(
U
(
£i
'll
. a
m, j
J-2
i-l J
o1 ]
n+1 n+1
V.
m,i = q cf (3S2 /ol am i(z) bifl (z) dz )), [2-51]
and
S = v
m, l
n+1 n+1 ,
< j-2 ( 1=1 J,1 am,i(2) bi,l (z) <
C() dz]
[2-52]
In the process of numerical integration, the definite
integral is given by equations [2-48] through [2-52]. Since
these equations are very complex, an explicit expression can
not be obtained. However, this integral can be effectively


121
for both soils and were highly dependent upon the cation
concentrations in solution and on the exchange phase as well
as upon cation valence and upon the pH of the applied HC1
solution.
Greater quantities of basic cations were leached from
soil columns that received pH 3.9 solution than of pH 4.9.
. 2+ 2+
Specifically, the total losses of divalent Ca and Mg
ions from the topsoil were 0.32 and 0.23 mmole(+),
respectively, during application of pH 3.9 and 4.9 HC1
solutions. For the subsoil these losses were only 0.12 and
0.08 mmole(+) for pH 3.9 and 4.9 HCl treatments,
respectively. Application of HCl solution definitely
accelerated leaching losses of cation nutrients from the
Cecil soil. Charge-balance errors ranged from -10 to -33%
and were likely due to undetermined H+ in solution and on
the exchange phase for the soil, as well as to negatively-
charged surfaces of Fe oxides, experimental error, soil
chemical reactions that act as sinks for applied H+, and
3+
acid dissolution that provides a source for Al to enter
into exchange reactions though the Column of Cecil soil
received solution with a ten-fold difference in HCl
concentration, the total quantities of basic cations removed
differed by less than two-fold. Therefore, leaching by the
HCl solution not only involved cation exchange between
monovalent, divalent, and trivalent ions, but also
apparently involved the dissolution of gibbsite and other
Al-bearing compounds (Sardin et al., 1986).


8
approximations. Their numerical simulations included
homovalent binary cation exchange with different values for
the cation exchange capacity and dispersion coefficient
parameters. Valocchi et al. (1981) extended this technique
to a two-dimensional (axially symmetric) model with the use
of isoparametric quadrilateral elements in order to solve a
ground-water contamination problem for an aquifer. They
concluded that, for a binary system, ion concentration
profiles consist of a single advancing exchange front while,
for a ternary system, two fronts may be separated by a
plateau zone. These phenomena were actually observed in
a a a "f 2^ 2 ^
their field simulation of Na Mg and Ca breakthrough
curves for well-water downstream from an injection well.
Jennings et al. (1982) followed the approach of Rubin and
James (1973) and applied equilibrium interaction chemistry
(speciation, etc.) independently of the
convective-dispersive transport equation. A set of
algebraic chemistry equations was coupled to the mass
transport equation and a numerical solution was obtained by
the Galerkin finite-element method applied over the space
domain. A backward finite-difference approximation was used
for the time derivative, and a surface complexation sorption
model allowed the consideration of complex metal and ligand
species at soil surfaces. The sorption reaction was assumed
to occur under instantaneous equilibrium conditions. Using
concepts from multispecies ion chromatography as given by
Valocchi et al. (1981), and mobile-immobile water theory as


Concentration (mmole (+)/l)
152


ACKNOWLEDGEMENT
The author wishes to express her sincere appreciation
to Dr. R. S. Mansell, chairman of the graduate supervisory
committee, for guidance, valuable discussions, and
suggestions throughout her entire course of study.
Sincere appreciations are also extended to Drs. E. A.
Hanlon, C. C. Hsu, W. W. McFee, and R. D. Rhue for their
valuable discussions and helpful suggestions made during
this work and their review of the manuscript.
Special appreciation is expressed to Dr. S. A. Bloom,
Scientific Programmer, for assistance and counsel in
plotting graphs, to Dr. C. C. Hsu for generously lending the
LSODE subroutine and to a friend, Mr. Fang-Yin Lee, for
providing x-ray analyses for each of the soil samples.
This research was supported in part by the U.S.
Environmental Protection Agency under Project A0457-06,
entitled "Effects of Acid Deposition on Ion Mobilities in
Selected Soils". Partial support by the Soil Science
Department is also greatly appreciated.
Deepest gratitude is expressed to the author's parents
for their support and to her husband Ming-Hsiung for his
understanding, consideration, and encouragement.
in


62
using these two additional sets of CEC values was to
3+
determine if exclusion of exchangeable Al from the CEC, or
if exclusion of all of the existing cations species except
2+ 2+
Ca and Mg would improve simulated results. First,
modified cation-exchange capacity values were obtained by
summing the exchange phase concentrations of all cations
3+
species except Al over all depths as given in Tables 2-3
and 2-4, and then taking means for topsoil and subsoil,
respectively. Magnitudes for subsoil and topsoil were 12.73
and 4.97 mmole(+) Kg ^ soil, respectively. Using these
modified cation exchange capacity values, calculated results
2+
for Mg concentration distributions in solution and
adsorbed phases are given in Figs. 2-15 and 2-16 for subsoil
and in Figs. 2-17 and 2-18 for topsoil, respectively.
Agreement between simulated and experimental data was better
2+
for the subsoil than for the topsoil. Simulations for Mg
concentrations in the topsoil showed an overestimation of
2+
Mg concentrations in both the solution and exchange
phases.
The second method for obtaining a better estimation of
cation exchange capacity values was obtained by summing the
2+ 2+
exchange-phase concentrations of Ca and Mg for all
depths (Tables 2-3 and 2-4) and then taking the mean for
topsoil and subsoil, respectively. Magnitudes of CEC for
subsoil and topsoil were 12.1 and 4.7 mmole(+) Kg 1 soil,
respectively. Based upon these second modified CEC values,
2+
predicted results for distributions of Mg concentrations


Concantration (mmole (+) /l)
with 3.6 pore volumes.


132
Darcy velocity was within 3 % for most columns. Large
differences with regard to the dispersion coefficients
between soil columns were assumed absent due to the small
variations in bulk density and Darcy flux.
Method for Dissection, Extraction and Chemical Analysis of
Soil Columns
After liquid flow was terminated, each column was
equilibrated overnight to insure that the whole system was
at equilibrium. The column was placed in the vertical
position, and the tape on the outside of the column was
removed carefully. As the outflow endplate was removed, a
piece of parafilm was placed over the soil cross section and
a small-diameter steel wire was used to slice the
consecutive rings of the column. Each section of soil then
was carefully placed onto another piece of prepared parafilm
before being packed into a prenumbered small centrifuge tube
with a predrilled small hole in the bottom. A Whatman no.42
filter paper was cut and placed inside the tube over the
hole in the bottom of the tube. Then each small tube was
transferred into a large-size centrifuge tube with a glass
bead separating the extraction solution from the small
centrifuge tube, and spun at 4000 rpm for 30 minutes. The
soil sample was then removed from the small centrifuge tube
and placed into a plastic weighing boat. The weight of the
wet soil was recorded, soil in the weighing boat was
air-dried, and the air-dry weight was recorded. The
concentrations of basic cations in the exchange phase were




101
solution as compared to columns receiving pH 4.9 HC1
solution. This can be explained by increased solubility and
mobility of complex aluminum as acidity increased.
Concentrations of Cations in Solution and Exchange Phases
Distributions of Ca2+, Mg2+, K+, Na+ and Al2+ in
solution and exchange phases for columns of Cecil topsoil
after leaching with pH 3.9 and 4.9 HC1 solutions are
presented in Tables 3-3 and 3-4, respectively. When an acid
solution is displaced through a soil column, cations with
higher affinities for exchange sites would be expected to
exchange strongly or tend to displace exchangeable cations
with lesser affinities from exchange sites (Helfferich,
1962; Mansell, 1983). For the case where equivalent
fractions of cations initially in the exchange phase are
approximately equal for all ion species, concentrations in
the solution phase of K+ and Na+ should be higher than
those of Ca2+, and Mg2+ and Al2 + For the Cecil soil the
situation was more complicated since the initial composition
3+
of the exchange phase was relatively high in trivalent A1
2+ 2+
as well as divalent Ca and Mg species. For the exchange
2+ 2+ 3+
phase, concentrations of Ca Mg Al would be dominant
over monovalent species. Results in Tables 3-3 and 3-4
indicate that, in the corresponding solution phase, cation
concentrations were in the order K+ = Na+ = Al3+ > Ca2+ >
. 2+
Mg
Tables 3-5 and 3-6 present distributions of cation
concentrations in solution and exchange phases for columns


45
Table 2-4 Concentrations of cations in solution and
exchange phases for subsoil after miscible
displacement with 3.6 pore volumes
Depth Ca Mg K Na Al Sum
(cm) Solution phase
mmole(+) L
1
0.188
9.420
0.143
0.470
0.064
10.285
2
0.148
9.510
0.190
0.518
0.060
10.426
3
0.148
9.250
0.176
0.511
0.056
10.141
4
0.144
9.220
0.135
0.483
0.055
10.037
5
0.212
8.950
0.205
0.435
0.052
9.854
6
0.244
8.890
0.203
0.424
0.051
9.812
7
0.224
8.490
0.131
0.477
0.049
9.371
8
0.299
8.630
0.137
0.497
0.048
9.611
9
0.435
8.760
0.174
0.351
0.044
9.764
10
0.667
8.300
0.258
0.407
0.042
9.674
11
0.853
8.110
0.240
0.370
0.040
9.613
12
1.600
7.340
0.184
0.306
0.039
9.469
13
2.110
7.180
0.209
0.282
0.019
9.800
14
3.450
5.930
0.276
0.337
0.024
10.017
15
3.730
5.730
0.143
0.157
0.024
9.784
16
4.420
4.530
0.171
0.157
0.021
9.299
17
5.140
3.790
0.258
0.209
0.022
9.419
18
5.360
3.420
0.194
0.170
0.020
9.164
19
5.540
3.620
0.269
0.235
0.020
9.684
20
6.560
2.070
0.371
0.365
0.016
9.382
Average 9.731
Depth Ca Mg K Na Al Sum
(cm) Exchange phase
mmole(+) Kg
1
0.609
13.700
0.177
0.235
*

2
0.509
13.000
0.184
0.226
1.993
15.912
3
0.489
12.100
0.197
0.243
*
*
4
0.549
11.600
0.258
0.243
4.663
17.313
5
0.499
11.300
0.230
0.226
*

6
0.589
11.200
0.235
0.226
4.974
17.224
7
0.599
10.900
0.238
0.235
*
*
8
0.793
11.200
0.287
0.243
4.396
16.919
9
0.913
10.000
0.317
0.243
*

10
1.300
10.500
0.333
0.235
4.072
16.440
11
1.200
9.960
0.243
0.226
*
*
12
2.590
9.710
0.266
0.226
4.264
17.056
13
3.540
7.570
0.261
0.252
*
*
14
4.340
6.670
0.304
0.243
4.266
15.824
15
6.090
5.760
0.279
0.235
*

16
4.740
7.160
0.289
0.261
4.511
16.961
17
8.280
4.530
0.312
0.217
*
*
18
8.930
3.870
0.327
0.226
4.534
17.887
19
9.430
3.130
0.404
0.243
*
*
20
10.300
2.470
0.476
0.235
5.190
18.671
* undetermined
Average 17.020




CHAPTER V
SUMMARY AND CONCLUSIONS
Summary
Cecil (Typic Hapludult) soil was used in investigations
of cation movement during steady displacement of electrolyte
solution and of cation leaching during application of acid
solutions under constant-flux conditions. Cecil soil was
characterized as a highly weathered soil. The principal
clay minerals in topsoil (0-30 cm depth) and subsoil (30-60
cm depth) were interstratified or interlayered vermiculite,
kaolinite, and quartz. Gibbsite was found only in the
subsoil. Topsoil and subsoil textures were classified as
sandy loam and sandy clay loam, respectively. Organic
matter (O.M) contents for topsoil and subsoil were 1.60 and
1.04%, respectively.
Studies of cation transport were conducted using
columns filled with water-saturated Cecil topsoil or
subsoil. Using a steady liquid flux of 1 cm h soil
2+
columns were initially saturated with Ca using 0.005 M
CaC^, and then miscibly displaced by 0.005 M MgC^
solution. After displacing 4.5 and 3.6 pore volumes of
MgCl2 solution for topsoil and subsoil columns,
respectively, the flow was terminated. Soil columns were
equilibrated overnight, before dissection into sections the
next day. Cations in the solution and exchange phases were
206


142
were 60.89, 94.86 and 186.75 mmole(+) L respectively.
For columns that received pH 4.9 HCl solution,
concentrations of 33.51, 145.62 and 139.72 mmole(+) were
+ 2+ 2+
observed for K Ca and Mg respectively. Beginning
with the third collected sample (about 0.5 pore volume) of
effluent, cation concentrations underwent a drastic decrease
to below 10 mmole(+) L ^ for all of the pretreated topsoil
and subsoil columns. Concentrations of other cations for
each soil column were detectable but usually so small as to
be negligible.
High concentrations of cations that appeared in the
first few collected effluent samples from each pretreated
soil column can be explained by a "salt effect" and by the
replacement efficiency of H+ for exchangeable cations
(Wiklander, 1975; Reuss and Johnson, 1986). All air-dry
pretreated topsoil and subsoil contained 0.6 and 1% water
content by volume, respectively. Since the soil columns
were initially air-dry, as the acid solution infiltrated
into each soil column H+ in the moving wetting front tended
to replace cations from variably-charged sites effectively.
This resulted in high concentrations of cations in the
wetting front. Thus, due to the high ratio of 6M/6H for the
chemically pretreated soil columns, the replacing efficiency
of H+ for basic cations (Wiklander and Andersson, 1972) was
enhanced. Thereafter, these high concentrations of cations
3+ +
induced cation exchange with exchangeable (Al + H ),
resulting in low pH for the soil solution. This phenomenon


217
laminar boundary-layer flow, p.497-504. In Numerical
Methods in Laminar and Turbulent Flow. C. Taylor and B.A.
Schrefler (eds.). Pineridge Press, Swansea, UK.
Hutchinson, T.C., and M. Havas, (eds.). 1980. Effects of
Acid Precipitation on Terrestrial Ecosystems. Plenum, New
York.
Jennings, A.A., D.J. Kirkner, and T.L. Theis. 1982.
Multicomponent equilibrium chemistry in groundwater
quality models. Water Resour. Res. 18:1089-1096.
Johnson, D.W., and D.W. Cole. 1980. Anion mobility in soil:
Relevance to nutrient transport from forest ecology.
Environ. Internat. 3:79-80.
Johnson, D.W., J. Turner, and J.M. Kelly. 1982. The effects
of acid rain on forest nutrient status. Water Resour. Res.
18:449-461.
Keng, J.C.W., and G. Uehera. 1974. Chemistry, mineralogy and
taxonomy of oxisols and ultisols. Soil Crop Sci. Soc. FI.
Proc. 33:119-126.
Kissel, D.E., E.P. Gentzsch, and G.W. Thomas. 1971. Hydrogen
of nonexchangeable acidity in soils during soil
extractions of exchangeable acidity. Soil Sci.
111:293-297.
Krishnamoorthy, C., and R. Overstreet. 1950. Behavior of
hydrogen in ion-exchange reactions. Soil Science
69:87-93.
Krug. E.C., and C.R. Frink. 1983. Acid rain on acid soil: A
new perspective. Science 221:520-525.
Krylov, V.I. 1962. Approximation calculation of integrals.
Macmillen, New York.
Lai, S.H., and J.J. Jurinak. 1971. Numerical approximation
of cation exchange in miscible displacement through soil
columns. Soil Sci. Soc. Am. Proc. 35:849-899.
Lapidus, L., and N.R. Amundson. 1952. Mathematics of
adsorption in beds: VI. The effect of longitudinal
diffusion in ion exchange and chromatographic columns. J.
Phys. Chem. 56:984-988.
Mansell, R.S. 1983. Ion exchange coupled with
convective-dispersive transport of cations during acid
rain infiltration in soil: A review, p.256-264. In Acid
Deposition: Causes and Effects. A.E.S. Green and W.H.
Smith (eds.). Government Institute, Inc., Rockville, MD.


208
The use of cubic spline functions as shape functions enabled
employment of a Galerkin finite-element formulation over the
spatial and time domain. The resulting ordinary
differential equations were solved by a method based on
backward differentiation formulation (Gear, 1969).
Verification of the numerical model was performed using
an analytical model for nonreactive solute transport during
miscible displacement, where the retardation factor (R) is
assumed to be unity. Verification was also performed for
the case of non-preferential ion exchange with a selectivity
coefficient equal to unity and cation-transport retardation
R = 1 + [(a CT)/(0 CT)].
Sensitivity analyses for dispersion coefficient,
volumetric water content, bulk density, selectivity
coefficient and cation exchange capacity parameters were
performed for the numerical model with respect to the
experimental data from the columns of Cecil soil.
Sensitivity analysis showed cation exchange capacity to be
the most critical parameter in the model. Relatively small
values of CEC gave the best simulations for measured cation-
concentration distributions with depth in the solution and
exchange phases. Use of CEC values obtained from 1 M NH^OAc
extraction resulted in discrepancies between observed and
predicted cation distributions within the columns.
Leaching of soil cations was investigated during
displacement of acid solutions under constant liquid flux
through columns of initially air-dry Cecil topsoil and


11
relationship between and C^. Details of this analysis
for are given in the next section.
Equation for Instantaneous Cation Exchange
The reversible, equilibrium-controlled cation-exchange
reaction involving ion species A with valence z^ and ion
species B with valence can be expressed as
z2 A(ad) + Z1 B(sol) = Z1 B(ad) + z2 A(soir 12-3]
The preference for soil exchange sites for competing cations
can be expressed in quantitative terms by the law of mass
action (Helfferich, 1962) as
[A]
[B]
Z1
[2-4]
where [A] and [B] denote activities of cation A and B
adsorbed onto soil exchange sites, respectively; [A] and [B]
denote activities of cations A and B in solution,
respectively; and K is the thermodynamic exchange constant
which is an indicator of the affinity of exchange sites for
ion B relative to affinity for ion A.
If Ma and Mg are given in units of mole per kg on the
exchange phase of ion species A and B, respectively, mole
fractions for ion species A and B are defined as


177
Table 4-12 Concentrations of cations in solution
and exchange phases for Ca-topsoil after
leaching with pH 3.9 HCl solution
Depth
(cm)
Ca
Mg
l
K
Solution
Na
ph^se
Al
Sum
1.0
0.799
0.726 0.184*
1.210
0.002
2.921
2.0
1.260
0.792
0.490
1.780
0.017
4.339
3.0
0.948
1.120
0.127
0.939
0.060
3.194
4.0
0.741
1.330
0.122
0.998
0.022
3.213
5.0
0.633
0.437
0.134
1.430
0.066
2.700
6.0
0.723
0.318
0.166
1.390
0.217
2.814
7.0
0.804
0.207
0.364
2.410
0.009
3.794
8.0
0.656
1.220
0.136
1.350
0.009
3.371
9.0
0.838
0.592
0.350
2.320
0.007
4.107
10.0
1.320
1.000
0.364
2.110
0.004
4.798
11.0
0.912
0.918
0.200
1.130
0.012
3.172
12.0
1.320
0.067
0.219
1.410
0.038
3.053
13.0
1.190
0.481
0.127
1.370
0.012
3.180
14.0
0.858
1.670
0.274
3.990
0.407
7.199
15.0
0.705
0.489
0.076
0.743
0.054
2.067
16.0
0.907
1.550
0.246
1.860
0.046
4.609
17.0
0.880
0.141
0.087
10.200
0.018
11.326
18.0
0.979
0.896
0.186
1.530
0.008
3.599
19.0
1.010
0.444
0.269
1.260
0.007
2.990
20.0
0.859
0.222
0.158
1.680
0.006
2.925
Depth Ca Mg K Na Al Sum
(cm) Exchange phas|
1.0
3.620
i
0.041
nmole ( + )
0.192
Kg "
0.337
soil
5.182
9.372
3.0
10.500
0.041
0.294
0.304
1.511
12.650
5.0
10.400
0.021
0.237
0.283
1.156
12.097
7.0
9.360
0.021
0.211
0.261
1.023
10.876
10.0
11.700
0.041
0.301
0.337
1.012
13.391
11.0
12.700
0.041
0.269
0.359
1.201
14.570
14.0
10.600
0.041
0.269
0.283
0.867
12.060
16.0
11.700
0.062
0.326
0.370
0.845
13.303
18.0
12.000
0.082
0.499
0.413
0.978
13.972
20.0
10.900
0.082
0.288
0.304
0.789
12.363


Concentration (mmole (+)/l)
Pore Volumes
Figure 3-4 The effect of input solution pH upon the breakthrough curves of summed
concentrations of Ca2+, Mg^+, K+ and Na+ in effluent from topsoil
columns.


I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
^7^ TTlS 'TVfC 7^-
W. W. McFee
Professor of Soil Science
This dissertation was submitted to the Graduate Faculty of
the College of Agriculture and to the Graduate School and
was accepted as partial fulfillment of the requirements
for the degree of Doctor of Philosophy.
August, 1987
lege of Agriculture
Dean, Graduate School


187
Table 4-19 Concentrations of cations in solution and
exchange phases for mixed-cation subsoil
after leachingwith pH 4.9 HCl solution
Depth Ca Mg K Na A1 Sum
(cm) Solution phase
mmole (+) L
1.0
0.062
0.041
0.414
0.120
0.006
0.643
2.0
0.047
0.033
0.267
0.122
0.011
0.480
3.0
0.027
0.013
0.354
0.086
0.018
0.498
4.0
0.035
0.008
0.247
0.107
0.011
0.408
5.0
0.057
0.016
0.421
0.183
0.017
0.695
6.0
0.032
0.008
0.656
0.087
0.000
0.784
7.0
0.030
0.016
0.344
0.124
0.022
0.537
8.0
0.025
0.008
0.342
0.126
0.011
0.512
9.0
0.092
0.021
0.384
0.217
0.011
0.725
10.0
0.025
0.008
0.265
0.122
0.006
0.426
11.0
0.027
0.008
0.307
0.130
0.006
0.478
12.0
0.027
0.004
0.288
0.098
0.006
0.423
13.0
0.020
0.008
0.434
0.135
0.028
0.625
14.0
0.037
0.012
0.404
0.167
0.017
0.637
15.0
0.027
0.012
0.377
0.133
0.011
0.561
16.0
0.077
0.037
0.794
0.128
0.022
1.059
17.0
0.007
0.008
0.287
0.104
0.028
0.435
18.0
0.020
0.008
0.411
0.200
0.028
0.667
19.0
0.075
0.025
0.625
0.170
0.020
0.915
20.0
0.018
0.008
0.375
0.091
0.028
0.520
Depth
Ca
Mg
K
Na
A1
Sum
(cm)
Kg 1 !
1.0
3.590
3.620
1.430
0.313
2.635
11.588
3.0
4.540
2.960
3.480
0.196
1.190
12.366
5.0
4.490
2.630
4.550
0.200
0.956
12.826
7.0
4.690
2.300
4.940
0.196
1.012
13.138
9.0
4.040
2.570
5.350
0.200
0.878
13.038
11.0
3.940
2.500
5.550
0.183
0.756
12.929
14.0
4.040
2.390
5.830
0.130
0.812
13.202
16.0
4.190
2.330
6.060
0.191
0.701
13.472
18.0
4.090
2.220
5.940
0.235
0.689
13.174
20.0
4.240
2.100
6.640
0.243
0.767
13.990


174
Table 4-10 Concentrations of cations in solution
and exchange phases for Mg-subsoil after
leaching with pH 3.9 HC1 solution
Mg K
Solution
mmole(+)
Depth
(cm)
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0
16.0
17.0
18.0
19.0
20.0
Ca
0.362
0.472
0.267
0.364
0.327
0.359
0.377
0.349
0.324
0.487
0.514
0.589
0.509
0.589
0.574
0.444
0.576
0.556
0.474
0.464
0.078
0.119
0.103
0.144
0.115
0.123
0.123
0.140
0.128
0.152
0.144
0.136
0.148
0.156
0.169
0.111
0.136
0.111
0.136
0.132
0.187
0.243
0.139
0.164
0.114
0.159
0.079
0.113
0.132
0.132
0.104
0.212
0.169
0.180
0.182
0.157
0.175
0.155
0.153
0.088
Na
phase
L
1.130
1.800
0.785
1.280
0.991
1.110
1.330
1.510
1.390
1.770
1.680
2.410
1.680
1.520
1.980
1.440
1.690
1.720
1.480
1.610
A1
0.003
0.001
0.002
0.003
0.008
0.003
0.002
0.003
0.004
0.000
0.000
0.002
0.002
0.002
0.001
0.004
0.004
0.002
0.010
0.001
Sum
1.761
2.635
1.296
1.955
1.555
1.754
1.912
2.115
1.978
2.541
2.442
3.349
2.508
2.447
2.906
2.156
2.581
2.544
2.253
2.295
Depth Ca Mg K Na Al Sum
(cm) Exchange phase
mmole(+) Kg soil
2.0
1.210
5.550
0.179
0.391
9.329
16.659
4.0
0.861
8.020
0.179
0.337
3.269
12.666
5.0
0.724
8.640
0.192
0.228
1.390
11.174
7.0
0.624
7.820
0.185
0.217
1.401
10.247
9.0
0.636
8.230
0.217
0.239
1.301
10.623
11.0
0.761
8.840
0.205
0.304
1.379
11.489
13.0
0.736
8.840
0.441
0.457
1.379
11.853
15.0
0.686
8.840
0.230
0.283
1.223
11.262
18.0
0.699
8.020
0.281
0.326
1.223
10.549
20.0
0.674
8.020
0.365
0.391
1.368
10.818


Concentration (mmole (+)/l)
144


28
becomes inefficient and a method that is more suitable for
stiff equations should be employed. The LSODE solver
developed by A. C. Hindmarsh at the Lawrence Livermore
National Laboratory was used in this study as a part of the
main subroutine throughout the program. The LSODE
subroutine (Hindmarsh, 1980, 1983) is capable of solving
systems of ordinary differential equations of the form
dy
= f(t,y) [2-55]
dt
and y(t,0) = fQ
where y, f, and fQ are vectors of length N.
In the computation, the spatial discretization was made
to give a small element-size in the immediate vicinity of
the inlet boundary, and gradually coarser elements were used
for increasing distances from the inlet. Element sizes were
obtained by trial and error in order to provide solutions
without oscillations. Mass-balance error was not allowed to
exceed 2% in a given simulation. A small initial time step
(5 10 ^ sec) was used for generating stable solutions,
after which larger time steps (300 sec) were used. All
computations were performed with the IFAS computer network
on a VAX 11/750 computer at the University of Florida.
Double-precision arithmetic was used in all computations.
Material and Methods
Soil
The Cecil (Typic Hapludult) soil used in this study was
obtained from a forest site located at Clemson University in


214
effects of acid deposition are likely to go unnoticed.
However, for certain forest soils, periodical fertilizer
application may be needed in the future to minimize adverse
effects of acid deposition upon soil fertility.


BIOGRAPHICAL SKETCH
Ko-Hui Liu was born on November 5, 1951, in Taichung,
Taiwan, Republic of China. After graduating from high
school she entered National Chung-Hsing University,
Taichung, Taiwan, where she received her Bachelor of Science
degree in 1974. She then taught high school in the city of
Taipei. In the fall of 1979 she enrolled as a graduate
student in the Department of Soil Science at the University
of Florida. After receiving her Master of Science degree in
1982, she remained to perform graduate study toward the
Ph.D. degree.
She is married to Ming-Hsinug Chen. She is a member of
Gamma Sigma Delta, the Honor Society of Agriculture, and is
also an associate member of Sigma Xi.
221


Concentration (mmole (+) /l)
00
V£>


105
Table 3-6 Concentrations of cations in solution and
exchange phases for subsoil after leaching
with pH 4.9 HC1 solution
Depth Ca Mg K Na A1 Sum
(cm) Solution phase
mmole (+) L
1.0
0.084
0.033
0.116
0.551
0.010
0.794
2.0
0.072
0.029
0.087
0.515
0.020
0.723
3.0
0.067
0.029
0.060
0.224
0.016
0.396
4.0
0.080
0.033
0.097
0.365
0.024
0.599
5.0
0.094
0.040
0.084
0.407
0.036
0.660
6.0
0.082
0.037
0.063
0.372
0.031
0.585
7.0
0.107
0.041
0.055
0.350
0.018
0.571
8.0
0.080
0.033
0.061
0.228
0.020
0.422
9.0
0.108
0.043
0.067
0.315
0.016
0.548
10.0
0.126
0.053
0.101
0.393
0.014
0.687
Depth Ca Mg K Na A1 Sum
(cm) Exchange phase
mmole (+) Kg soil
1.0
2.200
0.913
0.271
0.174
2.0
3.590
1.190
0.261
0.157
3.0
4.190
1.230
0.281
0.191
4.0
4.590
1.330
0.279
0.065
5.0
4.640
1.320
0.315
0.122
6.0
4.840
1.300
0.330
0.148
7.0
4.790
1.370
0.350
0.157
8.0
5.190
1.390
0.363
0.178
9.0
5.240
1.440
0.427
0.209
10.0
4.990
1.370
0.379
0.178
6.883 10.441
6.616 11.814
6.282 12.174
5.671 11.935
6.194 12.591
5.938 12.556
6.093 12.760
6.004 13.125
6.049 13.365
5.871 12.788


119
to the fact that not all ion species (i.e. NH+4) were
included in the analyses. Essentially all of the column
effluent and soil-solution phase had a pH of less than 5.6
to 6.0, as shown in Fig. 3-1 and 3-5. Another reason could
be due to experimental error to soil chemical reactions that
act as sinks for applied H+, and to chemical dissolution of
3+
A1 from nonexchangeable form in oxides and clay minerals.
The overall charge balance of major cations in each
soil column was described in equation [3-5]. A sixth term
would include sinks for H+, and a seventh term would include
3+
a source for A1 by acid dissolution of soil oxides and
clay minerals. Although these two terms were not measured
in this investigation, they are important to the overall
balance. The reported charge-balance values are thus in
error, but do give apparent charge-balance values.
Conclusions
Cecil soil is known to be a highly weathered acid soil.
The principal soil minerals observed in Cecil topsoil and
subsoil were kaolinite, interlayer-hydroxy vermiculite, and
quartz. Gibbsite was also observed in the subsoil. A "salt
effect" caused the first few effluent samples to be
uncommonly low in pH and high in concentrations of several
cation species. Application of HC1 solutions with two
different pH values to the Cecil soil resulted in larger
quantities of cations being leached by pH 3.9 solution
relative than of pH 4.9. The reverse effect was observed
3+
for quantities of Al exported, however. Concentrations of


LIST OF TABLES
Table Page
2-1 Soil parameters used in column experiments 35
2-2 Properties of Cecil topsoil and subsoil 35
2-3 Concentrations of cations in solution and exchange
phases for topsoil after miscible displacement
with 4.5 pore volumes 44
2-4 Concentrations of cations in solution and exchange
phases for subsoil after miscible displacement
with 3.6 pore volumes 45
3-1 Physical and chemical parameters for Cecil topsoil
and subsoil columns 85
3-2 Initial concentrations of exchangeable cations, pH,
and CEC for Cecil topsoil and subsoil 86
3-3 Concentrations of cations in solution and exchange
phases for topsoil after leaching with pH 3.9
solution 102
3-4 Concentrations of cations in solution and exchange
phases for topsoil after leaching with pH 4.9
solution 103
3-5 Concentrations of cations in solution and exchange
phases for subsoil after leaching with pH 3.9 HC1
solution 104
3-6 Concentrations of cations in solution and exchange
phases for subsoil after leaching with pH 4.9 HCl
solution 105
3-7 Topsoil selectivity coefficients as determined
after leaching with pH 3.9 HCl solution 108
3-8 Topsoil selectivity coefficients as determined
after leaching with pH 4.9 HCl solution 109
3-9 Subsoil selectivity coefficients as determined
after leaching with pH 3.9 HCl solution 110
3-10 Subsoil selectivity coefficients as determined
Vll


25
are chosen to be the interpolation (shape) functions of the
assumed solution, such as
Computational Method
After rearranging,
9 C (t)
IQ] ( 2 } = ([R]
9 t
where:
[2-45]
equation [2-44] becomes
- [U]) {C_j (t)} + ({V}-{S})Cf ,
[2-46]
[Q]
fL (1 +
J0
a
Q
F) Nm(z)
n+1
Nj(z)dx
n+1 9*N.(z)
[ri = /; v*> 3=1 j
9 x
n+1 9N.(z)
[U] = v r N (z) £, r
J q m 3-1 9.
dx
dx
{V} = D r Nm(z)
J0 m
9 B1(z)
dx
9 x
9B.(z)
and {S} = v + Nm(Z)
dx
[2-47]
In equation [2-46], undetermined coefficients Cj(x,t)
do not appear explicitly but are embedded in the function F.
This nonlinear term is linearlized by employing the previous
time-step solution of (x,t) into the F term for
manipulation. For example, if we consider m = 2, 3,...,
n+1, the matrix coefficients at the left-hand side of
equation [2-37] can be written as


210
about 5 pore volumes of effluent for nontreated soil, 3 pore
volumes for treated soil, and 3.5 pore volumes for mixed
soils. Between 5 to 30 pore volumes, effluent pH was in the
range of 6.0 6.5, but cation concentrations decreased in a
gradual manner. The H+ ions were obviously removed from the
soil solution at a fairly constant rate during the last 25
pore volumes of effluent as exchangeable cations were
leached from the soil.
During application of pH 3.9 and 4.9 HCl solutions, the
total quantities of basic cation eluted in effluent were
0.286 and 0.238 mmole(+), respectively, from columns of
nontreated topsoil; 0.395 and 0.306 mmole(+), respectively,
from nontreated subsoil; 4.204 and 2.207 mmole(+),
respectively, from Ca-topsoil; 5.697 and 5.55 mmole(+),
respectively, from K-topsoil; 9.917 and 4.221 mmole(+),
respectively, from Mg-topsoil; 15.007 and 14.273 mmole(+),
respectively, from Ca-subsoil; 11.360 and 7.002 mmole(+),
respectively, from K-subsoil; 23.105 and 22.676 mmole(+),
respectively, from Mg-subsoil; 22.626 and 21.066 mmole(+),
respectively, from mixed subsoil; and 5.621 and 5.519
mmole(+), respectively, from mixed topsoil. Also, during
application of pH 3.9 and 4.9 HCl solutions, total
quantities of aluminum were 0.110 and 0.017 mmole(+),
respectively, from nontreated topsoil; 0.001 and 0.001
mmole(+), respectively, from nontreated subsoil; 0.116 and
0.193 mmole(+), respectively, from Ca-topsoil; 2.910 and
2.518 mmole(+), respectively, from K-topsoil; 0.739 and


186
Table 4
Depth
(cm)
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0
16.0
17.0
18.0
19.0
20.0
Depth
(cm)
1.0
2.0
3.0
5.0
7.0
9.0
12.0
15.0
18.0
20.0
18 Concentrations of cations in solution and
exchange phases for mixed-cation subsoil
after leaching with pH 3.9 HC1 solution
Ca Mg K Na Al Sum
Solution phase
mmole (+) L
0.050
0.016
0.142
0.178
0.017
0.403
0.082
0.037
0.151
0.165
0.011
0.446
0.085
0.062
0.205
0.167
0.011
0.530
0.062
0.058
0.129
0.100
0.011
0.360
0.040
0.021
0.288
0.139
0.000
0.487
0.032
0.016
0.260
0.115
0.006
0.429
0.015
0.025
0.285
0.133
0.013
0.471
0.027
0.021
0.326
0.148
0.022
0.544
0.060
0.037
0.365
0.202
0.006
0.669
0.000
0.000
2.530
0.154
0.000
2.684
0.078
0.035
0.523
0.334
0.060
1.029
0.057
0.021
0.386
0.243
0.050
0.757
0.035
0.016
0.362
0.189
0.000
0.602
0.015
0.012
0.365
0.165
0.000
0.557
0.042
0.020
0.375
0.219
0.033
0.689
0.023
0.005
0.324
0.236
0.014
0.602
0.012
0.015
0.301
0.130
0.007
0.464
0.027
0.010
0.335
0.157
0.027
0.555
0.033
0.015
0.275
0.193
0.020
0.536
0.045
0.020
0.410
0.237
0.060
0.772
Ca
Mg
K
Na
Al
Sum
2.990
0.716
0.491
0.222
8.117
12.536
4.640
3.040
1.010
0.183
0.912
9.785
5.240
3.130
1.370
0.191
1.007
10.938
4.940
2.960
3.500
0.196
0.845
12.441
4.690
2.710
4.450
0.174
0.790
12.814
4.790
2.630
5.650
0.191
0.899
14.160
4.790
2.140
6.270
0.200
0.723
14.123
4.140
2.330
6.040
0.226
0.801
13.537
4.890
2.410
6.500
0.217
0.634
14.651
4.240
2.350
6.340
0.252
0.656
13.838


78
vermiculites and interstratified forms of these minerals
typically have constant surface charge regardless of
solution concentration or pH (Gast, 1977). Colloids with
constant surface potential and variable surface charge are
in turn commonly found in soils which are extensively
weathered and dominated by sesquioxides of Fe and A1 or 1:1
kaolinitic minerals. The surface charge density for
colloids of this type varies with pH and salt concentration
(Keng and Uehera, 1974). Soil organic matter also has
pH-dependent charge, arising from dissociation of phenolic
OH and carboxylic groups.
Cation-Exchange Equilibria
The exchange reaction between an exchange-phase cation
1 with valence z^ and a cation 2 of valence z2 in solution
can be described by the equation
z2 Cx + zi C2 = C2 + z2 C1 [3-1]
For a reversible reaction such as equation (3-1) at
chemical equilibrium, one type of exchange selectivity
coefficient (Ks) can be expressed as


Concentration (mmole (+)/l)
167


Full Text



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INGEST IEID E62TNW52G_0O6YYM INGEST_TIME 2011-11-03T18:21:27Z PACKAGE AA00004842_00001
AGREEMENT_INFO ACCOUNT UF PROJECT UFDC
FILES



LEACHING OF CATIONS DURING DISPLACEMENT BY ACID
SOLUTIONS THROUGH COLUMNS OF CECIL SOIL
BY
KO-HUI LIU
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN
PARTIAL FULFILLMENT OF THE REQUIREMENTS
FOR THE DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1987

To My Parents

ACKNOWLEDGEMENT
The author wishes to express her sincere appreciation
to Dr. R. S. Mansell, chairman of the graduate supervisory
committee, for guidance, valuable discussions, and
suggestions throughout her entire course of study.
Sincere appreciations are also extended to Drs. E. A.
Hanlon, C. C. Hsu, W. W. McFee, and R. D. Rhue for their
valuable discussions and helpful suggestions made during
this work and their review of the manuscript.
Special appreciation is expressed to Dr. S. A. Bloom,
Scientific Programmer, for assistance and counsel in
plotting graphs, to Dr. C. C. Hsu for generously lending the
LSODE subroutine and to a friend, Mr. Fang-Yin Lee, for
providing x-ray analyses for each of the soil samples.
This research was supported in part by the U.S.
Environmental Protection Agency under Project A0457-06,
entitled "Effects of Acid Deposition on Ion Mobilities in
Selected Soils". Partial support by the Soil Science
Department is also greatly appreciated.
Deepest gratitude is expressed to the author's parents
for their support and to her husband Ming-Hsiung for his
understanding, consideration, and encouragement.
in

TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS iii
LIST OF TABLES vii
LIST OF FIGURES X
ABSTRACT XV
CHAPTER
I INTRODUCTION 1
Description of Problem 1
Hypotheses 2
Objectives 3
II MODEL SIMULATIONS OF BINARY CATION EXCHANGE AND
TRANSPORT IN COLUMNS OF CECIL SOIL 5
Introduction 5
Theory 9
Transport Equation 9
Equation for Instantaneous Cation
Exchange 11
Transport with Ion Exchange 15
A Galerkin Finite-Element Numerical Method... 18
Finite-Element Method 18
Interpolation Function 19
Method of Weighted Residuals 23
Computational Methods 25
Material and Methods 28
Soil 28
Column Experiment 31
Cation Exchange Isotherms from Soil
Columns 34
Results and Discussion 34
Soil Properties 34
Verification of the Numerical Model 36
Exchange Isotherm Curves for Columns of
Cecil Soil 38
Exchange Selectivity Coefficients (Ks)
for Soil Columns 43
Model Sensitivity Analysis 46
Conclusions 73
IV

III CATION LEACHING DURING CONTINUOUS DISPLACEMENT
BY AQUEOUS HYDROCHLORIC ACID SOLUTION THROUGH
COLUMNS OF CECIL SOIL 75
Introduction 75
Basic Theory 77
Surfaces of Soil Particles 77
Cation Exchange Equilibria 78
Effects of Acidification 79
Materials and Methods 80
Physical and Chemical Properties of Soil... 80
X-Ray Diffraction 81
Column Preparation and Displacement
Procedure 82
Dissection of Soil Columns, Extraction, and
Chemical Analysis 83
Results and Discussion 85
Concentrations and pH of Column Effluent .. 87
Concentrations of Cations in Solution
and Exchange Phases 101
Estimated Selectivity Coefficients of
Ion Pairs 106
Charge Balance of Major Cations for
Topsoil and Subsoil 114
Conclusions 119
IV CATION LEACHING DURING CONTINUOUS DISPLACEMENT BY
HYDROCHLORIC ACID SOLUTION THROUGH COLUMNS OF
CHEMICALLY-PRETREATED CECIL SOIL 123
Introduction 123
Cation Exchange Reaction 124
Saturation Mechanisms for Soil Exchange Sites
with a Single+Cation Species 124
Mechanisms of H Replacement of
Exchangeable Cations on Soil Exchange
Sites 126
Materials and Methods 128
Preparation of Pretreated Soil 128
Soil Column Preparation and Procedure for
Displacing HC1 Solutions through Columns. 130
Method for Dissection, Extraction and Chemical
Analysis of Soil Columns 132
Results and Discussion 133
Exchange Sites for Chemically Pretreated
Soil 138
Effluent pH for Treated Soil Columns 138
Cation Concentrations in Effluent from
Treated Soil Columns 139
Cation Concentrations in Effluent from
Chemically Pretreated Mixed Soil Columns. 154
Concentrations of AlJ in Effluent from Mixed
Soil Columns 165
Concentrations of Cations in Solution and
v

Exchange Phases for Treated and Mixed
Soil Columns after Application of 25 Pore
Volumes of HCl Solution 165
Charge Balance Using All Major Cations
for Treated and Mixed Soil Columns 190
Conclusions 203
V SUMMARY AND CONCLUSIONS 206
Summary 206
Conclusions 212
REFERENCES 215
BIOGRAPHICAL SKETCH 221
vi

LIST OF TABLES
Table Page
2-1 Soil parameters used in column experiments 35
2-2 Properties of Cecil topsoil and subsoil 35
2-3 Concentrations of cations in solution and exchange
phases for topsoil after miscible displacement
with 4.5 pore volumes 44
2-4 Concentrations of cations in solution and exchange
phases for subsoil after miscible displacement
with 3.6 pore volumes 45
3-1 Physical and chemical parameters for Cecil topsoil
and subsoil columns 85
3-2 Initial concentrations of exchangeable cations, pH,
and CEC for Cecil topsoil and subsoil 86
3-3 Concentrations of cations in solution and exchange
phases for topsoil after leaching with pH 3.9
solution 102
3-4 Concentrations of cations in solution and exchange
phases for topsoil after leaching with pH 4.9
solution 103
3-5 Concentrations of cations in solution and exchange
phases for subsoil after leaching with pH 3.9 HC1
solution 104
3-6 Concentrations of cations in solution and exchange
phases for subsoil after leaching with pH 4.9 HCl
solution 105
3-7 Topsoil selectivity coefficients as determined
after leaching with pH 3.9 HCl solution 108
3-8 Topsoil selectivity coefficients as determined
after leaching with pH 4.9 HCl solution 109
3-9 Subsoil selectivity coefficients as determined
after leaching with pH 3.9 HCl solution 110
3-10 Subsoil selectivity coefficients as determined
Vll

after leaching with pH 4.9 HCl solution Ill
3-11 Mass balance of cations for columns of topsoil ...117
3-12 Mass balance of cations for columns of subsoil ...118
4-1 Concentrations of exchangeable cations for
nontreated topsoil and subsoil 134
4-2 Soil parameters for chemically pretreated topsoil
columns after leaching with HCl solutions 134
4-3 Soil parameters for chemically pretreated subsoil
columns after leaching with HCl solutions 135
4-4 Soil parameters for mixed soil columns after
leaching with HCl solutions 136
4-5 Concentrations of exchangeable cations for
pretreated and mixed topsoil and subsoil 137
4-6 Concentrations of cations in solution and
exchange phases for K-subsoil after leaching
with pH 3.9 HCl solution 168
4-7 Concentrations of cations in solution and
exchange phases for K-subsoil after leaching
with pH 4.9 HCl solution 169
4-8 Concentrations of cations in solution and
exchange phases for Ca-subsoil after leaching
with pH 3.9 HCl solution 171
4-9 Concentrations of cations in solution and
exchange phases for Ca-subsoil after leaching
with pH 4.9 HCl solution 172
4-10 Concentrations of cations in solution and
exchange phases for Mg-subsoil after leaching
with pH 3.9 HCl solution 174
4-11 Concentrations of cations in solution and
exchange phases for Mg-subsoil after leaching
with pH 4.9 HCl solution 175
4-12 Concentrations of cations in solution and
exchange phases for Ca-topsoil after leaching
with pH 3.9 HCl solution 177
4-13 Concentrations of cations in solution and
exchange phases for Ca-topsoil after leaching
with pH 4.9 HCl solution 178
4-14 Concentrations of cations in solution and
vm

exchange phases for K-topsoil after leaching
with pH 3.9 HCl solution 180
4-15 Concentrations of cations in solution and
exchange phases for K-topsoil after leaching
with pH 4.9 HCl solution 181
4-16 Concentrations of cations in solution and
exchange phases for Mg-topsoil after leaching
with pH 3.9 HCl solution 183
4-17 Concentrations of cations in solution and
exchange phases for Mg-topsoil after leaching
with pH 4.9 HCl solution 184
4-18 Concentrations of cations in solution and
exchange phases for mixed-cation subsoil after
leaching with pH 3.9 HCl solution 186
4-19 Concentrations of cations in solution and
exchange phases for mixed-cation subsoil after
leaching with pH 4.9 HCl solution 187
4-20 Concentrations of cations in solution and
exchange phases for mixed-cation topsoil after
leaching with pH 3.9 HCl solution 188
4-21 Concentrations of cations in solution and
exchange phases for mixed-cation topsoil after
leaching with pH 4.9 HCl solution 189
4-22 Charge balance of cations for columns of
Ca-topsoil 191
4-23 Charge balance of cations for columns of
K-topsoil 192
4-24 Charge balance of cations for columns of
Mg-topsoil 193
4-25 Charge balance of cations for columns of
Ca-subsoil 194
4-26 Charge balance of cations for columns of
K-subsoil 195
4-27 Charge balance of cations for columns of
Mg-subsoil 196
4-28 Charge balance of cations for columns of
mixed-cation subsoil 201
4-29 Charge balance of cations for columns of
mixed-cation topsoil 202
ix

LIST OF FIGURES
Figure
Page
2-1 Numerical and analytical solutions obtained using
topsoil parameters for the case where the binary
exchange selectivity coefficient equals zero 39
2-2 Numerical and analytical solutions obtained
using topsoil parameters for the case where
the exchange selectivity coefficient equals unity.. 40
2+
2-3 Mg exchange isotherm curve obtained from the
topsoil column after miscible displacement with
4.5 pore volumes 41
2+
2-4 Mg exchange isotherm curve obtained from the
subsoil column after miscible displacement with 3.6
pore volumes \ 42
2+
2-5 Experimental distributions of Mg concentrations
in the solution phase of the topsoil column after
miscible displacement with 4.5 pore volumes, along
with calculated results obtained using three values
for the dispersion coefficient 47
2+
2-6 Experimental distributions of Mg concentrations
in the solution phase of the subsoil column after
miscible displacement with 3.6 pore volumes, along
with calculated results obtained using three values
for the dispersion coefficient 48
2+
2-7 Experimental distributions of Mg concentrations
in the solution phase of the topsoil column after
miscible displacement with 4.5 pore volumes, along
with calculated results obtained using three values
for volumetric water content 50
2+
2-8 Experimental distributions of Mg concentrations
in the solution phase of the subsoil column after
miscible displacement with 3.6 pore volumes, along
with calculated results obtained using three values
for the volumetric water content 51
2+
2-9 Experimental and simulated distributions of Mg
concentrations for three values of bulk density for
the topsoil column after miscible displacement with
4.5 pore volumes 53
x

2-10
2-11
2-12
2-13
2-14
2-15
2-16
2-17
2-18
2-19
2-20
2 +
Experimental and simulated distributions of Mg
concentrations for three values of bulk density for
the subsoil column after miscible displacement with
3.6 pore volumes 54
2+
Experimental distributions of Mg concentrations for
the topsoil column after miscible displacement with
4.5 pore volumes, along with simulation results for
three values of the selectivity coefficient 56
2+
Experimental distributions of Mg concentrations for
the subsoil column after miscible displacement with
3.6 pore volumes, along with simulated results for
three values of the selectivity coefficient 57
2+
Experimental distributions of Mg concentrations for
the topsoil column after miscible displacement with
4.5 pore volumes, along with simulation results for
two values of the cation exchange capacity 59
2+
Experimental distributions of Mg concentrations for
the subsoil column after miscible displacement with
3.6 pore volumes, along with simulation results for
two values of the cation exchange capacity 60
2+
Calculated and experimental distributions of Mg
concentrations in the solution phase for the subsoil
column after miscible displacement with 3.6
pore volumes 63
2+
Calculated and experimental distributions of Mg
concentrations in the exchange phase for the subsoil
column after miscible displacement with 3.6
pore volumes 64
2+
Calculated and experimental distributions of Mg
concentrations in the solution phase for the topsoil
column after miscible displacement with 4.5
pore volumes 65
Calculated and experimental distributions of Mg
concentrations in the exchange phase for the
topsoil column after miscible displacement with
4.5 pore volumes
2+
66
2+
Calculated and experimental distributions of Mg'
concentrations in the solution phase for the topsoil
column after miscible displacement with 4.5
pore volumes 68
2+
Calculated and experimental distributions of Mg
concentrations in the exchange phase for the topsoil
column after miscible displacement with 4.5
pore volumes 69
xi

2-21 Simulation results a^d experimental data for
distributions of Mg concentrations in the solution
phase for the subsoil column after miscible
displacement with 3.6 pore volumes 70
2-22 Simulation results a^d experimental data for
distributions of Mg^ concentrations in the exchange
phase for the subsoil column after miscible
displacement with 3.6 pore volumes 71
2-23 Effluent pH values for the topsoil and subsoil
columns 72
3-1 Breakthrough curves for pH in the effluent from
Cecil topsoil columns which had received two input
HCl solutions with different values of pH 88
3-2 Breakthrough curves for cation concentrations in the
effluent from Cecil topsoil columns which had
received pH 3.9 input HCl solution 89
3-3 The effect of input+solution pH upon the break¬
through curves of K from Cecil topsoil columns.... 91
3-4 The effect of input solution pH upon the break-
thrcj>ugh+curves o| summed concentrations of Ca^ ,
Mg^ , K , and Na in effluent from topsoil columns. 92
3-5 The effect of input ^lution pH upon the break¬
through curves of Al-3 from Cecil topsoil
columns 93
3-6 Breakthrough curves for pH in the effluent from
Cecil subsoil columns which received two input HCl
solutions with different values of pH 94
3-7 Breakthrough curves for cations in the effluent
from Cecil subsoil columns which received pH 4.9
input HCl solution 96
3-8 The effect of input ^olution pH upon the break¬
through curves of Ca from Cecil subsoil columns . 97
3-9 The effect of input solution pH upon the brea£-
th^ugh+curves o£ summed concentrations of Caz ,
Mgz , K , and Na in effluent from subsoil columns. 98
3-10 The effect of input ^lution pH upon the break¬
through curves of AlJ from Cecil subsoil columns . 99
4-1 Breakthrough curves for pH in the effluent from
Ca-topsoil columns which received input HCl
Xll

solutions with two different pH values
140
4-2 Breakthrough curves for pH in the effluent from
Ca-subsoil columns which received input HC1
solutions with two different pH values 141
4-3 Breakthrough curves of K+ from K-topsoil columns
which received input HC1 solutions with two
different pH values 144
2+
4-4 Breakthrough curves of Ca from Ca-topsoil
columns which received input HCl solutions with
two different pH values 145
2+
4-5 Breakthrough curves of Mg from Mg-topsoil columns
which received input HCl solutions with two
different pH values 146
4-6 Breakthrough curves of K+ from K-subsoil columns
which received input HCl solutions with two
different pH values 147
2+
4-7 Breakthrough curves of Ca from Ca-subsoil columns
which received input HCl solutions with two
different pH values 148
2+
4-8 Breakthrough curves of Mg from Mg-subsoil columns
which received input HCl solutions with two
different pH values 149
3+
4-9 Breakthrough curves of Al from K-subsoil columns
which received input HCl solutions with two
different pH values 151
3+
4-10 Breakthrough curves of Al from Ca-subsoil columns
which received input HCl solutions with two
different pH values 152
3+
4-11 Breakthrough curves of Al from Mg-subsoil columns
which received input HCl solutions with two
different pH values 153
3+
4-12 Breakthrough curves of Al from K-topsoil columns
which received input HCl solutions with two
different pH values 155
3+
4-13 Breakthrough curves of Al from Ca-topsoil columns
which received input HCl solutions with two
different pH values 156
3+
4-14 Breakthrough curves of Al from Mg-topsoil columns
which received input HCl solutions with two
different pH values 157
xiii

4-15
Breakthrough curves of cations in the effluent
from a mixed-cation topsoil column which received
pH 3.9 input HCl solution 158
4-16 Breakthrough curves of cations in the effluent
from a mixed-cation subsoil column which received
pH 3.9 input HCl solution 159
4-17 Breakthrough curves of K+ from mixed-cation topsoil
columns which received input HCl solutions with two
different pH values 161
2+
4-18 Breakthrough curves of Ca from mixed-cation topsoil
columns which received input HCl solutions with two
different pH values 162
4-19 Breakthrough curves of K+ from mixed-cation subsoil
columns which received input HCl solutions with two
different pH values 163
2+
4-20 Breakthrough curves of Mg from mixed-cation subsoil
columns which received input HCl solutions with two
different pH values 164
3+
4-21 Breakthrough curves of A1 from mixed-cation topsoil
columns which received input HCl solutions with two
different pH values 166
3+
4-22 Breakthrough curves of Al from mixed-cation subsoil
columns which received input HCl solutions with two
different pH values 167
xiv

Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy
LEACHING OF CATIONS DURING DISPLACEMENT BY ACID
SOLUTIONS THROUGH COLUMNS OF CECIL SOIL
By
KO-HUI LIU
August, 1987
Chairman: R.S. Mansell
Major Department: Soil Science
Cation transport under conditions of steady liquid flow
was investigated, using columns filled with water-saturated
Cecil (Typic Hapludult) topsoil and subsoil. Initially the
2+
soils were saturated with Ca , using CaC^ solution, which
was then miscibly displaced by MgC^ solution.
A Galerkin finite-element method with cubic-spline
shape functions was used to numerically solve the equation
for one-dimensional transport and binary exchange of cations
in the Cecil soil columns. The numerical model was verified
by assuming that the solute was non-reactive solute or that
paired cations had no preference for soil exchange sites.
Cation exchange capacity (CEC) was shown to be the most
sensitive input parameter when the model was used to
simulate cation transport in the soil columns. Increase of
CEC increased retardation of cation movement. Relatively
xv

small values of CEC gave reasonable predictions for the
cation distributions in the soil columns.
Dilute HCl solutions with a pH of 3.9 and 4.9 were
applied at 1.0 cm h ^ Darcy flux to columns of air-dry soils
to simulate the effects of acid rain upon leaching of soil
cations. Soil columns were prepared using Cecil topsoil and
+ 2+
subsoil initially saturated separately with K , Ca , and
2+
Mg , also using untreated and mixed-cation soils.
"Mixed-cation" soils were obtained by mixing equal masses of
+ 2+ 2+
K -, Ca -, and Mg - saturated soils.
The initial effluent samples from acid-treated soil
columns were high in basic and acidic cation concentrations
and low in pH. Dramatic decreases in cation concentrations
and increases in pH were observed with increasing volume of
effluent up to about 3 to 5 pore volumes. Between 5 to 30
pore volumes of effluent, pH was in the range from 6.0 to
6.5, and cation concentrations decreased gradually. Soil
base saturation in the columns was drastically reduced after
acid application, especially for columns receiving pH 3.9
acid solution. Experimental results from the leaching
experiments indicated that total quantities of cations
removed by the acid at pH 3.9 were 1.2 to 2.0 times more
than those at pH 4.9.
xvi

CHAPTER I
INTRODUCTION
Description of Problem
During recent decades, the environmental impact of acid
precipitation has become a major concern in many
industrialized countries. Concerns about possible harmful
effects on soil, vegetation and surface-water supplies have
resulted in intensive research in this area. The most
serious effects of acid deposition upon forest soils are
commonly thought to be the potentials for accelerating
cation leaching, for increasing soil acidity, and hence for
decreasing forest productivity. Acidification of surface
waters resulting in the release of toxic aluminum ions
3+
(Al ) from sediments in lakes and streams is harmful to
aquatic ecology (Hutchinson and Havas, 1980).
During rain events, rainwater which does not run off
the surface or undergo evapotranspiration infiltrates into
the soil profile. As the soil water moves by mass flow,
hydrodynamic dispersion mixes the native soil solution with
the incoming rainwater. Ion species moving with the soil
solution may undergo ion-exchange with counter ions
initially present on the soil exchange phase. In addition
to ion exchange phenomena, the presence of H+ in the
rainwater results in secondary reactions such as acid
1

2
3+
dissolution of sesquioxides and clay minerals to yield A1
ions.
To understand the mechanisms of ion movement during
acid-rain deposition in forest soils, the interaction
between rainwater and soil must be carefully examined. In
particular, ion-exchange processes are of great importance
(Wiklander, 1975).
Hypotheses
The working hypothesis for this research is that acid
precipitation increases nutrient leaching from forest soils
in direct proportion to the H+ concentration of incoming
rainwater. Direct sampling of soil and soil solution at
specific forest sites to determine changes in ionic
composition of soil exchange and solution phases is very
time-consuming and expensive. More importantly, forest
soils also commonly generate H+ ions (Mollitor and Raynal,
1982, Reuss and Johnson, 1985) due to biological processes.
A need exists to provide foresters and soil scientists
with predictive tools for describing the leaching of
2+ 2+ +
nutrient cations, such as Ca , Mg , K , etc., through soil
profiles. The usefulness of such predictive tools for
planning purposes should include assessment of the benefits
and consequences of forest management and fertilizing.
Furthermore, such a tool could provide information help in
controlling groundwater quality. Predicting changes in
ionic composition of the soil solution and exchange phases

3
as acid solution infiltrates soil is central to evaluating
acid-rain effects upon forest soils. Predictions based upon
established soil physical-chemical methods would be the most
reliable method of evaluating long-term effects of acid rain
on soil (Reuss, 1983).
Objectives
The ion-exchange process is one of the most important
soil chemical processes which influences cation leaching
during infiltration of acid rain into soil. Thus, a
computer model solely based on binary ion-exchange
equilibrium and saturated steady water flow was developed
for predicting the movement of cation species in soil. The
response of cation leaching to input acid solution at two
different pH values was determined using columns of Cecil
soil (Typic Hapludult).
There are three objectives in this study. The first
objective was to evaluate a numerical model by simulating
binary cation exchange and transport during miscible
displacement of electrolyte solutions through columns of
Cecil soil. The second objective was to experimentally
determine effects upon cation leaching of applying
artificial acid-rain solutions (hydrochloric acid) to
columns of Cecil soil . The third objective was to
determine the leaching effect of applied artificial acid-
rain solutions (hydrochloric acid) to columns of Cecil soil
pretreated to saturate exchange sites with specific cation

4
species. The format for this dissertation follows the
sequence of stated objectives.

CHAPTER II
MODEL SIMULATION OF BINARY CATION EXCHANGE
AND TRANSPORT IN COLUMNS OF CECIL SOIL
Introduction
The exchange of cations between exchange and solution
phases in a soil system is an important phenomenon which
greatly influences nutrient movement in soil, leaching of
cations by acid-rain infiltration, reclamation of
salt-affected soil, contaminant migration, and other
processes. Ion transport in packed exchanger beds and in
soil columns has been investigated for many decades and
several approaches have been used to model the ion-exchange
process. Thomas (1944) developed an equation applicable to
cation transport in columns of synthetic ion exchanger,
assuming that the exchange mechanism obeyed reversible,
second-order, reaction kinetics. Rible and Davis (1955)
used chromatographic theory of ion exchange to investigate
cation exchange and transport in soil columns, but neglected
the effect of hydrodynamic dispersion during transport.
Assuming chemical equilibrium between cations in solution
and on the exchange phase, Lapidus and Amundson (1952)
proposed a model for ion transport such that exchange
followed a linear isotherm, with hydrodynamic dispersion
5

6
then resulting in mixing of displacing and displaced
solutions in the porous media. In some investigations (Lai
and Jurinak, 1971; Reiniger and Bolt, 1972; Persaud and
Wierenga, 1982), empirical equations have been fitted to
measured adsorption data in order to obtain adsorption
isotherms for incorporation into the transport equation.
Ion chromatography theory is based upon differences of ionic
migration rates for different ions in a packed bed. In
modeling, the movement of these ionic species is based upon
the principle of conservation of mass. In multicomponent
chromatography theory (Bolt 1967; Helfferich and Klein,
1970), where the local equilibrium condition is also
assumed, the exchange relationship between any two given ion
species in the system can be described by a Vanselow
selectivity coefficient. This coefficient is valid when
ionic strength and ion-pair corrections are made for cation
activities in the solution phase (Babcock and Schulz 1963;
van Beek and Bolt, 1973). Therefore, quantitative
relationships between the equilibrium constants for ion
exchange, concentrations, and valences of each pair of ions
can be obtained. Using multicomponent chromatography, Rubin
and James (1973) proposed a general mathematical form for
transport and exchange for each of several ion species by
using a generalized Vanselow selectivity function. The
model was later used successfully to describe the processes
2+
of exchange and transport for three major cations (Ca ,
2+ +
Mg , Na ) in an aquifer system (Valocchi et al., 1981). In

7
that study, cation-exchange reactions were assumed to be
controlled by local equilibrium, the soil column was assumed
to be water saturated, water flow was assumed to be
one-dimensional and steady, and exchange selectivity
coefficients for each pair of ion species were assumed to be
constant. Although the model successfully described the
movement of several major cations, the selectivity
coefficients for binary pairs of ions are not constant in
soil but are known to vary as the solution composition
changes (Sposito, 1981; Mansell et al., 1986).
The convection-dispersion transport model for cations
in porous media is governed by a system of nonlinear partial
differential equations which can be solved by employing
different numerical techniques with the aid of a digital
computer. Lai and Jurinak (1971) used a finite-difference
method and a single-component exchange isotherm to model
2+ 2+
cation adsorption in soil. They found, for the Ca -> Mg
binary reaction (i.e. exchange sites initially occupied with
2+ 2+
Mg and displacement by Ca ), the use of a nonlinear
exchange function demonstrated good agreement between
computed and experimental results. Rubin and James (1973)
later formulated the governing transport equation for
multi-ion species in one-dimensional space by applying the
Galerkin finite-element method with linear-basis shape
functions over the space domain. The resulting system of
nonlinear ordinary differential equations was solved using
Crank-Nicholson method and predictor-corrector

8
approximations. Their numerical simulations included
homovalent binary cation exchange with different values for
the cation exchange capacity and dispersion coefficient
parameters. Valocchi et al. (1981) extended this technique
to a two-dimensional (axially symmetric) model with the use
of isoparametric quadrilateral elements in order to solve a
ground-water contamination problem for an aquifer. They
concluded that, for a binary system, ion concentration
profiles consist of a single advancing exchange front while,
for a ternary system, two fronts may be separated by a
plateau zone. These phenomena were actually observed in
• a a a "f 2^ 2^"
their field simulation of Na , Mg and Ca breakthrough
curves for well-water downstream from an injection well.
Jennings et al. (1982) followed the approach of Rubin and
James (1973) and applied equilibrium interaction chemistry
(speciation, etc.) independently of the
convective-dispersive transport equation. A set of
algebraic chemistry equations was coupled to the mass
transport equation and a numerical solution was obtained by
the Galerkin finite-element method applied over the space
domain. A backward finite-difference approximation was used
for the time derivative, and a surface complexation sorption
model allowed the consideration of complex metal and ligand
species at soil surfaces. The sorption reaction was assumed
to occur under instantaneous equilibrium conditions. Using
concepts from multispecies ion chromatography as given by
Valocchi et al. (1981), and mobile-immobile water theory as

9
given by van Genuchten and Wierenga (1976), Mansell et al.
(1986) constructed a numerical model to simulate the
leaching of cations in soil columns. The mathematical
solution was numerically approximated using a
Crank-Nicholson finite-difference technigue, and cation
transport was observed to be best simulated when selectivity
coefficients were given as functions of the equivalent
fractions of specific cations in the solution phase.
The first objective of this investigation was to
develop a finite-element computer model capable of
simulating exchange and transport of multiple species of
cations in soil columns. This computer model could then be
used by the soil scientists or foresters as a basic working
tool for predicting the movement of cations in soil. A
second objective was to experimentally determine selectivity
coefficients from cation concentrations in solution phase
and on exchange sites for soil columns. A third objective
was to evaluate the model as a means to simulate binary ion
exchange and transport in columns of Cecil soil by comparing
simulated with experimental data.
Theory
Transport Equation
The general form of the differential equation used to
describe one-dimensional, convective-dispersive transport of
each cation species i in uniform porous medium or soil under
steady water-flow conditions may be written as

10
3C. o 3C. 3 2C. 3C.
— + — = D = v -— i=l,2,...n [2-1]
3t © 3t 3X^ 3X
where C^(x,t) (mmole(+) L 1) is the aqueous-phase
concentration of species i, (mmole(+) Kg 1) is the
2 -1
adsorbed-phase (exchange) concentration, D (m h ) is the
dispersion coefficient, v (m h ^) is the average pore-water
velocity, a (Mg m 3) is the dry-soil bulk density, ©
3 -3
(mm ) is the volumetric water content, x (m) is distance
(downward) in the soil, and t (h) is time. The second term
on the left-hand side of equation [2-1] describes the time
rate of change of the exchange-phase concentration for ion
species i. If n cation species are considered, n equations
having the form of equation [2-1] must be solved
simultaneously subject to the following initial and boundary
conditions:
t = 0 and x > 0
t > 0 and x = 0
t > 0 and x = L
+ v Ci
[2-2]
where C^^(mmole(+) L ^) is the initial concentration of each
species i in the porous medium and is the input solution
concentration for ion species i. Before solving equation
[2-1] subject to auxiliary equations [2-2], the time rate of
change of the adsorbed concentration (C^) in equation [2-1]
with respect to should be obtained as a functional

11
relationship between and C^. Details of this analysis
for are given in the next section.
Equation for Instantaneous Cation Exchange
The reversible, equilibrium-controlled cation-exchange
reaction involving ion species A with valence z^ and ion
species B with valence can be expressed as
z2 A(ad) + Z1 B(sol) = Z1 B(ad) + z2 A(soir 12-3]
The preference for soil exchange sites for competing cations
can be expressed in quantitative terms by the law of mass
action (Helfferich, 1962) as
[A]
[B]
Z1
[2-4]
where [A] and [B] denote activities of cation A and B
adsorbed onto soil exchange sites, respectively; [A] and [B]
denote activities of cations A and B in solution,
respectively; and K is the thermodynamic exchange constant
which is an indicator of the affinity of exchange sites for
ion B relative to affinity for ion A.
If Ma and Mg are given in units of mole per kg on the
exchange phase of ion species A and B, respectively, mole
fractions for ion species A and B are defined as

12
M
B
and
M.
B
[2-5]
M,
T
where MT represents the sum of Mft and Mfi (mole per kg)
of the soil. The relationship between activities and mole
fractions for ion species in the exchange phase is given by
Sposito (1981) as
*
[A] = UA Ma
[2-6]
m = UB Mb ;
where and u0 are activity coefficients for cations A and
jlf
B on the exchange phase, and and Mfi are mole fractions
for cations A and B on the exchange phase, respectively.
The relationship between activities and concentrations
for the solution phase is given by Sposito (1981) as
[A] = rA Ma
[2-7]
[B] rB Mg ;
where rand rg are ion activity coefficients for cations A
and B in the solution phase and and Mg are molar
concentrations for cations A and B in the solution phase.
Substitution of equations [2-6] and [2-7] into equation
[2-8] yields
K
[2-8]

13
The activity coefficients rA and for the solution
phase may be calculated from the extended Debye-Huckel
equation as functions of ionic strength (I) as
r
i
exp
-0.5085 z2i Jl
1+0.328 ai Vi
[2-9]
where z^ is the valence of cation i (i
the ion-size parameter for ion A or B,
Equation (2-3) then can be rewitten as
zi z-'
[B] (rA Ma)
K. —
— Z2 Z1
[A] Z (rB Mg)1
= A, or i = B), a^ is
and 1 = 0.5 EfC.^2).
[2-10]
When an exchange reaction is reversible, it is useful
to measure the Vanselow selectivity coefficient (Kv) as a
function of the exchange composition. Any variation in Kv
is related directly to that of the activity coefficient of
the components of the exchange phase. Kv is defined by
Sposito (1981) as
In equation [2-11] the exchange-phase activity
coefficients are generally not known for soils. However,
the thermodynamic formulations of Gaines and Thomas (1953)
can be used for calculation of the equilibrium constant and
exchange-phase activity coefficients, yielding

14
In K = f1 In K dCD . [2-12]
J0 v B
An equilibrium-controlled cation exchange reaction is
defined as follows (Helfferich, 1962; Bolt, 1967):
z2 C1 + Z1 C2 = Z1 C2 + z2 C1 ' [2-13]
where 1 and 2 are exchanging species with and
z2 valences, respectively. Concentrations (mmole(+) kg ^
soil) of each exchange species are given as C^, and
concentrations (mmole(+) L 1) of dissolved species are given
as C^. Therefore, an ion-exchange selectivity coefficient
K can be defined as
s
[2-14]
where
*
and is called the equivalent fraction of ion i on the
exchange phase.
This form is reasonably suited to describe the ion-
exchange phenomenon. The magnitude of Ks changes with the
cation concentrations in the solution phase and also with
the equivalent fractions of individual ions on the exchange

15
sites (Helfferich, 1962; Cho, 1985). The value of CT is
assumed to be constant for a given soil material. For
numerical simulations in this work the magnitude of K
s was
assumed to be constant (Valocchi et al., 1981) during the
ion exchange transport process.
Transport with Ion Exchange
For the case of binary cation exchange and steady water
flow, the convective-dispersive mass-transport equation
[2-1] can be explicitly written as
3Cn a 3C. 32C1 3C..
± + — = D i- - v , [2-15]
3t 0 3t 3x 3x
and
3C- a 3C9 32C9 3C9
+ = D - v . [2-16]
3t 0 3t 3x2 3x
Equations [2-14] and [2-15] are coupled through additional
equations for the time rate of change of adsorbed-phase
terms (the second terms on the left-hand sides of equations
[2-15] and [2-16]) to specifically describe the cation-
exchange process. If one assumes the soil cation exchange
capacity CT to be time invariant at any given location in
the soil, it can be expressed as the local sum of the
concentrations of cations in the exchange phase as
CT
c + c
ul c2
[2-17]

16
and the total solution-phase concentration CT at any given
time and distance is the sum of the concentrations of ion
species present in the solution phase
CT = ci + c2 • [2-18]
If one further considers the simplified case where the
(input) solution has the same total normality CT as the
native solution (CT is constant), an explicit form for the
exchange isotherm can be obtained by substituting equations
[2-17] and [2-18] into equation [2-14]. This yields
1 + r
[2-19]
1/z, z 2/zi
where r = a/P, a = C_-C1/ and (3 = K C, .
T 1 s 1
This simplification reduces the binary-exchange problem to a
single-species exchange problem (Rubin and James, 1973;
Valocchi et al., 1981). If we define a parameter F as
3C- x
F = — = 2 ' [2-20]
3CX
1/z- _ 1/z.
where x = CT Kg CT, and e = CT + (Kg - 1)C1#
the chain rule may be used to obtain
3C1 3C, 3C. 3C1
— = — = F — . [2-20]
3t 3C1 3t 3t
Therefore, using equations [2-14], [2-20] and [2-21],
equations [2-15] and [2-16] can be combined to give one
equation with one dependent variable as given by

17
o 3C. 9 2C, 3C1
( 1 + — F ) — = D = v — . [2-22]
© 31 3 3 x
The term R= l+(a/©)F is referred to as the retardation
function for transport of ion 1 through the soil. For
binary nonpreferential (Kg = 1) homovaient exchange
F = CT/ CT and R = 1 + (a/0) (C^/C^), so that, for constant
cation exchange capacity, retardation of cation transport
tends to increase as CT decreases towards small values such
as those that normally occur in rain water. Also, for this
case, cation retardation can be expected to be greatest in
soils with highest values for CT and with highest
soil-to-solution ratios (a/0). Appropriate initial and
boundary conditions for equation [2-22] are
t = 0 x > 0 ci = cü , [ 2 — 23a ]
9 C1
t > 0 x = 0 v C. £ = - D + v C. and
3 x
9C1 [2-23b]
t > 0 x = L = 0 .
9 x
Partial differential equations given as [2-22] and
[2-23] constitute a mathematical description of cation
transport and exchange in a soil column of finite length L
during steady water flow, they were solved in this research
by use of a Galerkin finite-element method. For simplicity,
concentration for ion species 1 is denoted by C
throughout the remainder of the dissertation. Subscript or

18
superscript notation for C was only used for formulation
purposes in the finite-element method.
A Galerkin Finite-Element Numerical Method
Finite-Element Method
Finite-element methods typically incorporate an
approximating integral equation to replace the original
governing partial differential equation (Pinder and Gray,
1977). Variational and weighted-residual techniques are two
methods most commonly used to obtain the approximate
integral equation. The Galerkin finite-element weighted-
residual method has been widely used for the mass-transport
equation (Price et al., 1968; Pinder, 1973) and is the
method used here. In the finite-element method, the domain
of interest is discretized into a number of subdomains
called elements. In this study, a line-segment element was
used and a cubic-spline function was chosen as the
interpolation function. For the Galerkin approximation,
consider a linear differential operator of the form
L (u) =0 on domain D . (2-24]
To solve u, a trial function u(x,t) is assumed which is
composed of a linear combination of approximation functions
containing time-dependent, undetermined coefficients G^(t)
and specified-shape functions N^(x) that satisfy the given
boundary condition of the problem. The trial function can
be expressed as
= u(x,t) = 2 G.(t) N.(x) .
j=l 3 3
u(x,t)
[2-24]

19
where n denotes the number of nodal points.
Substituting the trial function u into the linear
differential operator L for the exact solution u will result
in a residual R(x,t) as defined by
R(x,t) = L(u) = L ( [ 2 G. (t) N.(t) ] ) if 0 . [2-26]
j=l J 3
This residual is forced to zero in an average sense
over the entire domain D through the selection of
undetermined coefficients Gj(t). The Gj(t) values are
calculated by setting the weighted integral of the residual
to zero. In the Galerkin finite-element, weighted-residual
method, the shape functions are used as the weighting
functions and the resulting integral form is:
f R(x,t) N.(x) dx = 0 . [2-27]
JD
Interpolation Function
The use of cubic-spline functions as interpolation
functions in the finite-element method has been successfully
applied in solving boundary-layer flow problems (Hsu, 1976;
Hsu and Liakopoulos, 1981). In the present study, the
unknown function C(x,t) at a given depth in a soil column
(profile) is represented by classical cubic splines. Since
classical cubic-spline interpolation functions provide
expression of C(x,t) as continuous functions with continuous
first and second derivatives, classical cubic-spline

20
functions possess a number of desirable optimal properties
(Ahlberg et al., 1967).
For a selected soil column of length L, suppose that
the space interval 0 < X < L is properly discretized into n
interconnected elements with n+1 nodal points at 0 = x^ <
< <...< xn+1 = L, where values of C(Xj,t) and its
derivatives with respect to x at nodal point j are defined
as
and
c (Xj,t)
= Cjit)
SC
C.'(t) =
J
S x
2-
ff
9 C
Cj (t)= -
2
SX
[2-28]
For the ith element, one defines the element size h^ as
h^ = x^+1 - x^ and the local coordinate z as z = x - x^ with
0 < z < h^. One further expresses the cubic polynomial
function approximating C(x,t) in the ith element as g(z,t).
If g(z,t) is made to satisfy the conditions
g^C^t) = C±(t) ,
gi(h't) = ci+i(t) , [2-29]
g'V (0 , t) = C,,i( t) ,
and g"i+1(h,t) = C".+1(t) ,
g(z,t) is given by
g±(z,t) = -
z(z-h.)(z-2h.) „ z-h.
= ci (t) 1 Ci(t)
6h.
hi

21
z(z-h.)(z+h,) „
k—Ci- (t) +
hi
[2-30]
The requirement of slope continuity at nodes is further
imposed as
and
a’i = g'i+i(0) '
g'^0) = c' 2 (t)
g'n(hn) = C’n+l(t) •
[2-31]
The following system of n+1 equations is thus
obtained
1 "
_ c +
1
ll
—— c
- C-
„ (hj^i) ■
a J -3 3+1
j+1 r "
c 3+2
C .
J
1 1
- ( +
hj
‘j+i
> cj+1 +
hd+i
Cj+2
-Ü- C " + -A. c
, n
n
'n+1
3 n+1 hn h
n n
+ C
n+1 •
[2-32]
The system of equations given as equation (2-31) can be
written in matrix form simply as
[2-33]
where [A] and [B] are nonsingular, symmetric, tridiagonal
[A] {C^} = [B] {C±} + (S)
(n+1)-by-(n+1) constant matrices, and
fl m ff If if
( Ci J = [ C1 ' C2 ' Cn+1 ] '
{ C± }± = [ c1, c2,
' Cn+1 ]
[2-34]

22
and { S } = [ -C1 ,0,
'°' Cn+1 ]
Consequently, one has
{ C'^ } = [ A ]_1 [ B ] { } + [ A ]_1 { S } . [2-35]
Alternatively, in component form
ti n+1 i i
Ci <*>«=) + 6Biin+1Cn+1 (t) .
where [ a. . ] = [A]-1 [B] [2-36]
-*• / J
and [ B. . ] = [A]"1
/ J
Substituting equation (2-35) into equation (2-29), the cubic
polynomial approximating function g(z,t) for C(x,t) in the
ith element, in polynomial of degree three in z, is given by
the following formula:
n+1 , ,
gi(z't)=+1ai,:(z)cj(t) + bi,l,z)C l(t) + bi,n+lC n+l(t)
where
z3-3z2+2zh.2
— + ai+l,j
3 2
z -zh.
l
6hi
[2-37]
z-h.
6i,j
+ 6i+l,j
[2-38]
3 2 2
z -3zzh.+2zh.
t>i ! -*- / J- -*• • x V,
3 2
z -zh^
i+l,l
and z3-3z2hi+2zh.2 z3-zh2
bi,n+l(z) “_Pi,n+l “ + Pi+l,n+l ~
in which 6 is the Kronecker's delta. Therefore the cubic

23
polynomial g(z,t), approximating C(x,t) in the ith element,
is a linear function of all the nodal values of C(x,t) and
the slopes at extreme nodes. The resulting trial function
£(x,t) of classical cubic spline approximation for the
function C(x,t) at a specific length of soil column
(profile) is given by
C(x,t) = 2 6^ g.(x,t) where 6^ = 1 ^or xi < x < xi+l*
j=l 0 otherwise.
[2-39]
It is obvious that cubic spline function C(x,t) agrees with
C(x,t) at nodes and is twice continuously differentiable in
the interval of interest.
Method of Weighted Residuals
Substituting the boundary conditions of equation [2-23]
into equation [2-37], the approximation function g(z,t)
becomes:
n+1 v
g.(z,t) = £ a. •(z) C . (t) + b. - (C- -C-) . [2-40]
j=l -> 1'x D
Therefore, the unknown coefficients to be determined are C^,
C2, , ...., C Substituting equation [2-40] into
equation [2-39] yields
C(x,t) = ní1N.(z) C.(t) + B..(z) —— C. , [2-41]
j = l J J D
n v n
N, = £ 6. a. 1(z) + £ 6. b. ,(z) ,
1 i=l 1 1,1 D i=l 1 1,1
where

24
n
N. = E 6. a. .(z) j=2,3,....,n+l
3 i_l i i/J
n
and B. = 2 6. b. ,(z)
1 i=l 1 1,1
For the initial boundary-value problem given by
equation [2-22] that satisfies the boundary condition
[2 — 23b], the trial solution can be written as
C(x,t) = C(x, t) = n¿1 N . ( z ) C . (t) + B^z) — C- .
j=l 3 J D 1
j=l,2, n+1 [2-42]
Substituting equation [2-42] into equation [2-22] and
applying the method of weighted residuals one obtains
j; Nm(x)t (1 + — F)
3C
Tt"
- D
3 2C
3 X
3 C
+ v
3 x
Equation [2-42] can be explicitly rewritten as
n+1
3 C.
v
] dx = 0 .
[2-43]
3 C4
J¡ (1+ _ F) Nm(x)[ j£l Nj(z) -5^ + — Bl(Z) -3^ ] dx
n+1 a N.
= LN„ —^(t) + DC,
3 x
n+1 3 N .
3 B,(z)
3 x
3B, (z)
] dx
Jq Nm [j^i v Cj(t) + vCf 5x ] dx '[2-44]
where are weighting functions. Since there are n+1
unknown nodal values for the dependent variable C(x,t), a
set of n+1 weighting functions must be chosen for N^.
Therefore, using Galerkin's method, the weighting functions

25
are chosen to be the interpolation (shape) functions of the
assumed solution, such as
Computational Method
After rearranging,
9 C • (t)
[Q] { } = ( [R]
9 t
where:
[2-45]
equation [2-44] becomes
- [U]) (Cj(t)} + ({V}-{S})Cf ,
[2-46]
[Q]
fL (1 +
J0
a
e
F) Nm(z)
n+1
j£1 Nj(z)dx
9
n+1 9*N.(z)
[ri = ° /; v*> jSi —j
9 x
n+1 9N.(z)
[U] = V r N (z) •£, r
J q m 3-1 9.
dx
dx
{V} = D r N (z)
J0 m
9 B1(z)
dx
9 x
9B.(z)
and {S} = v + Nm(2)
dx
[2-47]
In equation [2-46], undetermined coefficients Cj(x,t)
do not appear explicitly but are embedded in the function F.
This nonlinear term is linearlized by employing the previous
time-step solution of (x,t) into the F term for
manipulation. For example, if we consider m = 2, 3,...,
n+1, the matrix coefficients at the left-hand side of
equation [2-37] can be written as

26
^ c j (t)
m, 3 3 t
n+l
= jSa/o1 Vi (z> 11 + e
n
( cT + w)
n+l
E a. . dz
i=l
3 Cj (t)
3 t
[2-48]
where n = CT Kg CT,
n+l n+l *
and W = CT + (K - 1) ( E 6. E a. . C,
1 s i=l 1 i=l 1/J 3
n+l
+ E 6. b. 1(-Cf q/D))
i=l 1 1,1 1
For the right-hand side of equation [2-46], the matrix
coefficients are
given as:
n+l
n+l
V, a
R , = Ü
m, j
(
j-2
(
A J
rhi ai
0
n+l
n+l
V,
U . = v
(
.£~
(
•2-, I
. a
m,D
J-2
l-l J
o1 ]
n+l n+l
V.
m,i = - q cf (3S2 /ol amii(z) (z) dz )), [2-51]
and
S 1 = v
m, l
n+l n+l , ,
< j-2 ( Á JqÍ Vi(z> bi,l (z> <
— C() dz]
[2-52]
In the process of numerical integration, the definite
integral is given by equations [2-48] through [2-52]. Since
these equations are very complex, an explicit expression can
not be obtained. However, this integral can be effectively

27
evaluated by using Gaussian-Legendre quadrature formula
(Krylov, 1962)
J- 1F«P) d* F^m)(M)
[2-53]
where A and cp ^ are the set of weighting coefficients
m m
and roots associated with M-th degree Legendre polynomials.
The quadrature formula is exact if F (cp) is a polynomial of
degree less than or equal to 2M-1. In the present work, m=4
was used. In applying equation [2-53] to the equations
[2-48] through [2-52] one must first transform the interval
[0, h^] onto [-1, 1]. This can be accomplished by the
transformation
W = — (1 + 2
[2-54]
The system of equations [2-46] is large and 'stiff'. This
is typical for the system of ordinary differential equations
arising from the application of the method of lines to
partial differential equations (Hindmarsh, 1981). In
solving the system of ordinary differential equations, if
the magnitude of eigenvalues cover a wide range, an
undesirably small time-step size is required. A problem of
this type is called 'stiff'. A computer model for
simulating convective-dispersive ion exchange/transport
consists of 28 elements with this proposed method, giving
rise to 29 ordinary differential equations to be solved
simultaneously. Due to the presence of stiffness,
conventional numerical integration of the equations [2-46]

28
becomes inefficient and a method that is more suitable for
stiff equations should be employed. The LSODE solver
developed by A. C. Hindmarsh at the Lawrence Livermore
National Laboratory was used in this study as a part of the
main subroutine throughout the program. The LSODE
subroutine (Hindmarsh, 1980, 1983) is capable of solving
systems of ordinary differential equations of the form
dy
= f(t,y) , [2-55]
dt
and y(t,0) = fQ
where y, f, and fQ are vectors of length N.
In the computation, the spatial discretization was made
to give a small element-size in the immediate vicinity of
the inlet boundary, and gradually coarser elements were used
for increasing distances from the inlet. Element sizes were
obtained by trial and error in order to provide solutions
without oscillations. Mass-balance error was not allowed to
exceed 2% in a given simulation. A small initial time step
(5 * 10 ^ sec) was used for generating stable solutions,
after which larger time steps (300 sec) were used. All
computations were performed with the IFAS computer network
on a VAX 11/750 computer at the University of Florida.
Double-precision arithmetic was used in all computations.
Material and Methods
Soil
The Cecil (Typic Hapludult) soil used in this study was
obtained from a forest site located at Clemson University in

29
Clemson, South Carolina. The exact location of the site was
reported earlier by Dr. V. L. Quisenberry (Cassel, 1985)
from the Agronomy Department of Clemson University.
Reported texture of the Cecil soil profile varied from site
to site, with the clay content of the Ap horizon ranging
from 6 to 38 percent depending upon the amount of subsoil
mixing which had occurred subsequent to soil erosion. Clay
content in the B horizon ranged from 42 to 72 percent
(Cassel, 1985). In situ values of unsaturated hydraulic
conductivity reported (Cassel, 1985) for the 0-30 cm depth
-4 -2 -1
ranged from 1.70 x 10 to 4.51 x 10 cm h , whereas those
for the 30-60 cm depth ranged from 4.32 x 10 4 to 4.6 x 10 1
cm h 1, respectively. In situ values of soil water content
3 -3
for the 0-30 cm depth ranged from 0.275 to 0.495 cm cm ,
3 -3
whereas values ranged from 0.409 to 0.560 cm cm for the
30-60 cm depth (Cassel, 1985). Typic Hapludult soils are
freely drained with great or moderate depth to hard rock,
have an ochric epipedon that is not both thick and sandy,
and have a loamy or clayey particle-size class in an
argillic horizon.
Cecil topsoil and subsoil bulk samples for this
research were obtained from the 0-30 and 30-60 cm depths,
respectively, of the profile. The soil was air-dried,
passed through a 2-mm sieve, and stored in covered plastic
buckets.
Values of pH for the soil samples were determined in a
soilrwater suspension (1:1 soil:water) using a glass

30
electrode. Organic matter content was determined by the
Walkley-Black method (Allison, 1965). Particle-size
distribution was determined by the pipette method (Day,
1965).
Exchangeable cation concentrations were determined
using neutral 1 M NH^OAc, by placing 5-g of 2-mm air-dried
soil in duplicate 50-ml centrifuge tubes, and adding 25 ml
of 1 M NH^OAc to each. All tubes were stoppered and shaken
for 30 minutes. The tubes were then placed in a centrifuge
and spun at 2000 rpm for 10 minutes, with number 42 Whatman
filter paper being used to collect the supernatant in a
50-ml volumetric flask. The same procedure was repeated and
finally the solution was brought to a volume of 50 ml with 1
M NK^OAc (Thomas, 1982).
3+
Exchangeable Al was determined by 1 H KC1 extraction
of 10-g of air-dried soil in duplicate 50-ml volumetric
flasks, using 25 ml of 1 M KC1. The soil and KC1 were
mixed, allowed to stand for 30 minutes, and then transferred
to Buchner funnels fitted with number 42 Whatman filter
paper mounted on 250-ml vacuum flasks. An additional 125
ml of KC1 was added in 25-ml increments to give a final
volume of 150 ml (Thomas, 1982).
Total potential acidity as determined by BaC^-TEA
extraction was obtained by placing 10-g soil samples in
duplicate 50-ml volumetric flasks. To each flask, 25 ml of
buffer solution was added, mixed well with the soil sample,
and allowed to stand for 1 hour. It was then transferred to

31
a 5.5-cm diameter Buchner funnel fitted with Whatman number
42 filter paper. Three 25-ml volumes of buffer solution
were then added to the suspension. These additions were
followed with 100 ml of replacement solution to give a final
volume of 200 ml. Also, a blank solution was prepared from
100 ml of buffer solution and 100 ml of replacing solution.
Two drops of bromocresol green indicator and 10 drops of the
mixed indicator were added. Finally, the solution was
titrated with 0.2 M HC1 to a repeatable endpoint in the
visual color range from green to purple. The same
procedure, using the same endpoint, was used for soil
leachates (Thomas, 1982).
Column Experiment
The cylindrical container for soil columns used in this
investigation was constructed by stacking 20 lathe-cut
_2
plexiglass rings with 3.75 x 10 m inside diameter and
0.01-m length each. At the top and bottom of the soil
columns endplates consisting of a fixed, thin-plastic disc
with small holes evenly distributed over the surface were
placed in contact with the soil. On the opposite side of
each endplate two outlets were designed, one for inflow or
outflow purposes and a second for flushing the solution, if
necessary. The cylindrical rings were held together by
carefully wrapping water-proof, acid-resistant electric tape
around the circumference. A check for water leakage was
made prior to packing soil into each column.

32
Two columns designated topsoil and subsoil were
prepared carefully by uniformly packing air-dried Cecil
topsoil and Cecil subsoil, respectively. Soil columns were
positioned vertically and placed between two wooden boards
supported by threaded steel rods to hold the soil and rings
in place. A Rainin model Rabbit peristaltic pump was used
to introduce solutions at predetermined and calibrated rates
into the bottom of these columns. Effluent from the top of
the column was collected by an ISCO model 430 fraction
collector. Soil columns were initially saturated with 0.01
mmole(+) CaC^ from the bottom of the columns. Periodic
2+
checks for Ca concentration in the effluent were made,
2+
until steady state was reached with respect to Ca
concentrations of input and output solutions. Soil exchange
2+
sites were then assumed to be saturated with Ca . Miscible
displacement was initiated by adding a 0.01 mmole(+) L ^
MgC^ exchanging solution into the bottom at constant flux.
When predetermined total amounts of exchanging solution had
been added to a given column, the flow was terminated. The
pore volume for each soil column was obtained as the weight
difference between wet and air-dried soil columns obtained
before and after each experiment. Pore-volume corrections
were made for the volume of entrapped solution inside the
two endplates. The columns were equilibrated overnight
before being dissected to ensure that soil exchange and
solution phases were of equilibrium. A centrifuge method
was used to separate the soil-solution phase from the

33
adsorbed phase for each section of every soil column. For
the centrifuge method, two different sizes of centrifuge
tube are required. A small hole was made at the bottom of
the smaller tubes (0.015-m diameter) and a number 42 Whatman
filter paper was cut and placed over that hole. Each column
section of soil was carefully transferred into a prenumbered
small centrifuge tube. Then, each small tube was placed
into a corresponding prenumbered larger centrifuge tube
(0.025-m diameter). A glass bead was placed between the
small and large tubes. After balancing pairs of tubes
within the centrifuge, they were spun at 4000 rpm for 30
minutes. Moist soil samples were quantitatively removed and
weighed. Weights of air-dry soil were also recorded. Each
dried sample was then ground and passed through a 2-mm
sieve. The exchanger phase concentrations of cations were
obtained by the forementioned extraction method. A
correction was made for concentrations of cations in
residual solution in the exchange phase of the soil sample.
In addition, one topsoil column and one subsoil column
were prepared to permit determination of solute dispersion
coefficients (D). Soil columns were set up vertically for
flow experiments. A peristaltic pump was calibrated and
used to introduce distilled water into the bottom of each
soil column. After one day of leaching, a check for zero
Cl concentration was obtained, and the distilled water was
changed to 0.001 M KCl input solution. The effluent was
fractionally collected, and the experiments were terminated

34
once the Cl concentration of the effluent had reached that
of the input concentration. The Cl dispersion-coefficient
values were obtained by using the resulting Cl breakthrough
curves and a least-squares fitting procedure (van Genuchten,
1981) was used to fit an analytical solution (Brenner, 1962;
van Genuchten and Alves, 1982) to experimental breakthrough
data.
Cation-Exchange Isotherms from Soil Columns
. 2+ 2+
The cation exchange isotherm for Mg -> Ca exchange
was obtained from columns of Cecil topsoil and subsoil,
2+ 2+
respectively. Concentrations of Ca and Mg in solution
and exchange phases as obtained by the centrifuge method
were used to determine the exchange isotherms. Tables 2-2
and 2-3 present concentrations of cations in the two phases
for Cecil topsoil and subsoil, respectively. CEC values for
each specific depth were obtained by taking the sum of the
basic and acidic cations. An average CEC value for the
whole column was used in this calculation. Total solution
concentrations of cations were assumed to have similar
magnitudes as those of the input solution. Concentrations
2+2+ .
of Ca and Mg were determined using an atomic absorption
spectrophotometer (Perkin Elmer model 460).
Results and Discussion
Soil Properties
Soil parameters used in the column experiments are
presented in Table 2-1. General soil properties, such as

35
soil pH, particle size distribution, clay content, and
cation exchange capacity, are presented in Table 2-2.
Table 2-1 Soil parameters used in the column experiments
Parameter
Topsoil
Subsoil
Darcy velocity (M H i
1.11 x 10^
1.08 x 10~l
Dispersion coeff. (M H x)
Bulk density (Mg M
3.03 x 10 4
1.85 x 10 4
1.64
1.42
Volumetric water content
(MJ M_J)
Bulk volume of soil (L)
Column length (M)
0.37
0.46
2.21 x 10_1~
20.05 x 10 ¿
2.21 x 10_19
20.05 x 10“^
Total concentration
0.01
0.01
(MMOLE(+) L i)
Porosity
0.38
0.46
Pore volume (L)
81.97 x 10 J
101.47 x 10
Total number of pore
4.50
3.62
volumes collected
Cation exchange., capacity
10.6
17.0
(MMOLE(+) Kg 1 soil)
Selectivity coeff.(KMg_>Ca)
0.225
0.798
Table 2-2 Properties of Cecil
topsoil and
subsoil
Topsoil
Subsoil
pH(1:1)
4.46
4.80
Sand(%)
76.90
61.60
Silt(%)
14.00
13.70
Clay(%)
9.10
24.70
O.M.(%)
1.60
1.04
CEC from NH¿
OAc+KCl
17.00
27.00
(mmole(+) Kg
CEC from
i 1 soil)
54.00
70.00
NH.OAc+BaCl9
(mmole(+) Kg
-TEA
\ soil)
Soil texture
Sandy
loam
Sandy clay loam
Clay minerals Interlayered-hydroxy
Interlayered-hydroxy
Vermiculite,
Vermiculite,
Kaolinite,
Kaolinite, Gibbsite,
Quartz
•
Quartz.
Amorphous
Al, Fe
hydrous
oxides
Al,Fe hydrous oxides

36
The two different CEC values for the Cecil soil
resulted from the two extraction methods used for
exchangeable acidity. Exchangeable acidity as determined by
BaC^-TEA extraction has more practical utility for
calcareous than for acid soils (Thomas and Hargrove, 1984),
and KCl extraction is reflects the immediate need for lime
(Thomas, 1982). Thomas (1982) suggests that the best method
for determining exchangeable acidity for acid soils is to
use a neutral, unbuffered salt to remove the acidity at the
pH of the salt solution-soil mixture.
Clay content of the Cecil subsoil was 2.7 times greater
than that for the topsoil, but organic matter content of the
topsoil was only 1.6 times greater than that for the
subsoil. The ratio of subsoil to topsoil CEC values was
somewhat less (1.3 to 1.6) than the 2.7 ratio for clay
contents. The higher clay content in the subsoil did,
however, result in a higher CEC and volumetric water content
for the subsoil. The texture of the topsoil was sandy loam
as compared to sandy clay loam for the subsoil. The type of
clay minerals in the topsoil and subsoil indicates that both
soils were highly weathered and had electrostatic charge
sites which were predominately pH-dependent charge surfaces.
Verification of the Numerical Model
Predictive accuracy of the computer program for the
numerical solution to the convective-dispersive ion-
transport equation was evaluated for a simple problem of
transport of a conservative solute (i.e. where Ks = 0) for

37
which an analytical solution was available, by comparing the
model simulation with the analytical solution. Assuming that
the retardation factor R = (l+(o/0)F) = 1 and that the
selectivity coefficient Ks = 0, the appropriate transport
equation for this problem is:
8C 32C 3C
R = D 5 v , [2-56]
31 3XZ 3X
where the following initial and boundary conditions were
assumed:
C(x,0) = Ci ,
ac
-Tl
4-
vC
X
II
o
II
<
o
o
o
IA
rt-
IA
rt
o
9*
x=0
and
9C
- n
9X
x=L
[2-57]
Ci =
0.000001
mmole(+) L ^
and
o
o
il
o
•
o
mmole(+) L 1 were used
as chosen values.
Brenner (1962) has given an analytical solution to this
boundary-value problem as:
1 n x
= erfc( ) + — exp(
2
1
2
u 2 u
3 Rx+vt
( 1+a + ) exp(a) erfc(
R u
)
pap R ?
+ T (1+ + ) exp(p - t> )
2 4 4R 4Dt

38
3 (3 v
-12p-a + + ( $) ] exp(p)
2 R 2D
R(2L-x)+vt
erfc( ) . [2-58]
u
where
$ = (2L-x+vt/R), u = 2(DRt)1/2,
T = (4v2t/nDR)1/2, (3 = v2t/D,
and a = vx/D, p = vL/D, n = Rx - vt
The numerical solution was obtained using the Cecil
topsoil parameters presented in Table 2-1. The result is
shown in Fig. 2-1 for the case Ks = 0 and R = 1.
Nonpreferential ion exchange with selectivity coefficient
Ks = 1 and R = (l+(o CT)/(© CT)) was also performed and is
given in Fig. 2-2. Excellent agreement between numerical
and analytical solutions demonstrates that the computer
program functioned as designed for the case of transport of
inert solutes as well as for the case of non-preferentialiy
reactive cations.
Exchange Isotherm Curves for Columns of Cecil Soil
2+ , 2+ 2+ •
The Mg exchange isotherms for Mg -> Ca binary
exchange on Cecil topsoil and subsoil are shown in Figs. 2-3
and 2-4, respectively. The magnitude of KjVjg_Ca indicates
2+
the relative preference of exchange sites for the Ca and
2+
Mg species. The shape of experimental isotherms for the
Cecil soil was concave relative to the diagonal (for
2+
normalized plots of equivalent fractions of Mg in the
. 2+
exchange phase plotted versus equivalent fractions of Mg

Relative Concentration (C/C
for the case where the binary exchange selectivity coefficient equals
zero.

Relative Concentration (C/C
for the case where the exchange selectivity coefficient equals unity.

Equlv. Fraction (Sorbed)
l . o

Equiv. Fraction (Sorbed)
1 . o
NJ
1 . o

43
in the solution phase). The selectivity coefficients for
2+ 2+
Mg -> Ca exchange are considerably less than unity at
all values of solution concentration, implying that exchange
2+ 2+
sites in Cecil topsoil and subsoil preferred Ca over Mg
The observed effect was greater for subsoil than for
topsoil, however. After displacing 4.5 pore volumes of
2+
effluent through the topsoil, Mg occupied 30% to 60% of
the cation exchange capacity throughout the column. After
displacing 3.6 pore volume of effluent through the subsoil,
2+
however, Mg occupied from 15% to 80% of the cation
exchange capacity. The average of the total solution cation
concentrations in both the topsoil and subsoil columns was
about 3% less than the CT value (Tables 2-3 and 2-4). This
3% may represent the H+ concentration in the solution phase.
The average of the total cation content on the exchange
sites of topsoil and subsoil columns was about 37% less than
the corresponding CT value (Tables 2-3 and 2-4). The
2+
displacing cation Ca , although initially saturating the
soil exchange sites, due to the unknown masking effects of
interlayer-hydroxy vermiculite (M+(Mg,Fe)3(Si,Al)(OH)2)
could become a non-exchange cation.
Exchange selectivity Coefficients (Ks) for Soil Columns
From the soil-column experiments, concentrations of
cations in the solution and exchange phases are given in
Tables 2-3 and 2-4 for Cecil topsoil and subsoil,
respectively. The selectivity coefficients were
obtained by using equation [2-14]. The cation exchange

44
Table 2-3 Concentrations of cations in solution and
exchange phases for topsoil after miscible
displacement with 4.5 pore volume
Depth
Ca
Mg
K
Na
Al
Sum
t \
phase
\ cm)
T 1
i
0.224
9.050
0.231
0.348
0.014
9.867
2
0.188
9.150
0.174
0.459
0.016
9.987
3
0.184
8.990
0.143
0.414
0.016
9.747
4
0.211
8.670
0.127
0.470
0.016
9.494
5
0.319
8.560
0.311
0.599
0.013
9.802
6
0.259
8.590
0.127
0.459
0.016
9.451
7
0.323
8.780
0.341
0.517
0.013
9.974
8
0.419
8.160
0.272
0.334
0.012
9.197
9
0.511
11.900
0.409
0.487
0.013
13.320
10
0.387
8.560
0.262
0.431
0.012
9.652
11
0.547
8.330
0.346
0.894
0.013
10.130
12
0.459
8.230
0.272
0.424
0.012
9.397
13
0.487
8.230
0.270
0.327
0.012
9.326
14
0.523
7.900
0.256
0.410
0.013
9.102
15
0.607
8.030
0.256
0.435
0.013
9.341
16
0.675
7.670
0.260
0.348
0.013
8.966
17
0.705
7.960
0.274
0.485
0.019
9.443
18
0.799
8.070
0.327
0.434
0.017
9.647
19
0.898
7.340
0.149
0.334
0.017
8.738
20
0.978
7.410
0.258
0.431
0.016
9.093
Average 9.684
Depth
Ca
Mg
K
Na
Al
Sum
/ ____ \
v cm j
i
0.609
6.580
0.125
0.265
*
*
2
0.614
4.940
0.146
0.257
4.280
10.237
3
0.544
4.860
0.113
0.261
*
*
4
0.564
4.120
0.107
0.265
5.592
10.648
5
0.584
3.950
0.133
0.270
*
*
6
0.659
3.700
0.113
0.261
5.792
10.525
7
0.589
3.460
0.105
0.270
*
★
8
0.664
3.460
0.125
0.257
5.859
10.365
9
0.709
3.790
0.110
0.257
*
*
10
0.828
3.620
0.128
0.261
5.826
10.663
11
0.813
3.540
0.194
0.287
*
*
12
0.973
3.790
0.141
0.278
5.992
11.174
13
0.913
3.540
0.164
0.270
*
*
14
0.938
3.290
0.153
0.287
5.603
10.271
15
1.060
3.790
0.166
0.261
*
★
16
1.070
3.370
0.189
0.278
5.692
10.599
17
1.100
3.210
0.248
0.270
*
*
18
1.140
3.290
0.177
0.283
5.647
10.537
19
1.270
3.290
0.215
0.278
*
*
20
1.500
2.960
0.205
0.287
6.014
10.966
* undetermined
Average 10.598

45
Table 2-4 Concentrations of cations in solution and
exchange phases for subsoil after miscible
displacement with 3.6 pore volumes
Depth Ca Mg K Na Al Sum
(cm) Solution phase
mmole(+) L
1
0.188
9.420
0.143
0.470
0.064
10.285
2
0.148
9.510
0.190
0.518
0.060
10.426
3
0.148
9.250
0.176
0.511
0.056
10.141
4
0.144
9.220
0.135
0.483
0.055
10.037
5
0.212
8.950
0.205
0.435
0.052
9.854
6
0.244
8.890
0.203
0.424
0.051
9.812
7
0.224
8.490
0.131
0.477
0.049
9.371
8
0.299
8.630
0.137
0.497
0.048
9.611
9
0.435
8.760
0.174
0.351
0.044
9.764
10
0.667
8.300
0.258
0.407
0.042
9.674
11
0.853
8.110
0.240
0.370
0.040
9.613
12
1.600
7.340
0.184
0.306
0.039
9.469
13
2.110
7.180
0.209
0.282
0.019
9.800
14
3.450
5.930
0.276
0.337
0.024
10.017
15
3.730
5.730
0.143
0.157
0.024
9.784
16
4.420
4.530
0.171
0.157
0.021
9.299
17
5.140
3.790
0.258
0.209
0.022
9.419
18
5.360
3.420
0.194
0.170
0.020
9.164
19
5.540
3.620
0.269
0.235
0.020
9.684
20
6.560
2.070
0.371
0.365
0.016
9.382
Average 9.731
Depth Ca Mg K Na Al Sum
(cm) Exchange phase
mmole(+) Kg
1
0.609
13.700
0.177
0.235
*
★
2
0.509
13.000
0.184
0.226
1.993
15.912
3
0.489
12.100
0.197
0.243
*
*
4
0.549
11.600
0.258
0.243
4.663
17.313
5
0.499
11.300
0.230
0.226
*
★
6
0.589
11.200
0.235
0.226
4.974
17.224
7
0.599
10.900
0.238
0.235
*
*
8
0.793
11.200
0.287
0.243
4.396
16.919
9
0.913
10.000
0.317
0.243
*
★
10
1.300
10.500
0.333
0.235
4.072
16.440
11
1.200
9.960
0.243
0.226
*
*
12
2.590
9.710
0.266
0.226
4.264
17.056
13
3.540
7.570
0.261
0.252
*
*
14
4.340
6.670
0.304
0.243
4.266
15.824
15
6.090
5.760
0.279
0.235
*
★
16
4.740
7.160
0.289
0.261
4.511
16.961
17
8.280
4.530
0.312
0.217
*
*
18
8.930
3.870
0.327
0.226
4.534
17.887
19
9.430
3.130
0.404
0.243
*
*
20
10.300
2.470
0.476
0.235
5.190
18.671
* undetermined
Average 17.020

46
capacity was approximated as being the average sum of the
2+ 2+ + + 3 +
concentrations of Ca , Mg , K , Na , and Al in the
exchange phase. Since 5 species were involved, the
2+ 2+
equivalent fractions of Ca and Mg did not sum to unity.
Thus, values obtained for Ks were approximated. Values for
I^g^a varied with depth since solution and exchange phases
of cation concentrations varied and ranged from 0 to 1. In
order to simplify model simulation, KMg_Ca was assumed
constant, and the input value for KMg_Ca was obtained by
taking the mean of KMg_Ca obtained for all depths for the
Cecil topsoil and subsoil columns, respectively. The
magnitude for KMg_Ca was 0.225 for Cecil topsoil, and 0.798
2+
for Cecil subsoil, indicating that Ca was preferred over
2+ 2+
Mg by both topsoil and subsoil but that Mg was preferred
more by subsoil exchange sites than by topsoil exchange
sites.
Model Sensitivity Analysis
A sensitivity analysis for dispersion coefficient (D),
volumetric water content (9), bulk density (a), selectivity
coefficient anc^ cation exchange capacity (CT) was
performed for the numerical model with respect to the
experimental data from the soil columns.
Dispersion coefficient. Figures 2-5 and 2-6 present
2+
predicted and observed distributions for Mg concentrations
in the soil solution phase with column depth where a
sensitivity analysis was performed for the dispersion
coefficient (D) for both topsoil and subsoil. Dispersion

«H
\
T
o
H
O
E
E
C
O
â– H
-M
0
L
•P
C
0
u
c
o
u
Figure 2-5 Experimental distributions of Mg2+ concentrations in the solution phase
of the topsoil column after miscible displacement with 4.5 pore volumes,
along with calculated results obtained using three values for the
dispersion coefficient.

along with calculated results obtained using three values for the
dispersion coefficient.
00

49
coefficients (D) of 1.85*10 4 and 3.03*10 4 m2/h were
obtained from experimental Cl breakthrough curves for
subsoil and topsoil columns, respectively. Values of the
dispersion coefficient that had ± 2% deviation from
experimental dispersion coefficients were used in model
simulations for both topsoil and subsoil. Experimental and
simulated cation-concentration distributions for D values of
3.09*10-4, 3.06*10-4 and 3.03*10-4 M2 h_1 for the topsoil
column are presented in Fig. 2-5. Experimental and
simulated cation-concentration distributions for D values of
1.90*10-4, 1.85*10~4, and 1.80*10'4 M2 h-1 for the subsoil
column are presented in Fig. 2-6. For both topsoil and
subsoil columns, the effect of ± 2% variation in D upon
2+ .
predicted profiles of Mg m the solution phase was
extremely small. This analysis revealed that the model is
relatively insensitive to small changes in values of D.
In these simulations, the effect of the dispersion
2+
coefficient upon distributions of Mg concentration in the
soil was apparently slight due to the fact that the
dispersion coefficient is independent from the cation-
retardation factor R.
Volumetric water content. Predicted and observed
. 2+
distributions of Mg concentration in the solution phase
with column depth are presented in Figs. 2-7 (topsoil) and
2-8 (subsoil), where a sensitivity analysis was performed
with respect to the volumetric water content (0). Average
volumetric water contents obtained experimentally from

rl
\
T
0)
M
0
E
E
C
0
Tl
P
<0
L
P
C
Q)
U
C
0
u
Figure 2-7 Experimental distributions of Mgz concentrations in the solution phase
of the topsoil column after miscible displacement with 4.5 pore volumes,
along with calculated results obtained using three values for volumetric
water content.
Ln
o

H
N
+
w
Q>
ri
0
E
E
c
0
-H
0
c.
c
0
u
c
o
Ü
Depth (M)
Figure 2-8 Experimental distributions of Mg + concentrations in the solution phase
of the subsoil column after miscible displacement with 3.6 pore volumes,
along with calculated results obtained using three values for the
volumetric water content.
i/i

52
3 -3
column experiments were 0.370 and 0.458 M M for topsoil
and subsoil, respectively. A range of volumetric water-
content values of ± 2% deviation from the experimental data,
such as 0.360 and 0.380 M^ M 3 for topsoil and 0.468 and
3 -3
0.448 M M for subsoil, respectively, was tested to
determine the sensitivity of 0 as an input parameter to the
model. Results show that the effect of variations in © on
2+
prediction of Mg concentration was small for topsoil and
had essentially no effect for subsoil. The effect of 0 is
shown by the term a/0 (the soil-to-solution ratio) in the
cation-retardation factor (R). The smaller values of © give
the higher ratios of a/0 and the most retarded cation
movement.
Bulk density. Computed and observed depth
2+
distributions of Mg concentration m the solution phase
are given in Figs. 2-9 and 2-10, where a sensitivity
analysis was performed for bulk density (a). Experimental
bulk density values obtained from the column experiment were
_3
1.64 and 1.42 Mg M for topsoil and subsoil, respectively.
Values with ± 2% deviation from the experimental data gave
values of 1.67 and 1.61 Mg M ^ and 1.45 and 1.39 Mg M ^ for
use in the sensitivity analysis, respectively. The effect
of a occurs through the ratio a/0 in R. The sensitivity
analysis revealed that even slight changes in values for a
could substantially influence simulated cation
concentrations.

Q)
H
o
E
E
C
o
•H
P
(U
L
P
C
Q)
U
c
o
u
displacement with 4.5 pore volumes.
en
LO

Q)
H
0
E
E
C
0
•H
â– P
(0
L
V
c
Q)
U
c
0
u
Ln

55
Selectivity coefficient. Figs. 2-11 and 2-12 present
2+ .
simulated and observed distributions for Mg in the
solution phase with depth for topsoil and subsoil columns,
respectively. The approximate selectivity coefficients
(K^g-ca) obtained from column experiments were 0.225 and
0.798 for topsoil and subsoil, respectively. A deviation of
± 2% from these experimental values were used in simulations
to determine sensitivity to this input parameter. These
values were 0.230 and 0.220 for topsoil and 0.782 and 0.814
for subsoil, respectively. The'effect of KMg_Ca upon the
2+
simulation of Mg concentration distributions in the
solution phase was minor for both topsoil and subsoil.
Although the selectivity coefficient occurs within the
cation retardation factor R, sensitivity analysis showed
that slight changes in KMg_Ca had little effect upon the
2+ . ...
Mg -concentration profile distribution.
Cation exchange capacity. Sensitivity of the model to
change in cation exchange capacity (CT or CEC) was examined
by using two values of CEC in separate simulations. Values
of the CEC of 70 and 54 mmole(+) Kg 1 soil were obtained
experimentally from the buffered 1 M NH^OAc plus BaC^-TEA
method, whereas values of 27 and 17 mmole(+) Kg ^ were
obtained from the buffered 1 M NH^OAc plus unbuffered 1 M
KC1 method, for original subsoil and topsoil, respectively.
CEC values of 17.0 and 10.6 mmole(+) Kg ^ soil were the mean
CEC values obtained from all dissected soil sections (Tables
2-3 and 2-4) in columns of subsoil and topsoil,

\
?
G)
rl
0
E
E
C
O
â– H
â– P
(D
L
-P
C
Q)
U
c
o
u
U1
cn

c
o
-H
â– M
(0
L
â– P
C
Q)
U
C
o
u
ui

58
respectively. The CEC for each section was obtained by
extraction with buffered 1 M NH^OAc plus unbuffered 1 M KCl,
2+
and then summing exchange-phase concentrations for Ca ,
Mg^+, K+, Na+ and Al^+. The CEC for the last set of
sections obtained from the soil column were used to
represent the CEC for experimental columns of subsoil and
topsoil, respectively. Column effluent pH values were below
pH 4.5 for both columns (Fig. 2-23). This acidity could be
3+ 2+
coming from A1 which underwent exchange with Ca and
2+
Mg . The pH values of the input solutions were 5.5 for
CaC^ and 5.7 for MgC^.
Figures 2-13 and 2-14 demonstrate the dramatic model
sensitivity to the cation exchange capacity parameter.
The cation exchange capacity values used were 10.6 and 54.0
mmole(+) Kg 1 soil for topsoil, and 17.0 and 70.0 mmole(+)
Kg ^ soil for subsoil, respectively. A large increase in
2+
CEC value the simulated movement of the Mg
front to be retarded during miscible displacement relative
to the experimental data. This effect was greatest for the
finer-textured Cecil subsoil.
Calculated and observed data did not coincide exactly
for either the topsoil or subsoil columns. Overall,
model-simulated curves for distributions of solution-phase
2+
concentrations of Mg with depth best described
experimental data when the smaller of the cation exchange
capacity values were used. This result was as expected,

Concentration (mmole ( + ) /l)
column after miscible displacement with 4.5 pore volumes, along with
simulation results for two values of the cation exchange capacity.

Concentration (mmole (+)/l)
Figure 2-14 Experimental distributions of Mg¿+ concentrations for the subsoil
column after miscible displacement with 3.6 pore volumes, along with
simulation results for two values of the cation exchange capacity.

61
since retardation R is a function of both CT and CT-
Therefore, using large values of CEC in the simulation would
tend to retard cation movement.
Discrepancies observed between predicted and observed
2+
distributions of Mg concentration using CEC values of 10.6
and 17.0 mmole(+) Kg-1 soil for topsoil and subsoil columns,
respectively, were attributed to several factors. First,
certain of the model assumptions were not strictly met.
Careful examination of the soil system reveals that a
contradiction occurs between some of the assumptions and
reality. The cation exchange capacity was not constant but
actually varied from point to point along the soil column as
shown in Tables 2-3 and 2-4. At any given point, the extent
that a specific ion could occupy soil exchange sites would
also be affected by the presence of other ion species in the
3+
system. Exchangeable Al comprised about 25% and 50% of
total exchangeable cations for Cecil subsoil and topsoil,
respectively, after leaching with MgCl2* This probably
2+
means that Ca occupied only 50-75% of the exchange sites
initially, which is considerably less than 100% as assumed
2+ 2+
for the model. Experimental conditions involved Ca , Mg ,
Al^+, K+, Na+ and H', whereas the model assumptions only
2+ 2+
allowed for Ca and Mg . Model simulations performed here
did not sufficiently account for this discrepancy.
Two other sets of cation exchange capacity values were
calculated for Cecil topsoil and subsoil. The reason for

62
using these two additional sets of CEC values was to
3+
determine if exclusion of exchangeable Al from the CEC, or
if exclusion of all of the existing cations species except
2+ 2+
Ca and Mg , would improve simulated results. First,
modified cation-exchange capacity values were obtained by
summing the exchange phase concentrations of all cations
3+
species except Al over all depths as given in Tables 2-3
and 2-4, and then taking means for topsoil and subsoil,
respectively. Magnitudes for subsoil and topsoil were 12.73
and 4.97 mmole(+) Kg ^ soil, respectively. Using these
modified cation exchange capacity values, calculated results
2+
for Mg concentration distributions in solution and
adsorbed phases are given in Figs. 2-15 and 2-16 for subsoil
and in Figs. 2-17 and 2-18 for topsoil, respectively.
Agreement between simulated and experimental data was better
2+
for the subsoil than for the topsoil. Simulations for Mg
concentrations in the topsoil showed an overestimation of
2+
Mg concentrations in both the solution and exchange
phases.
The second method for obtaining a better estimation of
cation exchange capacity values was obtained by summing the
2+ 2+
exchange-phase concentrations of Ca and Mg for all
depths (Tables 2-3 and 2-4) and then taking the mean for
topsoil and subsoil, respectively. Magnitudes of CEC for
subsoil and topsoil were 12.1 and 4.7 mmole(+) Kg 1 soil,
respectively. Based upon these second modified CEC values,
2+
predicted results for distributions of Mg concentrations

Concantration (mmole (+) /l)
with 3.6 pore volumes.

Concentration mmole (+) /Kg soil
with 3.6 pore volumes.

ion (mmole (-+-) /l)

Concentration mmole (+)/Kg soil
with 4.5 pore volumes.

67
in solution and exchange phases are given in Figs. 2-19 and
2-20 for topsoil and in Figs. 2-21 and 2-22 for subsoil,
respectively. Simulated results for the subsoil were
3+
greatly improved as compared to the case where Al was not
included among the exchangeable cations. Simulated results
for topsoil better approximated the observed data, but an
overestimation for concentrations in both the solution and
exchange phases was observed. Careful examination of
constituent cations located on exchange sites of the topsoil
3+
revealed that Al was the dominant cation species,
comprising about 50% of the total exchangeable cations.
Cation concentrations in the exchange phase for the topsoil
decreased in the order Al3 + > Mg2+ > Ca2+ > Na+ > K+. The
24-
topsoil column was obviously no longer dominated by Mg
2+ 3+
For the subsoil column, however, the order was Mg > Al >
2+ -+ +
Ca > K » Na . This phenomenon can be attributed to the
topsoil containing more interlayer-hydroxy vermiculites than
the subsoil. Displacing salt solution through either
2+ 2+
topsoil or subsoil resulted in the exchange of Ca or Mg
with Al3+. Additional acidity (Fig. 2-23) would be caused
3+
by the hydrolysis of Al , which would tend to induce
further mineral dissolution. The subsequent further
3+ 2+
production of Al would then compete with divalent Ca and
2+
Mg for soil exchange sites. The result would be a higher
. 3+
saturation of exchange sites with Al

with 4.5 pore volumes.

Concentration mmole (+)/Kg soil

miscible displacement with 3.6 pore volumes.

Concentration mmole (+)/Kg soil
miscible displacement with 3.6 pore volumes.

Effluent pH
6 . o

73
Conclusions
The principal minerals in the Cecil topsoil and subsoil
are kaolinite, interlayer-hydroxy vermiculite and quartz.
Gibbsite was also found in the subsoil. This highly
weathered acid soil also contains amorphous materials in the
form of A1 and Fe oxides. The clay content in the subsoil
is almost three-fold greater than for the topsoil, and
organic matter in the topsoil is 1.6 times greater than for
the subsoil.
2+ 2+
Exchange isotherms for Mg -> Ca reaction in Cecil
soil were concave in shape for both soils, indicating that
2+ . 2+
Ca was adsorbed preferentially to Mg on the soil
exchange sites. This result was as expected.
Excellent agreement between numerical and analytical
solutions demonstrated that the computer program for
convective-dispersive transport of two ion species
functioned as designed for the cases of both non-reactive
and reactive solute species.
Results from sensitivity analysis showed that the
model-simulation results were essentially insensitive to
small changes in the dispersion coefficient and selectivity
coefficient. The dispersion coefficient was apparently
independent from the cation retardation factor R, although
the selectivity coefficient is actually embedded in the
retardation factor. The volumetric water content and soil
bulk density both showed slight effects upon model-predicted
results, which can be explained by the inclusion in R by the

74
soil-to-solution ratio a/0. The exact magnitude of R could
not be obtained, since R involved unknown concentration
variables. The cation exchange capacity is the most
critical input parameter to the simulation. This is a
result of the cation retardation function R = (l+(a/0)F),
where the function F in equation [2-20] is a function of CT.
Therefore, cation movement undergoes greater retardation in
soil with a larger value of CEC (and thus a larger value of
R) than in soil with a small CEC.

CHAPTER III
CATION LEACHING DURING CONTINUOUS DISPLACEMENT
BY AQUEOUS HYDROCHLORIC ACID SOLUTION
THROUGH COLUMNS OF CECIL SOIL
Introduction
Acid rain is commonly considered to be a serious
environmental problem for industrialized nations. In
particular, soil scientists are concerned that acid
2+
atmospheric inputs could accelerate cation (examples: Ca ,
2+ +
Mg , K , etc.) leaching from the soil profile. Nutrient
deficiency accelerated by leaching of cations and
+3
mobilization of toxic Al in the soil solution may lead to
eventual decline in productivity of certain soils. Since
agricultural soils routinely receive limestone and
fertilizer as a crop-management aid, whereas forest soils do
not, scientists are generally more concerned about effects
of acid precipitation upon forest soils than upon
agricultural soils. Acid rain in the forms of or HNO^
2+
may affect the status of forest nutrients such as Ca and
2+
Mg , either positively or negatively. This phenomenon has
been extensively investigated by Abrahamsen (1980). In
cases where nutrient cations are abundant and S and N
concentrations are at plant-deficiency levels in the soil,
moderate inputs of acid rain may actually cause increased
forest growth. At the other extreme, however, where soil
75

76
sites have adequate N and S concentrations but are deficient
in nutrient cations, acid rain in sufficient amounts may
decrease productivity (Johnson et al., 1982).
In all cases, anions associated with acid inputs or
present in the soil must be mobile in the soil solution if
basic cations are to be transported through the soil
profile. That is, cations cannot leach from soil without an
equivalent concentration of accompanying anions in solution.
Immobilization of anions can effectively prevent cation
leaching; therefore, the entire process of soil leaching is
strongly dependent on the input solution or on the internal
production of mobile anions (Johnson and Cole, 1980).
However, anion-leaching theory has been questioned by Krug
and Frink (1983). They point out that some of the factors
commonly considered to make soils susceptible to
acidification by acid rain are the same as those which
acidify soil through natural processes. Reuss (1983) used
2+
cation-exchange equilibrium to predict the leaching of Ca
3+
and Al following the application of to soil. Cosby
et al. (1985a) presented an equilibrium model which included
equilibrium soil-solution cation exchange, inorganic
aluminum reactions and dissolved inorganic reactions. The
model demonstrated the interaction of soil chemical
processes as a key to controlling stream water chemistry. A
mathematical model which used quantitative descriptions of
soil chemical processes to estimate long-term chemical
changes that occur in the soil, soil water and surface water

77
of catchments in response to changes in acid deposition was
proposed by Cosby et al. (1985b). Due to the lack of
long-term records of catchment-water quality, however,
results obtained from their model need further verification.
Any criteria used for assessing soil sensitivity to
cation leaching by acid rain should include cation-exchange
3+
capacity (CEC), base saturation and mobilized Al , pH and
carbonate content (McFee, 1980). Critical properties, such
as CEC and cation-selectivity coefficients, are especially
needed in the investigation of effects of acid deposition
upon soils.
The first objective of this study was to determine the
influence of input solution pH upon leaching of basic
cations during continuous displacement by aqueous HCl
solutions through hand-packed columns of Cecil topsoil and
subsoil. The second objective was to determine the
influence of input solution pH upon distributions of cation
concentrations in soil columns after leaching experiments,
and the third objective was to use cation concentrations in
the solution and exchange phases to calculate binary
selectivity coefficients for ion-pairs.
Basic Theory
Surfaces of Soil Particles
Constant electrostatic surface charge for a clay
4+
mineral is derived from isomorphous substitution of Si by
3+ 2+ 3+
Al or of Mg for Al within the crystalline structure.
Mica and related 2:1 lattice-type minerals, smectites,

78
vermiculites and interstratified forms of these minerals
typically have constant surface charge regardless of
solution concentration or pH (Gast, 1977). Colloids with
constant surface potential and variable surface charge are
in turn commonly found in soils which are extensively
weathered and dominated by sesquioxides of Fe and A1 or 1:1
kaolinitic minerals. The surface charge density for
colloids of this type varies with pH and salt concentration
(Keng and Uehera, 1974). Soil organic matter also has
pH-dependent charge, arising from dissociation of phenolic
OH and carboxylic groups.
Cation-Exchange Equilibria
The exchange reaction between an exchange-phase cation
1 with valence z^ and a cation 2 of valence z2 in solution
can be described by the equation
z2 Cx + zi C2 = z1 C2 + z2 C1 . [3-1]
For a reversible reaction such as equation (3-1) at
chemical equilibrium, one type of exchange selectivity
coefficient (Ks) can be expressed as

79
— *
The equivalent fractions (C^ ) for cations 1 and 2 in the
exchange phase are given by
where i and j refers to cations 1 or 2, (or C^) is the
concentration of exchangeable cation 1 or 2 in moles of
positive charge (equivalents per Kg of soil), and is the
solution-phase concentration (mmole(+) L of cation 1 or
2. The magnitude of Ks indicates the relative preference of
exchange sites for cation 2 over cation 1. If and
Ks = 1 the exchange sites show no preference for either of
two ions, whereas Ks < 1 indicates that cation 1 is adsorbed
preferentially, and Ks > 1 indicates that cation 2 is
preferred by the exchange sites.
Effects of Acidification
Continuous addition of acid solution to a soil tends to
increase total acidity of the soil and to decrease pH. The
extent to which soil pH is decreased by addition of acid is
greatly determined by the buffering capacity of a given
soil. A number of associated effects are also observed upon
addition of acid to soil. One of the more important effects
• 2+ 2+ 4"
is the loss of basic cations such as Ca , Mg , K , and
Na+. Basic cations are leached with co-anions, such as
bicarbonate, chloride, nitrate, sulphate, or organic anions.
A second effect is the displacement of cations from
weak-acid exchange sites such as occur on humus and on

80
poorly-ordered alumino-silicates and hydrous oxides. A
third effect is a decrease in CEC as the pH drops. Aluminum
ions are mobilized by acid dissolution of soil components,
and thus strongly compete with other cations for soil
exchange sites.
Materials and Methods
Physical and Chemical Properties of the Soil
Cecil soil used in this study was obtained from a
forest site located near Clemson University in Clemson,
South Carolina. The exact location was reported earlier by
Dr. V. L. Quisenberry (Cassel, 1985), Agronomy Department,
Clemson University. Reported texture varied from site to
site, with the clay content of Ap horizon ranging from 6 to
38 percent depending upon the amount of subsoil mixing which
occurred subsequent to soil erosion. Clay content in the B
horizon ranged from 42 to 72 percent (Cassel, 1985). In
situ values of unsaturated hydraulic conductivity reported
(Cassel, 1985) for the 0-30 cm depth ranged from 1.70*10 ^
to 4.51*10 ^ (cm h ^), and those for the 30-60 cm depth
-4 -1 -1
ranged from 4.32*10 to 4.6*10 (cm h ), respectively.
In situ values of soil-water content for the 0-30 cm depth
3 -3
ranged from 0.275 to 0.495 cm cm , and for the 30-60 cm
3 -3
depth ranged from 0.409 to 0.560 cm cm (Cassel, 1985).
The Cecil soil used in this research is classified as a
Typic Hapludult. Topsoil and subsoil bulk samples were
obtained from depths of 0-30 and 30-60 cm, respectively.

81
Soil samples were air-dried, passed through a 2-mm sieve,
and stored in covered plastic buckets.
Values of pH for the soil samples were determined in
soil-water suspensions (1:1 soil:water) using a glass
electrode. Organic matter content was determined by the
Walkley-Black method (Allison, 1965). Particle-size
distribution was estimated by the pipette method (Day,
1965). Exchangeable cations were determined with neutral 1
M NH^OAc, by placing 5 g of 2-mm air-dried soil in duplicate
50-ml centrifuge tubes, and adding 25 ml of 1 M NH^OAc to
each. All tubes were then stoppered and shaken for 30 min,
with the tubes then being placed in a centrifuge and spun at
2000 rpm for 10 min. Number 42* Whatman filter paper was
used to collect the supernatant into a 50-ml volumetric
flask. The same procedure was repeated, with the volume
then brought up to 50 ml with 1 M NH^OAc (Thomas, 1982).
Exchangeable Al^+ was determined by 1 H KCl extraction
of 10-g, air-dried, soil samples in duplicate 50-ml
volumetric flasks, with 25 ml of KCl. The soil and KCl were
mixed, allowed to stand for 30 minutes, and then transferred
to Buchner funnels fitted with number 42 Whatman filter
paper mounted on 250-ml vacuum flasks. An additional 125 ml
volume of KCl solution was added in 25-ml increments to give
a final volume of 150 ml (McClean, 1965; Thomas, 1982).
X-Ray Diffraction
X-ray diffraction analysis of the soil clay was
performed for topsoil and subsoil, respectively, by the

82
method of Whittig (1965). The soil was treated with
hypochlorous acid to remove carbonates and organic matter,
followed by use of the dithionite method to remove Fe
oxides. The clay fraction was separated by alternatively
adding pH-10 water followed by centrifuging for different
combinations of speed and time. The clay (< 2 mu) fraction
was prepared on a ceramic tile such that one was Mg-glycerol
saturated and air-dried, and the other was K-saturated and
air-dried. The samples were then X-rayed at room
temperature (25° C). Samples were next heated at 110 °C and
300 °C by sucessive treatment and X-rayed after each
treatment. As the last step, K-saturated sample was heated
at 550 °C before being X-rayed.
Column Preparation and Displacement Procedure
The column consisted of a stack of 1-cm diameter
lathe-cut plexiglass cylinders, with dimensions of 0.10 m
length and 0.0375 m inside diameter to give a total internal
-4 3
volume of 1.105 x 10 m . The rings were held together by
wrapping water-proof, acid-resistant electrical tape along
the circumference in order to give a water-impervious
column. Soil was held in the column by placing fine nylon
mesh and Whatman number 42 filter paper over a thin plastic
disc with small holes distributed on the surface in each of
the inflow and outflow endplates. A check for water leaks
through the column wall was made prior to packing soil into
each column. Each column was then placed in the vertical
position and was sequentially packed by slowly adding

83
increments of air-dry soil until the total quantity of soil
required was obtained, the sides of the column being gently
tapped during packing to provide the desired bulk density.
The whole column was mounted vertically between two wooden
support boards and fastened with four threaded steel â–  rods
to give mechanical support. After the end of the
experiment, the pore volume of each column was obtained from
the mass difference between wetted soil columns and oven-dry
soil columns, with a correction being made for the amount of
solution held inside the endplates. Solutions of HCl were
displaced through columns of Cecil topsoil and subsoil with
an average Darcy velocity of 1.06 (± 2%) cm h 1. Displacing
solutions were prepared from a HCl stock solution with pH
was adjusted to either 3.9 or 4.9. A Rainin model Rabbit
peristaltic pump was calibrated and used to deliver solution
to the bottom of each soil column. The soil column was
initially air-dry, so transient flow occurred when the
experiments were started. Eventually (after displacement of
1 to 2 pore volumes of effluent) steady-state water flow was
maintained for each column. Effluent from the top of the
column was collected in equal increments of 11.05 (± 2%) ml,
using a fraction collector. These samples were stored in
refrigerator for later analysis.
Dissection of Soil Columns, Extraction, and Chemical
Analysis
After flow had been terminated, columns were
maintained in a vertical position overnight to ensure that

84
the whole system was of equilibrium. The next day, with the
column still in the vertical position, the tape was removed
carefully. After removing the outflow endplate, a piece of
parafilm was placed over the end of the column and a fine
steel thread was forced between consecutive rings in order
to slice the column into sections. Resulting sections of
soil were carefully removed and placed on a piece of
parafilm. Each whole section of soil was then packed into
a prenumbered small centrifuge tube which had a predrilled
small hole on the closed end. A Whatman number 42 filter
paper was place on top of the hole, inside the tube. Each
small centrifuge tube was then placed into a corresponding
large-size centrifuge tube along with a glass bead to
separate the extracted solution from soil in the small
centrifuge tube. Paired tubes were carefully placed in the
centrifuge and spun at 4000 rpm for 30 min. Soil samples
were then removed from the small centrifuge tubes and placed
into a weighing boat, and wet soil weights were recorded.
Soil in each weighing boat was air-dried and the soil weight
2+ 2+ +
recorded. Exchange-phase concentrations of Ca , Mg , K ,
and Na+ were obtained using a neutral 1 M NH^OAc extraction
method (Thomas, 1982). Correction was made for entrapped
equilibrium solution remaining in the exchange phase after
centrifuging, by taking differences in equivalents per L for
the extractant and the residual solution. Unbuffered 1 M
KC1 (Thomas, 1982) was used in order to obtain exchangeable
3+ 2+ 2+ +
A1 concentrations. Concentrations of Ca , Mg , K and

85
Na+ in the column effluent, solution and exchange phases of
the soil were analyzed using an atomic absorption
3+
spectrometer. Total Al was determined by optical emission
spectroscopy (inductively coupled plasma argon ICAP).
Results and Discussion
Soil parameters used in the leaching experiment are
presented in Table 3-1. Clay minerals contained in the
Cecil topsoil and subsoil were kaolinite,
interlayered-hydroxy vermiculite, quartz, as well as Al and
Fe hydrous oxides. In addition, gibbsite was found in the
subsoil. Other soil properties, such as particle size
distribution and texture are presented in Table 2-2.
Concentrations of exchangeable cations in Cecil topsoil and
subsoil are presented in Table 3-2.
Table 3-1 Physical and chemical parameters for Cecil topsoil
and subsoil columns
Parameter
Topsoil
Topsoil
Subsoil
Subsoil
pH of input
3.9
4.9
3.9
4.9
solution
Bulk density^
1.57
1.58
1.37
1.37
(mg cm J)
Volumetric
water content
(cmJ cm ;
0.40
0.40
0.49
0.48
Pore velocity _
0.027
0.027
0.022
0.023
(cm h x 10z
)
Column length-
0.10
0.10
0.10
0.10
(cm x 10^ )
Pore volume (L)
Input total H
0.044
0.045
0.054
0.053
125
12.5
125
12.5
concentration
(mmole(+) L
x 10*3)
Total number
37.8
36.9
30
29
of pore volumes
collected

86
Table 3-2 Initial concentrations of exchangeable cations,
pH, and CEC for Cecil topsoil and subsoil
Parameter
Topsoil
Subsoil
pH (1
:1 water:
soil)
4.
.46
4,
.86
PHp (1
:1 KC1: soil)
3.
.85
*
3.
,95
Ca2+
(NH.OAc)
1.
.60
(11%)
8.
.80
(41%)
0 i
(mmole(+)
Kg 1
soil)
Mg2+
(NH.OAc)
2.
.50
(18%)
2.
.20
(10%)
(mmole(+)
Kg 1
soil)
K+
(NH.OAc)
0.
.70
( 5%)
0.
.80
( 4%)
(mmole(+)
Kg 1
soil)
Na+
(NH.OAc)
2.
.60
(18%)
2.
,80
(13%)
(mmole(+)
Kg 1
soil)
Al3
(KC1)
6.
.70
(48%)
7.
,00
(32%)
(mraole(+)
Kg 1
soil)
CEC (
NH OAc+KCl) ,
14.
,10
21.
,70
(mmole(+)
Kg x
soil)
* Numbers enclosed in parentheses represent fractions of
each ion in the exchange phase.
From Table 3-2, dominant basic cations in the topsoil
2+ 2+
in decreasing order of abundance are shown to be Mg , Ca
+ 2+ + 2+
and Na , but were Ca , Na and Mg in the subsoil. Base
saturation was 52% and 68% for topsoil and subsoil,
respectively. Soil pH values determined by KC1 were less
than those determined by distilled water (Table 3-2),
indicating that the variable-charge surfaces of the soil
particles were predominantly negatively charged. Also, K+
exchanged with H+ on the soil surfaces, resulting in the
solution becoming even more acid.

87
Concentrations and pH of Column Effluent
Figs. 3-1 and 3-2 show breakthrough curves (BTC) for pH
and cation concentrations in the effluent from the Cecil
topsoil column which received pH 3.9 HC1 solution. For the
first few effluent samples the pH reading was near pH 4.0
and the concentrations of all reported cations were high.
With increasing numbers of pore volumes of effluent, the pH
abruptly increased and concentrations of cations sharply
declined. From about 10 pore volumes to the end of each run
(30 to 37 pore volumes), concentrations of cations and pH
values for the effluent were essentially stable and the
effluent pH remained higher than that for the input
solution. These quasi-stable pH readings for the effluent
were also considerably higher than corresponding values for
stirred soil-water suspensions (Table 3-2). A similar
effect was observed for effluent collected from the topsoil
column that received pH 4.9 HCl input solution (data not
shown). Effluent pH was lower with the pH 3.9 input
solution than when pH 4.9 input solution was applied. Fig.
2+ 2+ + +
3-2 shows concentrations of Ca , Mg , K and Na in
effluent from the topsoil column that received pH 3.9
solution. For the first two collected effluent samples
2+ 2+
(0.14 and 0.28 pore volumes), Mg and Ca were the
dominant species. Thereafter, K+ was the dominant species
in the effluent until about 16 pore volumes. A similar
trend was observed for column effluent of input pH 4.9.
Concentrations of K+ in effluent from topsoil columns

pH of Ef fluent

Concentration (mmole (+) /l)
00
V£>

90
receiving pH 3.9 and 4.9 treatments (Fig. 3-3) were similar.
2+
Breakthrough curves for summed concentrations of the Ca ,
2+ + + . .
Mg , K , and Na species of basic cations in the effluent
from topsoil columns which received applications of pH 3.9
and 4.9 HCl solutions are presented in Fig. 3-4. Generally,
the more acidic the input solution the higher the
concentrations of cations observed in the leachate.
3+
Breakthrough curves for concentrations of A1 in the
effluent are reported in Fig. 3-5 for treatments pH 3.9 and
. . 3+
4.9, respectively. Initial Al concentrations in the
effluent were as high as 0.25 mmole(+) L 1, and a second
3+ -1
peak in the Al concentration of about 0.11 mmole(+) L
occurred after about 15 pore volumes elution for input pH
3.9. Corresponding values were 0.06 mmole(+) L ^ and 24
pore volumes for input pH 4.9. This elution pattern
3+
indicates that Al is much preferred on soil exchange
2+ 2+ + + 3+
sites over Ca , Mg , K , and Na which causes the Al BTC
curves to be retarded. The more acidic the input solution,
3+
the more Al which should come into the solution phase.
3+
Therefore the Al BTC for input pH 3.9 should be less
retarded than for input pH 4.9, and should also have a
higher peak concentration.
Effluent pH from Cecil subsoil columns which received
pH 3.9 and 4.9 input solutions, respectively, are presented
in Fig. 3-6. Effluent pH initially was 4.2 but abruptly
increased to 6.0 after about 2 pore volumes of elution.
Thereafter, the effluent pH decreased to a relatively stable

Concentrat ion (mmole (+) /l)
from Cecil topsoil columns.

Concentration (mmole (+)/l)
Pore Volumes
Figure 3-4 The effect of input solution pH upon the breakthrough curves of summed
concentrations of Ca2+, Mg^+, K+ and Na+ in effluent from topsoil
columns.
KD
K>

Concentration (mmole (+) /l)
Pore Volumes
Figure 3-5 The effect of input solution pH upon the breakthrough curves of Al^+
from Cecil topsoil columns.

pH of Effluent
which received two input HCl solutions with different values of pH.

95
value between 7 and 20 pore volumes of effluent. Between 20
and 28 pore volumes the pH gradually decreased once more
because the acid-buffering capacity of the soil had by then
been exceeded. As expected, effluent from treatment pH 3.9
had slightly lower pH compared to effluent from treatment pH
2+ 2+ + +
4.9. Effluent concentrations of Ca , Mg , K , and Na
from the subsoil column which received pH 4.9 HCl are
presented in Fig. 3-7. Magnitudes of cation concentrations
in the effluent from columns treated with either pH 3.9 or
2+ 2+ + +
4.9 solutions were in the order Ca > Mg > K > Na ,
which is approximately the same order as quantities of the
various ion species initially on the exchange phase of the
subsoil (Table 3-2).
2+
The pH effect of input HCl upon concentrations of Ca
2+
m the effluent is shown in Fig. 3-8. More Ca was leached
from the subsoil column receiving treatment pH 3.9 than for
• 2+ 2+
input pH 4.9. BTC for summed concentrations of Ca , Mg ,
K+, and Na"1" in the effluent from subsoil columns which
received pH 3.9 and 4.9 HCl solutions are presented in Fig.
3-9. The subsoil column (pH 3.9) which received tenfold
higher H+ concentrations, resulted in leaching of
approximately a two-fold greater quantity of basic cations
in the effluent. Fig. 3-10 indicates that the concentration
3+
of A1 in the effluent from columns of subsoil receiving
the two different pH treatments. Higher concentrations of
3+
Al were observed in the effluent for treatment pH 3.9.

Concentration (mmole (+) /l)
columns which received pH 4.9 input HC1 solution.
vo

Concentration (mmole (+)/l)
l. o
o. a
o. 6
o. A
o. 2
â– i r
1 1 i 1 1 1 r
i r
i i r
i—1—'—•—1—r
T-" »
O - pH 3.9 Ca
* - pH 4.9 Ca
2 +
2+ Í
°8
V£>
* So
*o *
♦P°
* * * * 8S& OqOOqOO q q
***********
O O
* *
o -
5 lO 15 20 25 30
Pore Volume (V/V ) of Effluent
O 2 +
Figure 3-8 The effect of input solution pH upon the breakthrough curves of Ca
from Cecil subsoil columns.

Concentration (mmole (+) /l)
columns.
V£>
oo

Concentration 10 (mmole (+) /l)
Figure 3-10 The effect of input solution pH upon the breakthrough curves of Al3+
from Cecil subsoil columns.

100
The first few samples (within 0.5 pore volume) of
column effluent had low pH and high concentrations of
cations in each case. This phenomenon can be explained as a
salt effect (Wiklander, 1975; Reuss and Johnson, 1985).
Topsoil and subsoil columns initially contained 0.6 and 1.0%
by volume of water before the leaching experiment was
initiated, respectively. As constant-flux infiltration
progressed with time and as the wetting front advanced
through the soil, soluble salts were accumulated in the
moving front. Resulting high concentrations of cations in
the wetting front replaced part of the exchangeable H+ and
3+
A1 , which decreased the pH of the soil solution. This
phenomenon is called a "salt effect". With continuous
+ 3+
application of dilute HC1, initially displaced H and Al
were subsequently leached resulting in an abrupt rise of
effluent pH once more. Another cause for the higher pH of
column effluent than of input HCl may have been removal of
the solution from contact with soil matrix. As the effluent
flowed from soil columns and was exposed to the atmosphere,
the CC>2 partial pressure of the solution would decline and
the pH of the effluent would increase somewhat. During the
elution of 28 pore volumes, effluent pH was always observed
to be higher than pH of the input solution. As HCl
infiltrated the soil, H+ ions in the acid input solution
underwent cation exchange with basic cations located on soil
+3
exchange sites. Larger amounts of displaced Al were found
from both topsoil and subsoil columns receiving pH 3.9 HCl

101
solution as compared to columns receiving pH 4.9 HC1
solution. This can be explained by increased solubility and
mobility of complex aluminum as acidity increased.
Concentrations of Cations in Solution and Exchange Phases
Distributions of Ca2+, Mg2+, K+, Na+ and Al2+ in
solution and exchange phases for columns of Cecil topsoil
after leaching with pH 3.9 and 4.9 HC1 solutions are
presented in Tables 3-3 and 3-4, respectively. When an acid
solution is displaced through a soil column, cations with
higher affinities for exchange sites would be expected to
exchange strongly or tend to displace exchangeable cations
with lesser affinities from exchange sites (Helfferich,
1962; Mansell, 1983). For the case where equivalent
fractions of cations initially in the exchange phase are
approximately equal for all ion species, concentrations in
the solution phase of K+ and Na+ should be higher than
those of Ca2+, and Mg2+ and Al2 + . For the Cecil soil the
situation was more complicated since the initial composition
3+
of the exchange phase was relatively high in trivalent A1
2+ 2+
as well as divalent Ca and Mg species. For the exchange
2+ 2+ 3+
phase, concentrations of Ca , Mg , Al would be dominant
over monovalent species. Results in Tables 3-3 and 3-4
indicate that, in the corresponding solution phase, cation
concentrations were in the order K+ = Na+ = Al3+ > Ca2+ >
. 2+
Mg
Tables 3-5 and 3-6 present distributions of cation
concentrations in solution and exchange phases for columns

102
Table 3-3 Concentrations of cations in solution and
exchange phases for topsoil after leaching
with pH 3.9 HC1 solution
Depth Ca Mg K Na Al Sum
(cm) Solution ph^se
mmole(+) L
1.0
0.062
0.016
0.146
0.174
0.040
0.439
2.0
0.030
0.016
0.176
0.191
0.088
0.501
3.0
0.023
0.016
0.116
0.146
0.155
0.456
4.0
0.042
0.021
0.188
0.200
0.127
0.578
5.0
0.022
0.016
0.102
0.113
0.110
0.363
6.0
0.032
0.023
0.132
0.146
0.400
0.733
7.0
0.042
0.045
0.183
0.193
0.614
1.078
8.0
0.034
0.069
0.172
0.176
1.880
2.331
9.0
0.040
0.118
0.223
0.192
1.720
2.293
10.0
0.080
0.112
0.377
0.310
1.440
2.319
Depth
(cm)
Ca
Mg
K
Na
Al
Sum
soil
1.0
0.262
0.021
0.122
0.217
7.850
8.472
2.0
0.412
0.041
0.166
0.239
9.096
9.954
3.0
0.374
0.021
0.141
0.217
16.857
17.610
4.0
0.661
0.041
0.179
0.217
8.451
9.549
5.0
0.786
0.041
0.147
0.065
9.040
10.079
6.0
0.936
0.021
0.122
0.152
8.084
9.314
7.0
1.350
0.062
0.160
0.337
7.639
9.548
8.0
1.530
0.082
0.160
0.326
7.405
9.504
9.0
1.200
0.144
0.166
0.348
6.672
8.530
10.0
1.140
0.288
0.198
0.391
6.916
8.933

103
Table 3-4 Concentrations of cations in solution
and exchange phases for topsoil after
leaching with pH 4.9 solution
Depth Ca Mg K Na A1 Sum
(cm) Solution pha^e
mmole (+) L
1.0
0.030
0.021
0.125
0.130
0.172
0.478
2.0
0.032
0.037
0.104
0.113
0.942
1.228
3.0
0.032
0.066
0.122
0.113
1.800
2.133
4.0
0.023
0.058
0.128
0.130
1.300
1.638
5.0
0.040
0.075
0.158
0.139
1.260
1.672
6.0
0.027
0.058
0.164
0.135
1.200
1.584
7.0
0.020
0.074
0.180
0.152
1.570
1.996
8.0
0.025
0.090
0.196
0.141
2.130
2.583
9.0
0.020
0.025
0.156
0.146
0.297
0.644
10.0
0.042
0.054
0.179
0.163
0.724
1.162
Depth
Ca
Mg
K
Na
(cm) -
Exchange phase
mmole
( + ) Kg
1.0
0.714
0.074
0.151
0.178
2.0
0.883
0.123
0.123
0.074
3.0
0.883
0.173
0.133
0.061
4.0
0.883
0.181
0.133
0.087
5.0
0.863
0.181
0.136
0.078
6.0
0.843
0.214
0.166
0.087
7.0
0.973
0.123
0.237
0.054
8.0
0.963
0.206
0.225
0.109
9.0
0.913
0.197
0.171
0.056
10.0
0.893
0.197
0.200
0.165
A1 Sum
soil -
7.895
9.012
7.917
9.120
7.984
9.234
7.583
8.867
8.117
9.375
7.828
9.138
6.638
8.026
7.394
8.897
5.715
7.053
6.427
7.882

104
Table 3-5 Concentrations of cations in solution
and exchange phases for subsoil after
leaching with pH 3.9 HC1 solution
Depth Ca Mg K Na A1 Sum
(cm) Solution phase
mmole (+) L
1.0
0.048
0.013
0.122
0.141
0.008
0.332
2.0
0.055
0.021
0.152
0.154
0.013
0.395
3.0
0.115
0.033
0.247
0.313
0.004
0.712
4.0
0.122
0.033
0.192
0.248
0.004
0.599
5.0
0.085
0.029
0.136
0.239
0.010
0.499
6.0
0.078
0.026
0.125
0.231
0.009
0.469
7.0
0.112
0.037
0.178
0.313
0.006
0.646
8.0
0.092
0.029
0.162
0.267
0.007
0.557
9.0
0.094
0.037
0.290
0.278
0.009
0.708
10.0
0.096
0.040
0.270
0.240
0.007
0.652
Depth
Ca
Mg
K
Na
Al
Sum
V v^Jil)
1.0
0.661
0.082
0.243
0.217
12.520
13.723
2.0
3.220
0.514
0.262
0.207
9.785
13.988
3.0
5.610
1.050
0.313
0.207
8.084
15.264
4.0
7.190
1.280
0.320
0.196
6.738
15.724
5.0
6.540
1.360
0.301
0.196
6.850
15.247
6.0
7.420
1.560
0.371
0.174
6.282
15.807
7.0
7.570
1.540
0.390
0.207
6.516
16.223
8.0
7.580
1.540
0.454
0.207
6.505
16.286
9.0
6.560
1.440
0.460
0.217
5.871
14.548
10.0
6.860
1.520
0.576
0.196
5.560
14.712

105
Table 3-6 Concentrations of cations in solution and
exchange phases for subsoil after leaching
with pH 4.9 HC1 solution
Depth Ca Mg K Na A1 Sum
(cm) Solution phase
mmole (+) L
1.0
0.084
0.033
0.116
0.551
0.010
0.794
2.0
0.072
0.029
0.087
0.515
0.020
0.723
3.0
0.067
0.029
0.060
0.224
0.016
0.396
4.0
0.080
0.033
0.097
0.365
0.024
0.599
5.0
0.094
0.040
0.084
0.407
0.036
0.660
6.0
0.082
0.037
0.063
0.372
0.031
0.585
7.0
0.107
0.041
0.055
0.350
0.018
0.571
8.0
0.080
0.033
0.061
0.228
0.020
0.422
9.0
0.108
0.043
0.067
0.315
0.016
0.548
10.0
0.126
0.053
0.101
0.393
0.014
0.687
Depth Ca Mg K Na A1 Sum
(cm) Exchange phase
mmole (+) Kg soil
1.0
2.200
0.913
0.271
0.174
2.0
3.590
1.190
0.261
0.157
3.0
4.190
1.230
0.281
0.191
4.0
4.590
1.330
0.279
0.065
5.0
4.640
1.320
0.315
0.122
6.0
4.840
1.300
0.330
0.148
7.0
4.790
1.370
0.350
0.157
8.0
5.190
1.390
0.363
0.178
9.0
5.240
1.440
0.427
0.209
10.0
4.990
1.370
0.379
0.178
6.883 10.441
6.616 11.814
6.282 12.174
5.671 11.935
6.194 12.591
5.938 12.556
6.093 12.760
6.004 13.125
6.049 13.365
5.871 12.788

106
of subsoil after leaching with pH 3.9 and 4.9 HC1 solutions,
respectively. Concentrations of cations in the solution
phase were of the order Na+ > K+ = Ca^+ > Mg^+ > Al^ + and
3+ 2+ 2+ +
for the exchange phase of the order Al > Ca > Mg > Na
= K+. The orders of cation concentration in the solution
phase for the topsoil and subsoil were thus dissimilar, but
were similar for the respective exchange phases.
A comparison of exchangeable basic cations before and
after leaching were made for the topsoil and subsoil and the
two different treatments. Comparison of Table 3-2 with
Tables 3-3, 3-4, 3-5 and 3-6 revealed leaching losses of
3+
basic cations and increased concentrations of Al for both
soils during application of the HCl solutions. Leaching
3+
losses of basic cations and Al , and final amounts of
3+
exchangeable Al , were not strictly proportional to the
input H+ concentration for either the topsoil or subsoil
columns, though greater losses of basic cations were
observed for the pH 3.9 treatment. The pH 3.9 treatment
3+
resulted in slightly higher magnitudes of Al than did the
pH 4.9 treatment for in the topsoil and subsoil columns.
Estimated Selectivity Coefficients for Ion Pairs
Based on information given in Tables 3-3, 3-4, 3-5 and
3-6, binary selectivity coefficients as defined by equation
(3-2) were approximated for each pair of ion species. These
values are only approximations, since experimental
conditions involved multiple species of ions rather than a
simple binary system. Estimates of the selectivity

107
coefficients are presented in Tables 3-7, 3-8, 3-9 and 3-10
for each pair of cations at specific column depths for both
topsoil and subsoil after displacement with the two HCl
solutions. The average cation exchange capacity for each
column was obtained by summing up the 'sums' in the exchange
phase that appeared for each depth in Tables 3-3, 3-4, 3-5
and 3-6, respectively, and then averaging them.
Corresponding total solution-phase concentrations for each
column were likewise obtained by summing up the 'sums' in
the solution phase for each depth. Also, in the calculation
of selectivity coefficients, the higher valenced species for
any two cations was assumed to pseudo-saturate the soil
exchange sites. For example, for the calculated selectivity
coefficient KK_>A2 Tai)le 3-5 for topsoil, the exchange
reaction for these two specific cation species can be
described by the equation Al-(ads) + 3 K+ -> 3 K-(ads) +
3+
A1 , with the cation concentrations at specific depths
being taken from the table. In the calculation of
selectivity coefficients, if two cation species had the same
valence, the cation with the greater atomic weight was
assumed to pseudo-saturate the soil exchange sites. For
example, for the calculated selectivity coefficients KMg_>Ca
in Table 3-5 for topsoil, the exchange reaction for these
two specific cation species can be described by the equation
2+ 2+
Ca-(ads) + Mg -> Mg-(ads) + Ca , and cation
concentrations in solution and exchange phases for specific
depth can be taken from the table. Solution activity

108
Table 3-7 Topsoil selectivity coefficients as determined
after leaching with pH 3.9 HCl solution
Mg-->Ca
K-->Ca
Na-->Ca
Na-->K
K-->Mg
1
0.29335
0.18174E-01
0.40481E-01
1.4925
0.61120E-01
2
0.18077
0.70553E-02
0.12418E-01
1.3267
0.39029E-01
3
0.75109E-01
0.97137E-02
0.14524E-01
1.2228
0.12933
4
0.12798
0.63549E-02
0.82523E-02
1.1396
0.49655E-01
5
0.69720E-01
0.63531E-02
0.10183E-02
0.4004
0.91123E-01
6
0.30525E-01
0.31815E-02
0.40369E-02
1.1264
0.10423
7
0.42872E-01
0.26237E-02
0.10465E-01
1.9971
0.61199E-01
8
0.26389E-01
0.20953E-02
0.83075E-02
1.9912
0.79398E-01
9
0.41085E-01
0.20387E-02
0.12087E-01
2.4349
0.49622E-01
10
0.18000
0.21101E-02
0.12170E-01
2.4015
0.11723E-01
Average selectivity values
0.10718
0.59700E-02
0.12376E-01
1.5533
0.67642E-01
Na-->Mg
Al-->Ca
Mg-->A1
K-->Al
Na-->A1
1
0.13614
4761.6
0.55214E-05
0.35506E-04
0.11803E-03
2
0.68694E-
01
37.536
0.15738E-03
0.96728E-04
0.22587E-03
3
0.19337
23.566
0.17981E-04
0.19721E-03
0.36056E-03
4
0.64482E-
01
10.694
0.19602E-03
0.15492E-03
0.22925E-03
5
0.14606E-
01
1.355
0.25008E-03
0.43499E-03
0.27915E-04
6
0.13225
0.148
0.19225E-03
0.46656E-03
0.66683E-03
7
0.24409
0.044
0.17958E-02
0.64156E-03
0.51104E-02
8
0.31480
0.
15444E-02
0.11899E-01
0.24405E-02
0.19267E-01
9
0.29419
0.
52535E-02
0.13200E-01
0.12700E-02
0.18333E-01
10
0.06761
0.
72402E-01
0.80550E-01
0.36022E-03
0.49893E-02
Average !
selectivity values
0.15302
483.50
0.10826E-01
0.60982E-03
0.49328E-02

109
Table 3-8 Topsoil selectivity coeffients as determined
after leaching with pH 4.9 HC1 solution
Mg-->Ca
K-->Ca
Na-->Ca
Na-->K
K-->Ca
1
0.15043
0.10667E-01
0.13705E-01
1.1335
0.70911E-01
2
0.12198
0.89593E-02
0.27394E-02
0.55296
0.73449E-01
3
0.09647
0.76123E-02
0.18604E-02
0.49436
0.78906E-01
4
0.08007
0.48023E-02
0.19921E-02
0.64407
0.59975E-01
5
0.11313
0.60545E-02
0.25930E-02
0.65443
0.53520E-01
6
0.12076
0.58130E-02
0.23563E-02
0.63668
0.48137E-01
7
0.03417
0.62203E-02
0.45791E-03
0.27132
0.18206
8
0.05909
0.59719E-02
0.27082E-02
0.67341
0.10106
9
0.17471
0.45946E-02
0.57266E-03
0.35304
0.26298E-01
10
0.17483
0.10347E-01
0.84928E-02
0.90598
0.59182E-01
Average selectivity values
0.11256 0.71042E-02 0.37478E-02 0.63197 0.75350E-01
Na-->Mg
Al-->Ca
Mg-->A1
K-->A1
Na-->A1
1
0.91103E-01
0.88631
0.38408E-02
0.11703E-02
0.17042E-02
2
0.22458E-01
0.01999
0.90790E-01
0.59979E-02
0.10141E-02
3
0.19284E-01
0.00557
0.16127
0.89009E-02
0.10754E-02
4
0.24879E-01
0.00323
0.15917
0.58600E-02
0.15657E-02
5
0.22922E-01
0.02439
0.59357E-01
0.30165E-02
0.84548E-03
6
0.19513E-01
0.00837
0.21037
0.48441E-02
0.12502E-02
7
0.13402E-01
0.00089
0.44839E-01
0.16450E-01
0.32855E-03
8
0.45829E-01
0.00121
0.17083
0.13278E-01
0.40550E-02
9
0.32777E-02
0.02230
0.23916
0.20856E-02
0.91769E-04
10
0.48577E-01
0.04832
0.11060
0.47880E-02
0.35605E-02
Average selectivity values
0.31125E-01
0.10206
0.12502
0.66392E-02
0.15491E-02

110
Table 3-9 Subsoil selectivity coefficients as determined
after leaching with pH 3.9 HC1 solution
Mg-->Ca
K—>Ca
Na-->Ca
Na-->K
K-->Mg
1
0.45181
0.10565E-
-01 0.63078E-02
0.77267
0.23385E-01
2
0.42541
0.18616E-
-02 0.11321E-02
0.77982
0.43760E-02
3
0.65423
0.12097E-
-02 0.32949E-03
0.52189
0.18491E-02
4
0.66015
0.17322E-
-02 0.38949E-03
0.47419
0.26239E-02
5
0.61230
0.23342E-
-02 0.32048E-03
0.37054
0.38122E-02
6
0.62193
0.33944E-
-02 0.21863E-03
0.25379
0.54578E-02
7
0.61580
0.26102E-
-02 0.23781E-03
0.30184
0.42387E-02
8
0.65112
0.35146E-
-02 0.26898E-03
0.27664
0.53978E-02
9
0.55946
0.13292E-
-02 0.32188E-03
0.49210
0.23759E-02
10
0.53739
0.23357E-
-02 0.34229E-03
0.38281
0.43464E-02
Average
selectivity values
0.57896
0.30887E-
-02 0.98689E-03
0.46263
0.57862E-02
Na-->Mg
Al->Ca
Mg-->A1
K-->A1
Na-->A1
1
0.13961E-01
26816.
0.34395E-05 0.
66319E-05
0.30593E-05
2
0.26611E-02
72.997
0.10547E-02 0.
94013E-05
0.44582E-05
3
0.50364E-03
773.49
0.36202E-03 0.
15129E-05
0.21505E-06
4
0.59001E-03
304.80
0.94389E-03 0.
41293E-05
0.44030E-06
5
0.52340E-03
27.830
0.82487E-02 0.
21377E-04
0.10875E-05
6
0.35153E-03
15.629
0.15392E-01 0.
50024E-04
0.81771E-06
7
0.38618E-03
121.03
0.19294E-02 0.
12122E-04
0.33335E-06
8
0.41310E-03
46.725
0.59079E-02 0.
30482E-04
0.64535E-06
9
0.57535E-03
35.173
0.49785E-02 0.
81711E-05
0.97375E-06
10
0.63695E-03
51.489
0.30140E-02 0.
15732E-04
0.88254E-06
Average
selectivity values
0.20602E-02
2826.5
0.41835E-02 0.
15958E-04
0.12913E-05

Ill
Table 3-10 Subsoil selectivity coefficients as determined
after leaching with pH 4.9 HCl solution
Mg->Ca
K-->Ca
Na-->Ca
Na->K
K-->Mg
1
1.0571
0.10071E-01
0.18402E-03
0.13517
0.95277E-02
2
0.83329
0.87928E-02
0.90796E-04
0.10162
0.10552E-01
3
0.68700
0.17035E-01
0.56657E-03
0.18237
0.24796E-01
4
0.70282
0.69391E-02
0.26874E-04
0.06223
0.98732E-02
5
0.67556
0.13804E-01
0.87994E-04
0.07984
0.20434E-01
6
0.59744
0.22818E-01
0.13039E-03
0.07559
0.38194E-01
7
0.74461
0.43823E-01
0.21775E-03
0.07049
0.58853E-01
8
0.64961
0.26035E-01
0.45399E-03
0.13205
0.40077E-01
9
0.69344
0.41166E-01
0.43954E-03
0.10333
0.59365E-01
10
0.65642
0.17224E-01
0.25094E-03
0.12070
0.26240E-01
Average selectivity values
0.72973
0.20771E-01
0.24489E-03
0.10634
0.29791E-01
Na-->Mg
Al->Ca
Mg-->A1
K-->Al
Na-->A1
1
0.17408E-03
540.47
0.21853E-02
0.43475E-04
0.10737E-06
2
0.10896E-03
18.528
0.31230E-01
0.19155E-03
0.20100E-06
3
0.82470E-03
13.935
0.23269E-01
0.59562E-03
0.36127E-05
4
0.38238E-04
5.8117
0.59736E-01
0.23978E-03
0.57790E-07
5
0.13025E-03
5.1617
0.59731E-01
0.71390E-03
0.36332E-06
6
0.21824E-03
3.6995
0.57643E-01
0.17921E-02
0.77406E-06
7
0.29243E-03
26.964
0.15311E-01
0.17667E-02
0.61877E-06
8
0.69886E-03
6.7631
0.40534E-01
0.16153E-02
0.37196E-05
9
0.63386E-03
27.173
0.12271E-01
0.16023E-02
0.17678E-05
10
0.38228E-03
54.483
0.51913E-02
0.30626E-03
0.53854E-06
Average
selectivity values
0.35019E-03
70.299
0.30710E-01
0.88669E-03
0.11761E-05

112
coefficients were assumed to be unity for all cations specie
in the calculations.
After leaching, exchangeable Al3 + comprised 75-95% of
the total exchangeable cations in topsoil columns for the pH
3.9 HCl treatment and 80-86% for the pH 4.9 treatment.
3+
These values greatly exceed the 48% of Al initially
present on the soil exchange phase. The acid leaching
3 +
processes obviously resulted in more exchangeable Al as a
consequence of acid dissolution of soil clay minerals.
3+
Exchangeable Al comprised about 40-60% of total
exchangeable cations in the subsoil after leaching with both
3+
treatments of HCl solution, where as Al initially
accounted for only 32% of total exchangeable cations. Hence
acid leaching also resulted in forming more exchangeable
Al3+ in the subsoil column. However, the magnitudes were
not as large as observed for the topsoil. These
3 +
observations suggest that, of all the cation species, Al
was the most preferred ion for exchange sites of both
topsoil and subsoil, and also dominant in terms of
exchangeable and nonexchangeable forms for this acid Cecil
3+ 2+
soil. Calculated selectivity coefficients for Al -> Ca
3+
revealed a significant preference of exchange sites for Al
2+
over Ca in the subsoil but the opposite in the topsoil.
Overall, the approximate values of selectivity coefficients
for the same ion pair varied from depth to depth, and were
highly dependent upon the local concentrations of cations in

113
solution and on the exchange phase as well as upon cation
valence and pH of the applied HCl solution.
If one assumed the input solution concentration for H+
to be equal to the total solution concentration for all
cation species in the soil column and the cation-exchange
capacity of the soil column to be invariant with depth and
time then, by taking differences between input solution
concentrations and the sum of solution-phase concentrations
in Tables 3-3, 3-4, 3-5 and 3-6, the solution-phase
concentrations of H+ can be obtained for each treatment and
depth of topsoil and subsoil. In the same manner,
subtracting the sum of exchangeable cations at each depth in
Tables 3-3, 3-4, 3-5 and 3-6 from the appropriate choice of
CEC obtained from Table 3-2, gives the exchange-phase
concentrations of H+ for each depth of topsoil and subsoil
in the different treatments. Therefore, the selectivity
coefficients between basic cations and H+ can be calculated.
Calculations were not performed initially for H+ versus
basic cations, for the reason discussed earlier by
Krishnamoorthy and Overstreet (1950) that the exchangeable
hydrogen in clays and soil colloids is not completely
disassociated. Thus, conventional ion exchange formulations
are not valid for calculating these selectivity
coefficients. Obtaining such selectivity coefficients for
H+ is especially difficult for Cecil topsoil and subsoil,
which contain substantial amounts of Fe and Al hydrous
oxides as well as of interlayer-hydroxy vermiculite, which

114
each have pH-dependent characteristics. Poorly-crystalline
clay minerals that are coated with Al compounds act as sinks
for H+ by transforming the soil exchange phase from H+- to
3+
Al - saturated (Thomas and Hargrove, 1984). Hydrolysis of
3+ +
Al in the soil then causes the formation of H during
extraction. This so-called 'exchangeable' H+ is a result of
hydrolysis and really does not exist as such on the exchange
sites of soil clay minerals or organic matter (Kissel et
al., 1971). Therefore, the ion-exchange behavior of H+ in
acid soil is not easily described in a meaningful way
(Thomas and Hargrove, 1984).
Charge Balance of Major Cations for Topsoil and Subsoil
The charge balance of major cations in columns of
topsoil and subsoil which received two HCl solutions with
different pH values are given in Tables 3-11 and 3-12,
respectively, with units of mmole(+). The overall charge
balance of major cations in each soil column can be
described by the following relationship:
Total H+ added as HCl + All cations initially present on
soil exchange sites
(1) (2)
= Total H+ exported or leached in the column effluent
(3)
+ Total cation exported or leached in the column effluent
(4)
+ All cations still remaining in the soil columns in the
exchange and solution phases after leaching with the
HCl solutions.
(5)
[3-5]

115
where the first term (1) was obtained from the product of
the concentrations of input solution H+ (mmole(+) L and
the total volume of input solution (1). The second term (2)
was obtained as the cation exchange capacity (mmole(+) kg 1)
of a given soil times the weight of soil (kg) residing in
the column. The third term (3) was obtained by integrating
breakthrough curves of effluent pH and converting mmole(+).
The fourth term (4) was obtained by integrating
breakthrough curves for each cation species and then summing
for all species. The last term (5) accounted for remaining
cations in the solution and exchange phases. Total charge
of cations in the solution phase was taken as the sum of the
charge of each individual cation as obtained from the
product of its cation concentration, volumetric water
3-3
content (MM ) of the soil and total volume of soil (L).
In the same manner, the total charge of cations in the
exchange phase was taken as the sum of the charge of each
individual cation on the exchange phase obtained using the
concentrations of cations (mmole(+) kg ^) as obtained from 1
M NH^OAc extraction multiplied by the weight of soil in the
columns (kg) to give the masses of individual cation
species.
Using the previously stated concept of charge balance,
the initial charge (total input of H+ ions and cations
initially present in the column) and final charge (total H+

116
and cations exported + cations still remaining in the
column) were 2.733 mmole(+) and 2.086 mmole(+),
respectively, for pH 3.9 input solution and topsoil (Table
3-11). Overall, charge balance error was - 7.5% for the pH
3.9 treatment, indicating a loss of 0.647 mmole(+) of charge
during application of the HC1. The corresponding total
charge balances were 2.087 mmole(+) and 1.869 mmole(+) for
input and output solutions, respectively, for pH 4.9 input
solution and topsoil. Overall charge balance error was -
10.5% for treatment pH 4.9, also indicating a loss in charge
during application of HCl to the soil.
From Table 3-12 for the subsoil column the total charge
balances of major cations for the initial column and after
leaching were 3.446 and 2.702 mmole(+) for the pH 3.9
treatment, respectively. The corresponding charge balance
error was - 28% indicating a sizeable loss in charge. For
pH 4.9 treatment, values of 3.285 and 2.197 mmole(+) were
observed for charge balance of major cations, respectively
for the initial column and after leaching. The
corresponding charge balance error was - 33%, also
indicating a sustantial loss in charge.
For all of the columns, outputs of cation charge were
less than inputs of charge for topsoil and subsoil,
indicating a net loss of charge. Sources of charge-balance
error can be attributed to the difficulty in precisely
determining H+ in the solution and exchange phases, to the
3+
fact that A1 analyses were not specific for A1 forms, and

117
Table 3-11 Charge balance of cations for columns of topsoil
Topsoil pH
3.9 (mmole(+))
2 +
.. 2+
, 3 +
H
Ca
Mg
K
Na
Al
Initial cations
0.278
0.043
0.121
0.451
1.162
Total input 0.202
Final #
1-820
1.970
7.920
8.040
2.870
solution phase
(*10 J)
Final #
0.150
0.012
0.027
0.044
1.527
exchange phase
Total 0.07
0.058
0.064
0.069
0.025
0.110
output in effluent
Topsoil pH
4.9 (mmole(+))
„ 2+
, 3 +
H
Ca
Mg
K
Na
Al
Initial cations
0.279
0.044
0.122
0.454
1.170
Total input 0.018
Final #
1.300
2.460
6.730
6.070
0.051
solution phase
(*10 J)
Final #
0.154
0.029
0.029
0.017
1.275
exchange phase
Total 0.068
0.040
0.043
0.064
0.023
0.017
output in effluent
# : undetermined

118
Table 3-12 Charge balance of cations for columns of subsoil
Subsoil pH
3.9 (mmole(+))
„ 2+
,, 3+
H
Ca
Mg
K
Na
A1
Initial cations
1.332
0.331
0.121
0.424
1.060
Total input 0.198
Final #
4,850
1.610
0.010
0.013
4.160
solution phase (*10
“3)
Final #
0.896
0.180
0.056
0.031
1.131
exchange phase
Total 0.006
0.230
0.090
0.040
0.030
0.001
output in effluent
Subsoil pH 4.
9 (mmole(+))
„ 2 +
2 +
,, 3 +
H
Ca
Mg
K
Na
Al
Initial cations
1.332
0.331
0.121
0.424
1.060
Total input 0.017
Final #
4,730
1.950
4.150
1.950
1.080
solution phase (*10
3)
Final #
0.670
0.200
0.049
0.024
0.933
exchange phase
Total 0.006
0.170
0.061
0.034
0.035
0.001
output in effluent
#: undetermined

119
to the fact that not all ion species (i.e. NH+4) were
included in the analyses. Essentially all of the column
effluent and soil-solution phase had a pH of less than 5.6
to 6.0, as shown in Fig. 3-1 and 3-5. Another reason could
be due to experimental error to soil chemical reactions that
act as sinks for applied H+, and to chemical dissolution of
3+
A1 from nonexchangeable form in oxides and clay minerals.
The overall charge balance of major cations in each
soil column was described in equation [3-5]. A sixth term
would include sinks for H+, and a seventh term would include
3+
a source for A1 by acid dissolution of soil oxides and
clay minerals. Although these two terms were not measured
in this investigation, they are important to the overall
balance. The reported charge-balance values are thus in
error, but do give apparent charge-balance values.
Conclusions
Cecil soil is known to be a highly weathered acid soil.
The principal soil minerals observed in Cecil topsoil and
subsoil were kaolinite, interlayer-hydroxy vermiculite, and
quartz. Gibbsite was also observed in the subsoil. A "salt
effect" caused the first few effluent samples to be
uncommonly low in pH and high in concentrations of several
cation species. Application of HC1 solutions with two
different pH values to the Cecil soil resulted in larger
quantities of cations being leached by pH 3.9 solution
relative than of pH 4.9. The reverse effect was observed
3+
for quantities of Al exported, however. Concentrations of

120
basic cations in the exchange phase were decreased and
3+
significant hydrolysis of Al in the soil occurred during
leaching with HCl. This effect was more pronounced for
topsoil that received pK 3.9 solution. For the subsoil,
only the end of the column that received acid input solution
showed significant losses of cations and dissolution of
3+
Al . Generally, exchange-phase concentrations of basic
cations as determined with NH^OAc extraction before and
after leaching with HCl solutions were decreased for both
soils. The percent of base saturation before HCl
application was 52%, for the topsoil. After HCl
application, base saturation wass 0.1% and 1.5% for pH 3.9
and 4.9 treatments, respectively. For the subsoil, base
saturation was initially 68%. After acid application, base
saturation was 5.4% and 4.4% for the pH 3.9 and 4.9
treatments, respectively.
The distribution of cations in the exchange phase
followed the order Al3+ > Ca2+ > Mg2+ > K+ = Na+ for both
3+
soils. Al was the preferred ion on the exchange sites, as
expected due to its large valence and large equivalent
fraction initially on the exchanger. In the solution phase,
the distribution of cation concentrations followed the order
K+ ~ Na = Al3+ > Ca2+ > Mg2+ for topsoil and Na+ > K+ * Ca2+
2+3+ . . .
>Mg > Al for subsoil. The exchange selectivity
coefficients for each pair of cations as estimated from
distributions of ion concentrations in solution and on
exchange phases at specific column depths varied with depth

121
for both soils and were highly dependent upon the cation
concentrations in solution and on the exchange phase as well
as upon cation valence and upon the pH of the applied HC1
solution.
Greater quantities of basic cations were leached from
soil columns that received pH 3.9 solution than of pH 4.9.
. 2+ 2+
Specifically, the total losses of divalent Ca , and Mg
ions from the topsoil were 0.32 and 0.23 mmole(+),
respectively, during application of pH 3.9 and 4.9 HC1
solutions. For the subsoil these losses were only 0.12 and
0.08 mmole(+) for pH 3.9 and 4.9 HCl treatments,
respectively. Application of HCl solution definitely
accelerated leaching losses of cation nutrients from the
Cecil soil. Charge-balance errors ranged from -10 to -33%
and were likely due to undetermined H+ in solution and on
the exchange phase for the soil, as well as to negatively-
charged surfaces of Fe oxides, experimental error, soil
chemical reactions that act as sinks for applied H+, and
3+
acid dissolution that provides a source for Al to enter
into exchange reactions though the Column of Cecil soil
received solution with a ten-fold difference in HCl
concentration, the total quantities of basic cations removed
differed by less than two-fold. Therefore, leaching by the
HCl solution not only involved cation exchange between
monovalent, divalent, and trivalent ions, but also
apparently involved the dissolution of gibbsite and other
Al-bearing compounds (Sardin et al., 1986).

122
Assuming an annual rainfall of 120 cm yr-1, columns of
topsoil and subsoil received 1.16 and 1.11 times the annual
rainfall equivalent during a period of only 7 days in these
study, such laboratory conditions are extreme compared to
field conditions, and greatly enhanced leaching of basic
soil cations. In nature, rainfall occurs during periodic
events separated by sometimes long periods without rain.
Such periodical wetting and drying of the soil tends to
limit cation exchange and cation transport, and allows time
for chemical reactions that inhibit the extent of leaching
of basic cations. Under forested conditions, it is possible
that Cecil soil could be largely depleted of most of the
2+ 2+
basic cations (Ca and Mg ) on exchange sites of the
topsoil if the annual quantity of acid rain was applied
continuously over a period of a few weeks to a few months.
Under such extreme conditions, application of lime and
fertilizer might be necessary in order to maintain the
production of forest located on Cecil soil.

CHAPTER IV
CATION LEACHING DURING CONTINUOUS DISPLACEMENT
BY HYDROCHLORIC ACID SOLUTION THROUGH COLUMNS OF
CHEMICALLY-PRETREATED CECIL SOIL
Introduction
Leaching of cations and movement of organic and
inorganic anions in response to acid rain deposition in
forest soils has been investigated by Mollitor and Raynal
(1982) and Ulrich et al. (1980). Cation exchange is
recognized as one of the important soil processes which
control detrimental effects of acid rain upon the nutrient
status of forest soils (Wiklander, 1975; Reuss, 1983; Cosby
et al., 1985a, 1985b). Experimental results have shown that
neutral salts added to soil-water suspensions or to dilute
solutions percolating through soil columns tend to decrease
acidification of the soil (Wiklander, 1975).
Very few published papers report investigations of the
leaching of soil cations during the displacement of aqueous
acid solutions through columns of soil where the exchange
sites have initially been saturated with a single specific
. . + 2+ 2+
cation species such as K , Ca , or Mg . Such an
investigation was performed during the research reported in
this chapter. The advantage of using chemically-pretreated
soil is that the soil system involves fewer species of
cations and thus the data are more easily interpreted.
123

124
The first objective of this study was to determine the
cation exchange capacity for chemically-pretreated Cecil
topsoil and subsoil, and a second objective was to determine
the influence of input solution pH upon cation leaching
during continuous displacement of HC1 solution through
hand-packed columns of chemically-pretreated Cecil topsoil
and subsoil, respectively. A third objective was to
determine the distribution of cation concentrations in
solution and exchange phases of each pretreated soil column
after leaching with HC1.
Cation-Exchange Reaction
Saturation Mechanisms for Soil Exchange Sites with a
Single Cation Species
Most mineral soils contain a mixture of colloids having
constant and variable charge-surfaces (Dixon and Weed,
1977), even though one type might tend to dominate over
others. Soils located in the Southeastern United States
which are highly weathered have properties commonly
dominated by sesquioxides of Fe and Al with their
pH-dependent charge, by 1:1 kaolinite-type crystalline clay
minerals and by 2:1 interlayer-hydroxy vermiculite minerals.
Soil organic matter also provides an important contribution
to the pH-dependent charge of such soils.
When a neutral-salt solution (examples: KC1, MgCl2, or
CaCl2) is added to a soil it causes a cation-exchange
reaction involving the transfer of multiple species of
cations between solution and exchange phases. Cation-

125
exchange sites in the soil result partially from broken
edges of the silica-alumina crystalline units, which give
rise to unsatisfied electrostatic charge and which is
balanced by exchangeable cations. Broken-edge charge is
often a source of variable charge. In kaolinite minerals,
broken edges are the major source for cation-exchange
capacity but, for vermiculite, broken edges account for only
a relatively small portion of the CEC. Isomorphous
substitutions of Al3+ for Si^+, and of Mg^+ for Al3+, that
occur within the crystalline lattice structure of clay
minerals result in unbalanced electrostatic charge that is
normally balanced by exchangeable cations. Such charge is
referred to as permanent (pH-independent) charge.
Exchangeable cations resulting from lattice substitution are
found mostly on cleavage surfaces of vermiculitic clay
minerals (Grim, 1968). In general, the order of replacement
of exchangeable-cation species for soil exchange sites is
+ + + 7 + 7+ 1 +
Na < NH4 < K < Mg < Ca < Al .
For pH-dependent charge colloids such as hydrous Al and
Fe oxides, organic matter and some clay minerals, both
active and potential acidic groups occur along with basic
groups. Active acid groups are directly equilibrated with
soil-solution cations, whereas potential acid groups are
activated only by an increase in the soil pH. Basic groups
can acquire a positive charge by uptake of H+ ions from the
soil solution. The positive charge is balanced by anion
. 2-
species such as Cl , NC>3 , SC>4 ,
H2PC>4 etc. Thus, such

126
soils are amphoteric, exhibiting both acidic and basic
properties and undergoing exchange with cations as well as
anions. Also, if neutral salt solution is added to a soil,
cations from the salt replace part of the exchangeable H+
3 +
and Al present on the soil exchange phase and thereby
increase the base saturation of the soil in proportion to
the magnitude of the exchange acidity. The resulting
acidity in turn decreases the pH of the soil solution. With
continuous addition of salt solution the initial acidity in
the solution will gradually be leached, resulting in a
corresponding rise of soil pH (Wiklander, 1975). Thus, the
higher the normality of the input neutral salt solution, the
more complete the saturation of exchange sites with a
specific cation species.
Mechanisms of H+ Replacement of Exchangeable cations on
Soil Exchange Sites
When an acid soil is transformed from (H+Al)-soil to
one saturated with a specific cation species (examples: K+,
2+ 2+
Mg , or Ca ), the acid groups in the soil are successively
neutralized and the base saturation of the soil is
increased. During subsequent removal of basic cations by
leaching with an acid solution, the replacement efficiency
of H+ for basic cations on the soil can be expressed by the
ratio 6M/6H (Wiklander and Andersson, 1972), where 6M is the
number of equivalents of cations removed and 6H is the
number of equivalents of H+ added. A single-species
cation-saturated soil always gives a high degree of base

127
saturation and increases the ratio 6M/6H. Exchangeable
2+ 2+ 4" *
cation nutrients such as Ca , Mg and K are easily
3+ .
replaced and lost by leaching. Trivalent A1 ions,
however, are much more resistant to removal by leaching,
with very concentrated salt solutions being required to
remove them from the exchange phase of the soil.
With continuous input of acid solution to soil, H+ ions
have been postulated to successively replace cations from
cation-saturated soil in two separate steps (Wiklander and
Andersson, 1972); this can be represented as:
MA + H+ -> HA + M+ [4-1]
+ 2+ 2+
where M is a given cation species (K , Ca , Mg ), A is the
variable charge of the soil, HA is a weak acid group in the
soil and MA represents the soil saturated with cation M.
Due to the high bonding energy of H+ in HA, which produces a
high 6M/6H ratio, the exchange will be practically complete
before the beginning of the next step of cation desorption
MP + H+ -> HP + M+ [4-2]
where P is the permanent charge, MP is from isomorphous
substitution, and HP behaves as a strong acid. This means
that H+ is weakly bound and has a low replacing power for
ion species M. Natural occurrence of large quantities of
3+
A1 as an exchangeable ion in most acid soils results in a
decrease of the replacing efficiency of H+ for cation
species M. With continuous application of H+ ions in
+ 3+
solution, H and Al concentrations will increase in the

128
soil solution, will cause more leaching of soil cations, and
will lower the content of exchangeable cations.
Materials and Methods
Preparation of Pretreated Soil
Cecil jtopsoil and subsoil materials used in this study
were obtained from the same site as described in chapter
two. Cylindrical columns used to house the soil samples
were constructed from acrylic plastic with of 0.3 m length
and 0.0832 m inside-diameter. The top and bottom endplates
obtained from commercially-available Tempe cells (Soil
Moisture Equipment Co., Santa Barbara, California) were
fitted to each column. Soil was held in each column by a
fine nylon mesh and a Whatman no.42 filter paper. Each
column was then placed in a vertical position and soil was
sequentially packed by adding increments of soil and tapping
the side of the column until it was full in order to obtain
the desired average bulk density. The endplates were
mounted onto ends of the column in order to hold the soil in
place. Using the procedure as stated, three soil columns
were prepared for topsoil and another three for subsoil.
Stock solutions of 10 mmole( + ) L ^ KCl, MgCl2 and CaCl2 were
prepared, respectively. Three topsoil columns were then
saturated with 1 mmole(+) L ^ KCl, MgCl2 and CaCl2 diluted
stock solutions by application to the bottom of each soil
column, respectively, in a vertical position. A
four-channel peristaltic pump as described in chapter two
was used to deliver each of the stock solutions at a rate of

129
1.10 cm h 1 (± 3%) Darcy velocity to each column. A check
for concentrations of cations in the column effluent was
made periodically. A conventional way to estimate if the
soil exchange sites are saturated with a specific cation is
by monitoring concentrations of the specific cation in the
effluent with time. If the cation concentration in the
effluent becomes equal to that of the input solution then
the soil exchange sites are commonly considered to be
saturated with that cation species. Such a technique,
however, is not without difficulties, particularly if the
exchange sites initially contained highly-preferred species
of cations. In this investigation concentrations of a
specific cation in the effluent reached 99% of the input
solution concentration after about 3-4.5 pore volumes of
elution, but very small concentrations of other ion species
remained even after leaching of the column for a month or
more. After the flow was terminated, the columns were
leached with 1.5 liters of 95% ethanol to remove all soluble
salts. Soil was then removed from each column, air-dried,
ground, passed through a 2-mm sieve and stored in large
plastic bottles for future use. Three columns of subsoil
were prepared similarly to the aformentioned procedure for
topsoil columns. Therefore, Ca-saturated, Mg-saturated,
K-saturated topsoil and subsoil materials were obtained.
Pretreated mixed-topsoil and mixed-subsoil were obtained by
carefully mixing equal weight ratios (1:1:1 for Ca:Mg:K) of
Ca-saturated, Mg-saturated, and K-saturated soil materials.

130
Concentrations of exchangeable cations in all of the treated
soils were determined by extraction with 1 M neutral NH^OAc
(Thomas, 1982).
Soil Column Preparation and Procedure for Displacing HC1
Solution Through Columns
Each soil column consisted of a stack of 1-cm thick
_2
acrylic plastic (plexiglass) rings with 3.72 x 10 m
inside-diameter. Water-proof, acid-resistant electrical
tape was tightly wrapped around the outside of the rings to
insure that lateral leakage of water did not occur during
runs. Each column had dimensions of 0.2 m length and 0.0375
m inside diameter, giving a total internal volume of 2.21 x
-4 3
10 m . The soil was held in the columns by a fine nylon
mesh and a piece of Whatman no.42 filter paper placed over a
thin plastic disc with small holes distributed over its
surface in each of the inflow and outflow endplates. A
check for water leaks was made prior to packing the soil
into a given column. Each column was then placed in a
vertical position and sequentially packed by slowly adding
incremental quantities of soil and tapping the side of the
column until a desired soil bulk density was obtained.
After packing, the entire soil column was mounted between
two wooden boards for support and fastened with four
threaded steel rods to hold the soil and rings in place.
Duplicate soil columns were constructed for each chemically
pretreated and mixed soil. Columns included Ca-saturated
topsoil, Mg-saturated topsoil, K-saturated topsoil,

131
Ca-saturated topsoil, Mg-saturated subsoil, K-saturated
subsoil and mixed subsoil, and mixed topsoil for a total of
16 soil columns. Miscible-displacement experiments were
performed for one of the pretreated and mixed soil columns
using pH 3.9 displacing HCl solution and for another column
using pH 4.9 HCl displacing solution. Darcy velocities
ranged from 1.09 x 10 ^ to 1.16 x 10 ^ (± 2%) mh "*■. A
four-channel peristaltic pump as described in an earlier
chapter was used to deliver the applied solution into the
bottom of each soil column. Effluent from the top of the
column was collected by the fraction collector described
previously and effluent samples were stored in a
refrigerator for later analysis. After termination of acid
application to a given column, the pore volume was obtained
from the mass difference between wetted and air-dried soil
columns. Corrections were made to cumulative effluent
volume for amounts of solution held inside each of the
endplates. Initially the soil was air-dry but water
saturation soon was approached. Eventually the soil columns
reached steady-state water flow, which was maintained
thereafter. Experimental measurements of dispersion
coefficient for each column were not conducted, but were
assumed using the magnitude of the dispersion coefficients
for the topsoil and subsoil as given in chapter two. Since
all of the soil columns have the same length, the deviation
of bulk density was within ± 3 and ± 1% for topsoil and
subsoil, respectively. Moreover, the deviation for the

132
Darcy velocity was within ± 3 % for most columns. Large
differences with regard to the dispersion coefficients
between soil columns were assumed absent due to the small
variations in bulk density and Darcy flux.
Method for Dissection, Extraction and Chemical Analysis of
Soil Columns
After liquid flow was terminated, each column was
equilibrated overnight to insure that the whole system was
at equilibrium. The column was placed in the vertical
position, and the tape on the outside of the column was
removed carefully. As the outflow endplate was removed, a
piece of parafilm was placed over the soil cross section and
a small-diameter steel wire was used to slice the
consecutive rings of the column. Each section of soil then
was carefully placed onto another piece of prepared parafilm
before being packed into a prenumbered small centrifuge tube
with a predrilled small hole in the bottom. A Whatman no.42
filter paper was cut and placed inside the tube over the
hole in the bottom of the tube. Then each small tube was
transferred into a large-size centrifuge tube with a glass
bead separating the extraction solution from the small
centrifuge tube, and spun at 4000 rpm for 30 minutes. The
soil sample was then removed from the small centrifuge tube
and placed into a plastic weighing boat. The weight of the
wet soil was recorded, soil in the weighing boat was
air-dried, and the air-dry weight was recorded. The
concentrations of basic cations in the exchange phase were

133
obtained extraction with neutral 1 M NH^OAc (Thomas, 1982).
Unbuffered 1 M KCl (Thomas, 1982) was used to obtain
3+
exchangeable Al . Concentrations were corrected for
entrapped equilibrium solution near the exchange sites.
• 2+ 2+ ^ *
Concentrations of Ca , Mg , K , and Na in the column
effluent, solution and exchange phases of each soil column
were analyzed by an atomic absorption spectrometer as
3+
described in previous chapters. The Al was determined by
optical emission spectroscopy (inductively coupled argon
plasma, ICAP) on a unit located in the Soil Testing
Laboratory, Soil Science Department, University of Florida.
Results and Discussion
Initial exchangeable cations in nontreated topsoil and
subsoil are presented in Table 4-1. The soil parameters
used for the miscible displacement experiments are presented
in Tables 4-2, 4-3 and 4-4 for chemically-pretreated
topsoil, pretreated subsoil, and mixed topsoil and subsoil,
respectively.
From Tables 4-2 through 4-4, the deviation of the bulk
density, volumetric water content and pore-water velocity of
hand-packed treated topsoil and subsoil columns were within
± 3 %, respectively. Similar deviations for the bulk
density, volumetric water content and pore water velocity
were also found for hand-packed mixed subsoil and topsoil
columns.

134
Table 4-1 Concentrations of exchangeable cations for
nontreated Cecil topsoil and subsoil
Soil
Exchangeable-cations CEC-
(mmole(+) Kg soil) (mmole(+) Kg" soil)
Ca
2+
Mg
2+
K
Na
Al
3 +
Topsoil 1.60 0.30 0.70 2.60 6.70 11.90
Subsoil 8.80 2.20 0.80 2.80 7.00 21.60
Table 4-2 Soil parameters for chemically pretreated topsoil
columns after leaching with HC1 solutions
Parameter Ca-topsoil Ca-topsoil Mg-topsoil
Input solution pH
3.9
4.9
3.9
Bulk density (MG M x)
1.61
1.64
1.64
Volumetric water __
0.37
0.38
0.37
content (MJ M ;
Dispersion ^
.. 3.03*10-4
3.03*10~4
3.03*10
coefficient (Mx h
_1)
Pore velocity (M h ;
0.030
0.028
0.030
Pore volume (L)
0.082
0.083
0.082
Column length (M)
0.20
0.20
0.20
Input concentration
-.0.125
0.0125
0.125
of H (mmole^+) L
)
Total amount of H
0.284
0.029
0.277
applied (mmole(+)
L_1)
Total no. of pore
26
28
26
volumes collected
Parameter
Mg-topsoil K-topsoil K-topsoil
Input solution pH __
Bulk density (MG M X)
Volumetric water
content (MJ M J)
Dispersion ~
coefficient (Mx
Pore velocity (M h x)
Pore volume (L)
Column length (M)
Input concentration
of H (mmole^_+) L
Total amount of H
applied mmole(+)
Total no. of pore
volumes collected
4.9
3.9
1.61
1.65
0.38
0.37
13.03*10-4
X)
3.03*10
0.029
0.034
0.083
0.081
0.20
0.20
.0.0125
i)
0.125
.025
0.348
27
34
4.9
1.64
0.37
3.03*10
0.028
0.083
0.20
0.0125
0.029
27

135
Table 4-3 Soil parameters for chemically pretreated subsoil
columns after leaching with HC1 solutions
Parameter Ca
.-subsoil
Ca-subsoil
Mg-subsoil
Input solution pH ,
3.9
4.9
3.9
Bulk density (MG M J)
1.47
1.47
1.41
Volumetric water __
0.42
0.42
0.44
content (MJ M J)
Dispersion y
11.85*10‘4
1.85*10"4
1.85*10-4
coefficient (M^ h
1)
Pore velocity (M h i)
0.023
0.021
0.024
Pore volume (L)
0.092
0.093
0.098
Column length (M)
0.20
0.20
0.20
Input concentration
.0.125
0.0125
0.125
of H (mmole^t) L
)
Total amount of H
0-271
0.024
0.271
applied (mmole(+)
L 1)
Total no. of pore
23
23
21
volumes collected
Parameter Mg
-subsoil
K-subsoil
K-subsoil
Input solution pH
4.9
3.9
4.9
Bulk density (MG M J)
Volumetric-.water
1.42
1.39
1.37
content (MJ M J)
0.44
0.47
0.47
Dispersion _
-4
-4
-4
coefficient (Mz h )
1.85*10 *
1.85*10 H
1.85*10 *
Pore velocity (M h x)
0.0248
0.0232
0.0228
Pore volume (L)
0.0977
0.1041
0.1034
Column length (M)
Input concentration
0.20
0.20
0.20
of H mmole(+) L
0.0125
0.125
0.0125
Testal amount of -
H applied mmole(+) L
Total no. of pore
0.024
0.271
0.026
volumes collected
21.1
19.3
18.3

136
Table 4-4 Soil parameters for mixed soil columns after
leaching with HC1 solutions
Parameter Mixed-cation topsoil Mixed-cation topsoil
Input solution pH 3.9 4.9
Bulk density (MG M J) 1.68 1.66
Volumetric water 0.36 0.36
content(MJ M j ,
Dispersion - _..3.03*10 3.03*10
coefficient XMf h 1)
Pore velocity (M x) 0.027 0.030
Pore volume (L) 0.079 0.800
Column length (M) 0.20 0.20
Input concentration 0.125 0.0125
of H (mmole(+) L i)
Total amount of H 0.253 0.026
applied (mmole(+) L i)
Total no. of pore 23 26
volume collected
Parameter Mixed-cation subsoil Mixed-cation subsoil
Input solution pH
3,
.9
4.
.9
Bulk density (MG M ;
1,
.47
1.
.47
Volumetric water __
0.
.43
0.
.44
content (MJ M J)
— A
Dispersion ,,
-I1'
.85*10 *
1.
.85*10
coefficient (M^ h
1)
Pore velocity (M h 1)
0.
.0253
0.
.0248
Pore volume (L)
0.
.0951
0.
.965
Column length (M)
0.
.20
0.
,20
Input concentration
-!?â– 
.125
0.
,0125
of H (mmole^+) L
Total amount of H
)
9i
.267
0.
,024
applied (mmole(+)
L ]
L)
Total no. of pore
22.
.3
22.
,0
volume collected
The cation compositions of pretreated and mixed soils
are listed in Table 4-4 and concentrations of exchangeable
cations for nontreated Cecil topsoil and subsoil are given
in Table 4-5.

137
Table 4-5 Concentrations of exchangeable cations for
pretreated and mixed topsoil and subsoil
Soil
Concentrations of exchangeable cations
(mmole(+) kg soil)
K
Na
Mg
Ca Al
K-topsoi
17.20
0.30
0.08
0.60 5.80
Mg-topsoil
0.20
0.30
11.70
0.90 0.50
Ca-topsoil
0.10
0.00
0.02
11.70 2.20
K-subsoil
50.20
0.40
0.10
1.40 0.70
Mg-subsoil
0.30
0.20
96.80
0.30 1.40
Ca-subsoil
0.20
0.00
0.10
54.40 0.20
Mixed-topsoil
6.10
0.60
6.50
5.10 3.00
Mixed-subsoil
16.10
0.50
31.50
26.30 0.80
CEC
. 1
Dominant cation %
mmole(+) kg
soil
for this specific
Al included
CEC with A1J
included
K-topsoil
23.68
(K) 72
Mg-topsoil
13.60
(Mg) 86
Ca-topsoil
14.02
(Ca) 84
K-subsoil
52.80
(K) 95
Mg-subsoil
99.00
(Mg) 98
Ca-subsoil
54.90
(Ca) 95
Mixed-topsoil
21.30
*
Mixed-subsoil
75.20
*
CEC
1
Dominant cation %
mmole(+) kg
soil
for this specific
Al not included
CEC with Al not
included
K-topsoil
18.18
(K) 95
Mg-topsoil
13.10
(Mg) 89
Ca-topsoil
11.82
(Ca) 99
K-subsoil
52.11
(K) 96
Mg-subsoil
97.60
(Mg) 99
Ca-subsoil
54.70
(Ca) 99.1
Mixed-topsoil
18.30
*
Mixed-subsoil
74.40
*

138
Exchange Sites for Chemically Pretreated Soil
Treating the Cecil soil with a specific cation tended
to increase the base saturation and CEC (Tables 4-1 and 4-5)
of the soil, with the largest effect being found for the
subsoil. The pretreated topsoil and subsoil materials were
non-homoionic with respect to cations in the exchange phase,
indicating that the soil exchange sites were not completely
saturated initially with any one specific ion. For example,
equivalent fractions of K+ in K-topsoil were 95 and 72% for
cases in which Al was excluded from and included in the CEC
2+
calculation, respectively. Equivalet fractions of Mg in
Mg-topsoil were 89 and 86% for similar cases, with
2+
corresponding values of Ca for Ca-topsoil 99 and 84%, 96
and 95% for K-subsoil, 99 and 98% for Mg-subsoil, and 99 and
95% for Ca-subsoil. Quantities of other basic cations in
the exchange phase were small compared with the dominant ion
for each of the pretreated soils.
3+
The subsoil had very little exchangeable Al following
the cation-saturation procedures. Saturation of topsoil
exchange sites was not as complete as it was for the
subsoil.
Effluent pH for Treated Soil Columns
Regardless of pH of the applied HC1 solution, effluent
pH of all columns of pretreated Cecil topsoil, subsoil, and
mixed-cation columns started at about 4.0-4.4 and then
quickly increased to about pH 6.7 within two pore volumes of
elution. Thereafter, readings fluctuated around pH 6.1-6.8

139
for the remainder (approximately 25 pore volumes) of each
run. Concurrently, high concentrations of basic and acidic
cations appeared early in the effluent and then greatly
decreased with increasing volumes of effluent. Finally,
fairly stable values for concentrations of basic cations in
the effluent were maintained. Using input HC1 solutions
with two different pH values resulted in similar effects
upon column effluent. Figs. 4-1 and 4-2 present the
effluent pH from Ca-topsoil and Ca-subsoil, respectively.
In general, columns that received pH 4.9 solution resulted
in higher pH values for the effluent than when pH 3.9
solution was applied.
Cation Concentrations in Effluent from Treated Soil Columns
Concentrations of specific basic cations in effluent
from pretreated topsoil columns were observed to be very
high for each of the first-collected samples (about
0.14-0.17 pore volume). For example, K-topsoil, Ca-topsoil
and Mg-topsoil columns that received pH 3.9 HCl solution had
. . . + 2+ 2+
initial concentrations of K , Ca and Mg of 71.63,
164.87, and 249.28 mmole(+) L ^, respectively. For columns
receiving pH 4.9 HCl solution, initial concentrations of
70.13, 101.60, and 204.03 mmole(+) L 1 were observed for K+,
2+ 2+
Ca , and Mg , respectively. High initial concentrations
of specific cations in effluent from correspondingly
pretreated subsoil columns were also observed. For
K-subsoil, Ca-subsoil, and Mg-subsoil columns that received
pH 3.9 HCl solution, concentrations of K+, Ca^+, and Mg^+

pH of Effluent
7 . O
t 1 r
1 1 i 1 1 1 1 r
“| 1 1 r~ ■ i
t i 1 r
**
6.4-
**
H
Q® ^OOq 0 Q°0 ° ° O Q
tt *
5.0-
H
O
O O
O o
O-
r* ****
5.2-
r
O - pH 3.9
* - pH A.9
4.6-^
x
O
j i i i L
-i 1 i L i.
-I I L.
±
_J L. 1
J.
. 1. L
5 lO 15 20
Pore Volume (V/V ) of Effluent
o
Figure 4-1 Breakthrough curves for pH in the effluent from Ca-topsoil columns
which received input HCl solutions with two different pH values.
25
140

pH of Effluent
7 . O
6.4
5 . e
5.2
4.6
4.0
,8?*
* «
000(ft)
***** * *%â–¡
*o
**>
o
o
L «
o
L o
-o
"54
O
i * * OO" o _ * o
«f M ** * a oQ -“-o ^
o o°° o 00 Q
* o o
Oo
*
* O °
8 ~
o o
O - pH 3.9
* - pH 4.9
^ lO 15 20
Pore Volume (V/V ) of Effluent
â–¡
25
Figure 4-2 Breakthrough curves for pH in the effluent from Ca-subsoil columns which
received input HCl solutions with two different pH values.
141

142
were 60.89, 94.86 and 186.75 mmole(+) L respectively.
For columns that received pH 4.9 HCl solution,
concentrations of 33.51, 145.62 and 139.72 mmole(+) were
+ 2+ 2+
observed for K , Ca and Mg , respectively. Beginning
with the third collected sample (about 0.5 pore volume) of
effluent, cation concentrations underwent a drastic decrease
to below 10 mmole(+) L 1 for all of the pretreated topsoil
and subsoil columns. Concentrations of other cations for
each soil column were detectable but usually so small as to
be negligible.
High concentrations of cations that appeared in the
first few collected effluent samples from each pretreated
soil column can be explained by a "salt effect" and by the
replacement efficiency of H+ for exchangeable cations
(Wiklander, 1975; Reuss and Johnson, 1986). All air-dry
pretreated topsoil and subsoil contained 0.6 and 1% water
content by volume, respectively. Since the soil columns
were initially air-dry, as the acid solution infiltrated
into each soil column H+ in the moving wetting front tended
to replace cations from variably-charged sites effectively.
This resulted in high concentrations of cations in the
wetting front. Thus, due to the high ratio of 6M/6H for the
chemically pretreated soil columns, the replacing efficiency
of H+ for basic cations (Wiklander and Andersson, 1972) was
enhanced. Thereafter, these high concentrations of cations
3+ +
induced cation exchange with exchangeable (Al + H ),
resulting in low pH for the soil solution. This phenomenon

143
is called a "salt effect" (Wiklander, 1975). As mass flow
occurred, the acid displacing solution mixed with the native
soil solution by hydrodynamic dispersion. Acidity caused by
the salt effect was gradually leached, resulting in
increased pH of the soil solution and effluent once more.
From about 5 to 25 pore volumes of effluent the pH ranged
from about 6.0 to 6.6, indicating strong buffering by the
soil. The buffering reflects that H+ ions which were
partially removed from the solution phase either by ion
exchange, dissolution of clay minerals, reactions involving
aluminum species, or a combination of the three. The
2+
initial effluent concentrations of Mg from Mg-topsoil or
2+
Mg-subsoil were relatively higher than Ca from Ca-topsoil
or Ca-subsoil and than K+ from K-topsoil and K-subsoil. The
cause of these differences was uncertain.
The effect of input solution pH upon concentrations of
eluted cations in column effluent showed that the lower pH
of input acid solution resulted in approximately the same
quantities of cations being leached as obtained at the
higher pH. This phenomenon was found for all pretreated
topsoil and subsoil columns, but was most obvious for the
topsoil (Figs. 4-3, 4-4, and 4-5). Concentrations of
cations in the effluent from pretreated subsoil columns are
given in Figs. 4-6, 4-7, 4-8 for K-subsoil, Ca-subsoil, and
Mg-subsoil columns, respectively. A greater effect of input
solution pH upon cation elution was found for pretreated
topsoil than for subsoil. This can be explained by the

ion (mmole ( + ) /l)
144

(mmo le ( + ) / 1)
30
145

5
\
T
Q)
H
Q
E
E
C
o
•H
-P
(U
L
-P
C
Q)
U
C
o
u
- tt
• 0
Mg
2+
O -
* =
pH 3.9
pH 4.9
2> o
*®On ° o
* 9 9 q
i—i—i i I i i i i I i i i i I i i i i I i i i i L_
o o*
5 lO 15 20 25
Pone Volume (V/V ) of Effluent
O
Figure 4-5 Breakthrough curves of Mg^+ from Mg-topsoil columns which received
input HCl solutions with two different pH values.
30
146

Concentration (mmole (+)/l)
147

ion (mmole ( + ) /l)
148

\
T
Q)
rH
o
E
E
C
o
-H
-P
(0
L
-P
c
Q)
U
c
Q
U
149

150
effect of soil organic matter. Nontreated topsoil contained
more organic matter and amorphous material than subsoil
(refer to Table 2-2). The variable-charge sites
attributable to organic matter or amorphous material tended
to saturate with a single basic cation. Therefore, the
replacement efficiency of H+ for cations in the topsoil
should have been greater than for subsoil (Chatterjee and
Marshall, 1950; Wiklander and Andersson, 1972).
Concentrations of A1 determined in the column effluent
3+ 3+
were assumed to be in the Al form. Al concentrations in
the first collected sample of effluent were approximately 1
mmole(+) L 1 for K-subsoil and Ca-subsoil columns. This
relatively high effluent concentration was attributed to the
3+ 3+
salt effect on exchangeable Al . For Mg-subsoil, the Al
concentration was as high as 6.67 mmole(+) L 1. For all
3+
columns, concentrations of Al in consecutive effluent
samples consistently decreased. Figs. 4-9, 4-10 and 4-11
gave data for K-subsoil, Ca-subsoil and Mg-subsoil columns,
respectively. There was no effect of different input
3+
solution pH on Al effluent concentration for all
pretreated subsoil columns.
3+
Concentrations of Al in the first collected effluent
sample for K-topsoil and Ca-topsoil columns were as high as
24.5 and 2.45 mmole(+) L ^, respectively. These high
concentrations were also attributed to the salt effect. The
3+
elution of Al was different for Mg-topsoil, in that a
concentration peak occurred at about 8.0-8.2 pore volumes.

Concentration (mmole (+)/l)
O . 4
H
0.3-
0.2-
0.1-0
H
Figure 4
T
t , 1 1 r
Al3+
o
K
pH 3.9
pH 4.9
p *£> IP WD. QittQ *n Qi Ck< G LififiQj ülQ ■ * m * .O* I CM . Q ,Qt , *
4 B 12 16 20
Pore Volume (V/V ) of Effluent
o _i_ O ,
-9 Breakthrough curves of Al from K-subsoil columns which received
input HCl solutions with two different pH values.
151

Concentration (mmole (+)/l)
152

Concentration (mmole ( + ) /l)
•1.5
K
1.0-
0.5-
*
O
'6
o . o’—
Figure
t 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 r
A 1
3 +
O
*
pH 3.9
pH 4.9
48—&—s I ffl jp—ig> UC >0 *0 <0 1 MQGH IMQI KQ J— O* 1-0—I
5 10 15
Pore Volume (V/V ) of Effluent
o
l — 11 Breakthrough curves of Al"^+ from Mg-subsoil columns which received
input HCl solutions with two different pH values.
20
153

154
The cause of this is uncertain. Figs. 4-12, 4-13, and 4-14
3+
present A1 concentrations in effluent from columns of
K-topsoil, Ca-topsoil and Mg-topsoil, respectively. The
. 3+
effect of input solution pH upon A1 concentration in
column effluent was such that, the more acidic the input
3+
solution, the more A1 was leached. This effect was not in
direct proportion to the H+ ion concentration, however.
Cation Concentrations in Effluent from Chemically Pretreated
Mixed Soil Columns
Figs. 4-15 and 4-16 present concentrations for cations
eluted from columns of mixed topsoil and mixed subsoil that
received pH 3.9 HC1 solution, respectively. Very high
concentrations of each cation were observed initially in
effluent. For example, for mixed topsoil that received pH
, 9+ 2+ +
3.9 HCl solution, initial concentrations of Ca , Mg , K
and Na+ were 58.8, 114.36, 24.0 and 0.63 mmole(+) L
respectively. For effluent from mixed topsoil columns that
received pH 4.9 HCl solution, initial concentrations of
Ca2+, Mg2+, K+ and Na+ were 54.8, 115.18, 25.84 and 0.56
mmole(+) L-1, respectively. For mixed subsoil that received
2+ 2+ + +
pH 3.9 HCl, initial concentrations of Ca , Mg , K and Na
in column effluent were 788.42, 756.89, 112.30 and 1.2
mmole(+) L ^, respectively; and for mixed subsoil that
received pH 4.9 HCl solution, initial concentrations of
Ca2+, Mg2+, K+, Na+ were 459.08, 699.03, 125.61 and 1.36
mmole( + ) L-'*', respectively. These observations can be
explained once more by the salt effect and by the replacing

Figure 4-12 Breakthrough curves of Al3+ from K-topsoil columns which received
input HCl solutions with two different pH values.
155

Concentration (mmole (+)/l)
156

Concentration (mmole (+)/l)
Figure 4-14 Breakthrough curves of Al^+ from Mg-topsoil columns which received
input HCl solutions with two different pH values.
30
157

ion (mmole ( + ) /l)
-M
(0
L
-P
C
Q)
U
C
o
u
Pore Volume (V/V ) of Effluent
o
Figure 4-15 Breakthrough curves of cations in the effluent from a mixed-cation
topsoil column which received pH 3.9 input HCl solution.
25
158

rH
\
7
0
H
â–¡
E
E
C
o
-H
-P
0
L
-P
C
0
u
c
o
u
Figure 4-16 Breakthrough curves of cations in the effluent from a mixed-cation
subsoil column which received pH 3.9 input HCl solution.
159

160
efficiency of H+ for basic cations described in the
aforementioned paragraph. After the first collected sample
of effluent, concentrations of cations were observed to
decrease drastically in the second or third samples, and
then afterwards concentrations gradually decreased with
time. The initially larger concentrations for mixed subsoil
than for mixed topsoil are attributed to the fact that the
CEC of the pretreated mixed subsoil was three-fold greater
than for mixed topsoil. For mixed topsoil and subsoil,
concentrations of K+ were the greatest, concentrations of
2+ 2+ +
Mg and Ca were less than for K , and concentrations of
2+ 2+
Mg and Ca were difficult to distinguish from each other.
The same concentration behavior was also found when pH 4.9
HCl was applied to columns of mixed topsoil and subsoil,
2+ 2+
respectively. This occurred because divalent Ca and Mg
cations are more preferred than monovalent K+ and Na+
cations for the Cecil soil exchange sites.
The effect of pH of the input HCl solutions upon
+ 2+
elution of K and Ca from mixed topsoil columns is shown
. 2+ +
in Figs 4-17 and 4-18, and the effect on Mg and K from
mixed subsoil is shown in Figs 4-19 and 4-20. The pH of
input HCl solution had a greater effect upon concentrations
+ 2+ 2+
of K in column effluent than on Ca or Mg . This
observation implies that a lower pH (higher H+
concentration) of input solution enhanced competition of H+
ions with monovalent cations such as K+ and Na+ for soil

c
o
-H
-p
ra
L
-p
c
0
u
c
â–¡
u
25
161

Concentration (mmole (+)/l)
162

c
o
•rl
â– P
(D
L
P
C
0
u
c
â–¡
u
25
163

Concentration (mmole ( + ) /l)

165
exchange sites, but was not as effective in enhancing
+ s 2+
competition of H ions with divalent cations such as Mg
_ 2+
and Ca
3+
Concentrations of Al in Effluent from Mixed Soil Columns
3+
Concentrations of Al in effluent from mixed
topsoil and subsoil columns that received HC1 solutions, are
presented in Figs. 4-21 and 4-22, respectively. Initial
3+ -1
concentrations of Al were approximately 2.80 mmole(+) L ,
for effluent from mixed topsoil that received pH 3.9 HCl
solution, and 0.47 mmole(+) L 1 from subsoil columns that
received pH 4.9 HCl solution. In general, concentrations of
eluted Al3+ in the effluent from columns of mixed subsoil
were quite low after the first few samples of effluent, and
no differences in these values were observed for applied HCl
solutions with different pH. For mixed topsoil columns,
3+
concentrations of Al decreased gradually and the pH of
3+
input HCl solution did effect the concentration of Al in
the effluent. Higher concentrations of Al3+ occurred
in initial effluent from columns receiving pH 3.9 solution
3+
than at pH 4.9. Total quantities of Al in the effluent
from columns receiving pH 3.9 solution were not reasonably
greater than for pH 4.9, however. The reason for this
observation was uncertain.
Concentrations of Cations in Solution and Exchange Phases
for Treated and Mixed Soil Columns after Application of 25
Pore Volumes of HCl Solution
Treated Subsoil. Concentrations of cations in solution
and exchange phases are presented in Tables 4-6 and 4-7 for

Concentration (mmole ( + ) /l)
166

Concentration (mmole (+)/l)
167

168
Table 4-6 Concentrations of cations in solution
and exchange phases for K-subsoil
after leaching with pH 3.9 HC1 solution
Depth Ca Mg K Na A1 Sum
(cm) Solution pha^e
mmole ( + ) L
1.0
0.354
0.058
0.215
1.130
0.014
1.771
2.0
0.287
0.054
0.413
1.230
0.009
1.992
3.0
0.619
0.107
0.640
2.420
0.014
3.801
4.0
0.372
0.062
0.454
1.480
0.007
2.374
5.0
0.344
0.049
0.370
1.310
0.046
2.119
6.0
0.489
0.099
0.570
3.700
0.008
4.865
7.0
0.564
0.115
0.532
2.680
0.009
3.900
8.0
0.531
0.099
0.350
1.930
0.021
2.931
9.0
0.473
0.064
0.390
1.530
0.008
2.465
10.0
0.459
0.066
0.384
1.220
0.110
2.239
11.0
0.297
0.078
0.480
1.720
0.024
2.600
12.0
0.437
0.084
0.502
2.210
0.009
3.242
13.0
0.312
0.058
0.434
1.200
0.029
2.033
14.0
0.374
0.064
0.454
2.180
0.011
3.083
15.0
0.803
0.140
0.734
2.960
0.009
4.646
16.0
0.713
0.104
0.962
2.680
0.009
4.468
17.0
0.342
0.058
0.315
1.340
0.014
2.069
18.0
0.332
0.069
0.465
1.580
0.028
2.474
19.0
0.743
0.118
0.622
2.990
0.019
4.492
20.0
0.813
0.111
0.458
2.320
0.006
3.708
Depth
Ca
Mg
K
Na
A1
Sum
(cm)
Ijau i id i ly l
¿-'lid & C.
Kg'1 i
1.0
0.661
0.041
1.820
0.652
9.885
13.059
3.0
1.070
0.041
13.400
0.685
0.512
15.708
5.0
1.100
0.123
14.100
0.674
0.701
16.698
7.0
1.520
0.103
14.800
0.739
0.467
17.629
9.0
1.250
0.041
15.100
0.652
0.789
17.832
11.0
1.380
0.082
13.000
0.674
0.556
15.692
13.0
1.330
0.062
14.300
0.652
0.441
16.785
16.0
1.470
0.062
14.100
0.685
0.311
16.628
18.0
1.170
0.062
14.400
0.652
0.523
16.807
20.0
1.160
0.062
14.100
0.696
0.478
16.496

169
Table 4-7 Concentrations of cations in solution
and exchange phases for K-subsoil after
leaching with pH 4.9 HCl solution
Depth Ca Mg K Na Al Sum
(cm) Solution pha^e
mmole (+) L
1.0
0.027
0.008
0.318
0.448
0.007
0.808
2.0
0.027
0.010
0.441
0.368
0.000
0.846
3.0
0.207
0.030
0.187
0.921
0.021
1.366
4.0
0.267
0.029
0.161
1.150
0.000
1.607
5.0
0.031
0.012
0.496
0.965
0.004
1.508
6.0
0.257
0.040
0.344
1.300
0.003
1.944
7.0
0.437
0.049
0.424
1.600
0.000
2.510
8.0
0.398
0.046
0.365
1.410
0.004
2.224
9.0
0.317
0.049
0.394
1.530
0.037
2.327
10.0
0.308
0.054
0.408
1.750
0.000
2.520
11.0
0.428
0.059
0.464
1.790
0.004
2.746
12.0
0.459
0.082
0.496
2.400
0.000
3.437
13.0
0.424
0.054
0.403
1.690
0.002
2.573
14.0
0.608
0.079
0.465
2.250
0.011
3.413
15.0
0.828
0.099
0.454
2.790
0.000
4.171
16.0
0.571
0.062
0.263
1.690
0.000
2.586
17.0
0.689
0.079
0.427
2.420
0.000
3.615
18.0
0.889
0.099
0.562
2.880
0.000
4.430
19.0
0.629
0.079
0.546
2.030
0.000
3.284
20.0
0.790
0.118
0.556
2.680
0.000
4.144
Depth
Ca
Mg
K
Na
Al
Sum
(cm)
pilu ^ L
Kg x so
1.0
1.280
0.226
9.790
0.739
3.614
15.649
3.0
1.200
0.165
13.900
0.772
0.901
16.938
5.0
1.150
0.062
13.700
0.652
0.678
16.242
7.0
1.410
0.062
15.500
0.696
0.812
18.480
9.0
1.330
0.041
14.100
0.685
0.756
16.912
11.0
1.360
0.062
13.600
0.707
0.645
16.374
14.0
1.270
0.062
14.500
0.652
0.623
17.107
16.0
1.410
0.062
15.100
0.696
0.645
17.913
18.0
1.240
0.062
14.000
0.717
0.689
16.708
20.0
1.330
0.062
14.800
0.739
0.645
17.576

170
K-subsoil columns after application with pH 3.9 and 4.9
input HCl solutions, respectively. In the solution phase,
. + + 2 +
cation concentrations were in the order Na > K = Ca >
2+ 3+
Mg > A1 , while for the exchange phase cation
concentrations were in the order K+ > Ca^+ = Al3+ = Na+ >
2+
Mg for both pH treatments. If one compared concentrations
of cations in the exchange phase in Tables 4-6 and 4-7 with
values in Table 4-4 for the initial K-subsoil, leaching loss
. . . 2+ 2+
of K was significant, while leaching losses for Ca , Mg ,
Na+ and Al^+ were small. A similar trend was observed for
both pH treatments.
Tables 4-8 and 4-9 present concentrations of cations in
solution and exchange phases for Ca-subsoil columns after
application of pH 3.9 and 4.9 HCl solutions, respectively.
Solution-phase concentrations of cations were of the order
â– f1 9+ 3+ 2+
Na > Ca > Al = K > Mg and, for the exchange phase,
• • 2+ 3+ 2+
concentrations of cations were Ca > Al > K = Na > Mg
for both pH treatments. If one compared cation
concentrations in the exchange phase in Tables 4-8 and 4-9
with values in Table 4-4 for the initial Ca-subsoil, the
2+
concentrations of Ca were dramatically decreased by
leaching, but concentrations of other species such as Na+
3+ 2+
and A1 were actually somewhat increased. Mg was
slightly decreased for both pH treatments, and K+ was
increased for the pH 3.9 treatment but not for the pH 4.9
case. The explanation for increased concentrations of
certain species in the exchange phase is that K+, Na+ and

171
Table 4-8 Concentrations of cations in solution and
exchange phases for Ca-subsoil after
leaching with pH 3.9 HC1 solution
Mg K Na
— Solution pha^e
— mmole (+) L
Depth
(cm) â– 
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0
16.0
17.0
18.0
19.0
20.0
Ca
0.385
0.385
0.417
0.349
0.313
0.531
0.442
0.858
0.359
0.409
0.339
0.404
0.344
0.806
0.489
0.614
0.430
1.190
0.851
0.873
0.053
0.043
0.063
0.056
0.043
0.045
0.066
0.095
0.045
0.058
0.049
0.037
0.054
0.078
0.058
0.058
0.067
0.099
0.103
0.115
0.161
0.210
0.214
0.191
0.214
0.137
0.152
0.243
0.320
0.165
0.107
0.334
0.265
0.148
0.141
0.171
0.125
0.637
0.246
0.217
0.918
1.240
1.300
0.835
1.260
1.580
1.120
1.960
0.978
1.420
0.861
0.939
0.874
1.360
1.230
1.280
1.330
3.150
1.430
2.280
Al
0.013
0.391
0.018
0.374
0.125
0.172
1.230
0.022
0.578
0.856
5.130
0.450
1.630
0.045
0.178
0.767
0.465
0.027
0.061
0.022
Sum
1.530
2.269
2.011
1.805
1.955
2.465
3.010
3.178
2.280
2.908
6.486
2.164
3.167
2.437
2.096
2.890
2.417
5.102
2.691
3.507
Depth
(cm)
Ca
Mg
K
Exchange
Na
Al
Sum
1.0
2.820
i
0.021
Timóle ( + )
0.185
Kg "
0.239
soil —
6.961
10.226
3.0
10.200
0.021
0.205
0.217
0.267
10.910
5.0
11.900
0.041
0.205
0.239
0.334
12.719
7.0
12.800
0.062
0.301
0.359
0.300
13.822
9.0
11.700
0.021
0.198
0.228
0.323
12.470
11.0
11.600
0.021
0.230
0.207
0.278
12.336
14.0
11.400
0.021
0.205
0.196
0.300
12.122
16.0
12.100
0.021
0.269
0.228
0.467
13.085
18.0
12.500
0.082
0.646
0.348
0.256
13.832
20.0
11.700
0.021
0.217
0.217
0.267
12.422

172
Table 4-9 Concentratons of cations in solution and
exchange phases for Ca-subsoil after
leaching with pH 4.9 HCl solution
Depth
Ca
Mg
K
Na
Al
Sum
(cm)
r 1
1.0
0.503
0.066
0.178
1.910
0.129
2.786
2.0
0.826
0.092
0.257
2.440
0.018
3.633
3.0
0.479
0.046
0.137
1.140
0.765
2.567
4.0
0.523
0.056
0.192
1.310
0.369
2.450
5.0
0.575
0.053
0.192
1.610
0.080
2.510
6.0
0.659
0.066
0.235
2.310
0.167
3.437
7.0
0.665
0.069
0.135
1.660
0.013
2.542
8.0
0.555
0.056
0.108
1.250
0.129
2.098
9.0
0.645
0.072
0.143
1.660
0.125
2.645
10.0
0.659
0.053
0.171
1.380
0.156
2.419
11.0
0.681
0.066
0.221
1.650
0.040
2.658
12.0
1.220
0.094
0.327
3.900
0.040
5.581
13.0
0.840
0.072
0.193
1.940
0.031
3.077
14.0
0.831
0.082
0.132
2.200
0.067
3.312
15.0
0.495
0.049
0.085
1.380
0.018
2.027
16.0
0.575
0.049
0.151
1.230
0.031
2.036
17.0
0.816
0.095
0.204
2.030
0.027
3.172
18.0
0.551
0.076
0.171
1.570
0.142
2.510
19.0
0.591
0.072
0.153
1.460
0.169
2.445
20.0
0.399
0.059
0.099
1.060
3.180
4.798
Depth
(cm)
Ca
Mg
K
Na
Al
Sum
1.0
8.980
0.123
0.205
0.261
0.979
10.548
3.0
10.400
0.041
0.173
0.304
0.289
11.207
5.0
11.600
0.041
0.256
0.283
0.300
12.480
7.0
10.500
0.041
0.198
0.326
0.289
11.354
9.0
11.000
0.041
0.147
0.370
0.322
11.880
11.0
11.500
0.041
0.160
0.391
0.334
12.426
12.0
9.610
0.041
0.192
0.348
0.311
10.502
15.0
10.500
0.021
0.179
0.174
0.311
11.185
17.0
10.500
0.041
0.166
0.196
0.300
11.203
19.0
11.600
0.041
0.179
0.380
0.322
12.522

173
2 +
Ca occur in nonexchangeable forms such as between lattices
or interlayers of interlayer-hydroxy vermiculite
(M+(Mg,Fe)3(Si,Al)4O10(OH)2)/ where M+ denotes cation
species located between lattices or interlayers (Dixon and
Weed, 1977; Bohn et al., 1985). A long period of leaching
with acid solutions will result in weathering of the
minerals, releasing nonexchangeable cations from within the
lattices or interlayers.
Tables 4-10 and 4-11 present concentrations of cations
in solution and exchange phases for Mg-subsoil columns after
application of pH 3.9 and 4.9 HC1 solutions, respectively.
In the solution phase, concentrations of cations were of the
order Na+ > Ca^+ > K+ = Mg^+ > Al"^+ but, for the exchanger
2+ 3+ 2+
phase, concentrations of cations were Mg > Al > Ca >
Na+ > K+ for both pH treatments. If we compare
concentrations of cations in the exchange phase in Tables
4-10 and 4-11 with values in Table 4-4 for initial
2+
Mg-subsoil, the concentrations of Mg were greatly
3+
decreased by leaching but Al concentrations were changed
2+ +
only slightly, Ca and Na concentrations were increased
and K+ was decreased. This change in cation concentrations
was found both for pH treatments 3.9 and 4.9. Usually,
cation species with the higher valence have a higher
affinity for exchange sites. Therefore, high concentrations
of divalent and trivalent species were observed in the
exchange phase compared to Na+ and K+. Cations with low
valence demonstrated lower affinity for exchange sites, such

174
Table 4-10 Concentrations of cations in solution
and exchange phases for Mg-subsoil after
leaching with pH 3.9 HC1 solution
Mg K
— Solution
— mmole(+)
Depth
(cm)
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0
16.0
17.0
18.0
19.0
20.0
Ca
0.362
0.472
0.267
0.364
0.327
0.359
0.377
0.349
0.324
0.487
0.514
0.589
0.509
0.589
0.574
0.444
0.576
0.556
0.474
0.464
0.078
0.119
0.103
0.144
0.115
0.123
0.123
0.140
0.128
0.152
0.144
0.136
0.148
0.156
0.169
0.111
0.136
0.111
0.136
0.132
0.187
0.243
0.139
0.164
0.114
0.159
0.079
0.113
0.132
0.132
0.104
0.212
0.169
0.180
0.182
0.157
0.175
0.155
0.153
0.088
Na
phase
L
1.130
1.800
0.785
1.280
0.991
1.110
1.330
1.510
1.390
1.770
1.680
2.410
1.680
1.520
1.980
1.440
1.690
1.720
1.480
1.610
A1
0.003
0.001
0.002
0.003
0.008
0.003
0.002
0.003
0.004
0.000
0.000
0.002
0.002
0.002
0.001
0.004
0.004
0.002
0.010
0.001
Sum
1.761
2.635
1.296
1.955
1.555
1.754
1.912
2.115
1.978
2.541
2.442
3.349
2.508
2.447
2.906
2.156
2.581
2.544
2.253
2.295
Depth Ca Mg K Na Al Sum
(cm) Exchange phase
mmole(+) Kg soil
2.0
1.210
5.550
0.179
0.391
9.329
16.659
4.0
0.861
8.020
0.179
0.337
3.269
12.666
5.0
0.724
8.640
0.192
0.228
1.390
11.174
7.0
0.624
7.820
0.185
0.217
1.401
10.247
9.0
0.636
8.230
0.217
0.239
1.301
10.623
11.0
0.761
8.840
0.205
0.304
1.379
11.489
13.0
0.736
8.840
0.441
0.457
1.379
11.853
15.0
0.686
8.840
0.230
0.283
1.223
11.262
18.0
0.699
8.020
0.281
0.326
1.223
10.549
20.0
0.674
8.020
0.365
0.391
1.368
10.818

175
Table 4-11 Concentrations of cations in solution
and exchange phases for Mg-subsoil after
leaching with pH 4.9 HC1 solution
Depth
(cm)
Ca
Mg
K
Solution
Na
phase
A1
Sum
mmole(+)
L
1.0
0.419
0.090
0.184
1.000
0.022
1.716
2.0
0.294
0.086
0.139
0.935
0.022
1.477
3.0
0.259
0.086
0.134
0.804
0.041
1.325
4.0
0.511
0.119
0.243
1.110
0.017
2.000
5.0
0.205
0.090
0.105
0.676
0.203
1.280
6.0
0.302
0.074
0.134
0.817
0.001
1.328
7.0
0.264
0.078
0.114
0.809
0.029
1.294
8.0
0.419
0.090
0.152
0.965
0.002
1.629
9.0
0.432
0.103
0.136
1.360
0.016
2.047
10.0
0.319
0.103
0.164
1.110
0.130
1.826
11.0
0.479
0.109
0.526
1.140
0.003
2.257
12.0
0.356
0.079
0.330
0.939
0.003
1.707
13.0
0.050
0.099
0.243
1.290
0.002
1.684
14.0
0.389
0.082
0.243
1.190
0.004
1.909
15.0
0.269
0.084
0.235
0.916
0.048
1.552
16.0
0.557
0.099
0.152
1.270
0.003
2.081
17.0
0.434
0.165
0.148
1.710
0.001
2.458
18.0
0.452
0.107
0.171
1.280
0.010
2.020
19.0
0.467
0.128
0.321
1.570
0.017
2.503
20.0
0.392
0.107
0.129
1.200
0.014
1.843
Depth
(cm)
Ca
Mg
K
Na
A1
Sum
2.0
0.823
9.050
0.192
0.359
3.514
13.938
4.0
0.749
9.870
0.211
.0.370
2.113
13.313
5.0
0.786
9.670
0.230
0.348
1.968
13.002
7.0
0.811
9.460
0.217
0.435
1.868
12.791
9.0
0.674
9.670
0.243
0.337
1.935
12.859
12.0
0.699
9.050
0.211
0.283
1.334
11.577
14.0
0.724
8.840
0.230
0.326
1.301
11.421
16.0
1.620
9.260
0.294
0.326
1.190
12.690
18.0
0.773
9.460
0.301
0.391
1.801
12.726
20.0
0.711
9.870
0.249
0.348
2.168
13.346

176
that the concentration of monovalent cations tended to be
higher in the solution phase. After leaching pretreated
subsoil with HC1 solution for about 20 pore volumes, the
initial cation species which had saturated the exchange
sites were observed to still be the most dominant
exchangeable cation in the soil as shown in Tables 4-6
through 4-11. The resultant CEC of the pretreated soil was
quite stable and had approximately the same quantity of
cations, but less than that for the nontreated soil, as
given in Table 4-5. Base saturation was greatly decreased
by continuous acid leaching from 90% initially to 55% after
application of acid for all cases. In the section of each
column which received acid input solution a high
3+
concentration of exchangeable Al was generally observed
and was attributed to poorly crystalline vermiculite or
hydrous oxides of Al being exposed as exchange sites.
Treated Topsoil. Tables 4-12 and 4-13 present
concentrations of cations in solution and exchange phases
for Ca-topsoil columns which received input HC1 solutions of
pH 3.9 and 4.9, respectively. Concentrations of cations in
+ 2+ 2+ +
the solution phase were in the order Na > Ca > Mg > K
3+ 2+ 3+ +
> Al and for the exchange phase were Ca > Al > K =
+ 2+
Na > Mg for both treatments. If concentrations of
cations in the exchange phase for Tables 4-12 and 4-13 are
compared with values in Table 4-4 for original Ca-topsoil,
2+ + +
the cation concentrations for Mg , K , and Na tended to
2+ 3 +
increase during acid leaching but Ca and Al

177
Table 4-12 Concentrations of cations in solution
and exchange phases for Ca-topsoil after
leaching with pH 3.9 HCl solution
Depth
(cm)
Ca
Mg
l
K
Solution
Na
ph^se
Al
Sum
1.0
0.799
0.726 0.184#
1.210
0.002
2.921
2.0
1.260
0.792
0.490
1.780
0.017
4.339
3.0
0.948
1.120
0.127
0.939
0.060
3.194
4.0
0.741
1.330
0.122
0.998
0.022
3.213
5.0
0.633
0.437
0.134
1.430
0.066
2.700
6.0
0.723
0.318
0.166
1.390
0.217
2.814
7.0
0.804
0.207
0.364
2.410
0.009
3.794
8.0
0.656
1.220
0.136
1.350
0.009
3.371
9.0
0.838
0.592
0.350
2.320
0.007
4.107
10.0
1.320
1.000
0.364
2.110
0.004
4.798
11.0
0.912
0.918
0.200
1.130
0.012
3.172
12.0
1.320
0.067
0.219
1.410
0.038
3.053
13.0
1.190
0.481
0.127
1.370
0.012
3.180
14.0
0.858
1.670
0.274
3.990
0.407
7.199
15.0
0.705
0.489
0.076
0.743
0.054
2.067
16.0
0.907
1.550
0.246
1.860
0.046
4.609
17.0
0.880
0.141
0.087
10.200
0.018
11.326
18.0
0.979
0.896
0.186
1.530
0.008
3.599
19.0
1.010
0.444
0.269
1.260
0.007
2.990
20.0
0.859
0.222
0.158
1.680
0.006
2.925
Depth Ca Mg K Na Al Sum
(cm) Exchange phas|
1.0
3.620
i
0.041
nmole ( + )
0.192
Kg "
0.337
soil —
5.182
9.372
3.0
10.500
0.041
0.294
0.304
1.511
12.650
5.0
10.400
0.021
0.237
0.283
1.156
12.097
7.0
9.360
0.021
0.211
0.261
1.023
10.876
10.0
11.700
0.041
0.301
0.337
1.012
13.391
11.0
12.700
0.041
0.269
0.359
1.201
14.570
14.0
10.600
0.041
0.269
0.283
0.867
12.060
16.0
11.700
0.062
0.326
0.370
0.845
13.303
18.0
12.000
0.082
0.499
0.413
0.978
13.972
20.0
10.900
0.082
0.288
0.304
0.789
12.363

178
Table 4-13 Concentrations of cations in solution
and exchange phases for Ca-topsoil
after leaching with pH 4.9 HC1 solution
Depth Ca Mg K Na Al Sum
(cm)
Solution
phase
T 1
1.0
1.330
0.204
0.565
0.268
0.006
2.373
2.0
0.913
0.103
0.453
1.090
0.012
2.571
3.0
0.606
0.086
0.413
0.891
0.016
2.012
4.0
0.718
0.174
0.632
1.020
0.016
2.560
5.0
0.731
0.197
0.577
0.939
0.014
2.459
6.0
0.521
0.089
0.445
0.646
0.018
1.719
7.0
0.687
0.215
0.465
1.100
0.016
2.483
8.0
0.599
0.148
0.256
0.630
0.019
1.652
9.0
0.695
0.109
0.200
0.522
0.009
1.535
10.0
0.692
0.207
0.387
0.770
0.018
2.074
11.0
0.674
0.070
0.224
0.500
0.012
1.480
12.0
0.958
0.074
0.216
0.600
0.012
1.860
13.0
0.852
0.194
0.401
0.852
0.011
2.310
14.0
0.888
0.140
0.380
0.826
0.012
2.246
15.0
0.946
0.156
0.299
0.750
0.014
2.166
16.0
0.727
0.046
0.176
0.496
0.023
1.469
17.0
0.862
0.099
0.259
0.665
0.022
1.907
18.0
1.080
0.155
0.186
0.565
0.076
2.062
19.0
1.230
0.270
0.265
0.609
0.020
2.394
20.0
1.010
0.165
0.164
0.435
0.039
1.813
Depth
i Ca
Mg
K
Na
Al
Sum
t \
phase
l cm)
Kg 1
1.0
6.610
0.082
0.249
0.130
6.249
13.320
3.0
10.500
0.082
0.288
0.174
5.393
16.437
6.0
9.480
0.062
0.160
0.272
5.526
15.500
8.0
10.100
0.062
0.205
0.217
5.582
16.166
10.0
10.900
0.062
0.275
0.283
5.582
17.102
12.0
11.100
0.021
0.230
0.261
5.315
16.927
14.0
10.500
0.021
0.179
0.283
5.404
16.387
16.0
11.500
0.000
0.217
0.304
5.010
17.031
18.0
13.000
0.103
0.294
0.326
4.759
18.482
20.0
11.400
0.103
0.480
0.370
6.416
18.769

179
concentrations tended to decrease. Increased concentrations
of cations in the exchange phase during acid leaching are
explained by the argument given in the section on treated
subsoil, since K , Na and Ca occur naturally between the
lattices or interlayers of interlayer-hydroxy vermiculite
(Dixon and Weed, 1977; Bohn et al., 1985). Due to the
dissolution or weathering of such minerals and of
carbonates, the release of cations from nonexchangeable
forms tends to offset leaching losses of cations due to acid
deposition. Calcium was not decreased greatly due to
2+
leaching for either of the acid treatments, since Ca was
more preferred on soilexchange sites.
Tables 4-14 and 4-15 provide concentrations of cations
in solution and exchange phases for K-topsoil columns which
received input HCl solutions with pH 3.9 and 4.9,
respectively. The concentrations of cations in the solution
• ^ 2 41 2 3
phase were in the order Na > Mg = K > Ca > Al , and
3+
for the exchange phase the concentrations were in order Al
> K+ > Ca2+ > Na+ > Mg^+. If one compared the
concentrations of cations in exchanger phase for Tables 4-14
and 4-15 with values in Table 4-4 for original K-topsoil,
concentrations of exchangeable K+ were significantly less.
2+ 2+ +
Concentrations of other cations such as Ca , Mg , Na and
Al^+ tended to increase for both treatments, however.
Reasons similar to those mentioned earlier were used to
explain the increased concentrations of specific cations in
the exchange phase. The column that received pH 4.9 HCl

180
Table 4-14 Concentrations of cations in solution
and exchange phases for K-topsoil after
leaching with pH 3.9 HC1 solution
Depth
(cm)
Ca
Mg
K Na
A1
Sum
mmole
0.090
( + \ T ~ ^ _
1.0
0.296
0.622
V ^
0.587
0.004
1.599
2.0
0.844
0.874
0.583
1.370
0.004
3.675
3.0
0.449
0.852
0.205
0.783
0.006
2.295
4.0
0.130
1.220
0.246
0.593
0.002
2.191
5.0
0.817
1.110
0.592
1.240
0.006
3.765
6.0
0.692
0.666
0.638
1.130
0.006
3.132
7.0
1.190
8.400
1.600
4.370
0.048
15.608
8.0
0.110
1.660
0.652
1.470
1.140
5.032
9.0
0.221
1.250
0.725
0.061
0.681
2.938
10.0
0.298
1.110
0.905
1.160
0.006
3.479
11.0
0.850
1.500
1.450
2.540
0.003
6.343
12.0
0.435
0.406
1.030
1.670
0.003
3.544
13.0
0.259
0.118
1.060
1.610
0.004
3.051
14.0
0.220
1.160
1.360
0.765
0.033
3.538
15.0
0.229
1.760
1.110
1.660
0.007
4.766
16.0
0.269
0.526
0.999
0.900
0.016
2.710
17.0
0.184
1.180
1.200
1.350
0.036
3.950
18.0
0.153
1.250
1.080
1.510
0.014
4.008
19.0
0.404
0.940
0.960
2.780
0.011
5.095
20.0
0.856
2.410
1.970
2.400
0.150
7.786
Depth Ca Mg K Na A1 Sum
(cm) Exchange phase
mmole(+) Kg soil
1.0
0.499
0.082
0.761
0.543
7.583
9.468
4.0
0.923
0.123
1.400
0.652
6.794
9.892
6.0
0.986
0.123
1.540
0.554
5.660
8.863
8.0
0.948
0.123
2.220
0.565
5.838
9.694
10.0
1.010
0.144
2.850
0.446
5.860
10.310
12.0
0.848
0.123
2.790
0.435
6.271
10.467
14.0
1.040
0.165
3.270
0.630
5.982
11.087
16.0
1.050
0.123
3.180
0.478
5.504
10.335
18.0
0.823
0.123
3.000
0.663
6.038
10.647
20.0
1.060
0.185
3.470
0.707
5.104
10.526

181
Table 4-15 Concentrations of cations in solution
and exchange phases for K-topsoil after
leaching with pH 4.9 HC1 solution
Depth
(cm)
Ca
Mg
K
Solution
Na
A1
Sum
ise
mmole(+)
L
1.0
0.407
1.330
0.426
2.050
0.006
4.219
2.0
0.292
1.620
0.463
0.761
0.012
3.148
3.0
0.182
1.420
0.478
0.946
0.016
3.042
4.0
0.139
0.259
0.511
0.528
0.016
1.453
5.0
0.135
2.120
0.744
1.150
0.014
4.163
6.0
0.212
2.710
0.700
1.230
0.018
4.870
7.0
0.355
1.050
0.565
0.487
0.016
2.473
8.0
0.208
0.449
1.140
1.580
0.019
3.396
9.0
0.164
2.420
0.770
0.661
0.009
4.024
10.0
1.150
1.460
0.919
1.500
0.018
5.047
11.0
1.380
0.518
1.170
1.720
0.012
4.800
12.0
0.436
0.992
1.080
0.763
0.012
3.283
13.0
0.120
0.062
0.721
0.380
0.011
1.294
14.0
0.092
0.045
0.733
0.283
0.012
1.166
15.0
0.144
0.089
1.040
0.430
0.014
1.717
16.0
0.103
0.037
0.967
0.274
0.023
1.404
17.0
0.045
0.052
1.040
0.215
0.022
1.374
18.0
0.076
0.059
1.110
0.215
0.076
1.536
19.0
0.112
0.089
1.170
0.313
0.020
1.704
20.0
0.501
2.100
0.944
1.050
0.039
4.634
)epth
cm)
Ca
Mg
K
Na
A1
Sum
mmole (+) Kg
1.0
0.561
0.041
0.582
0.217
2.891
4.292
3.0
0.599
0.062
1.300
0.239
1.768
3.968
5.0
0.674
0.082
1.920
0.261
1.568
4.505
7.0
0.699
0.082
2.620
0.207
1.423
5.031
9.0
0.561
0.062
2.290
0.196
1.579
4.688
11.0
0.649
0.103
2.650
0.239
1.501
5.142
13.0
0.674
0.082
3.200
0.217
1.390
5.563
15.0
0.836
0.082
3.010
0.239
1.446
5.613
17.0
0.836
0.103
3.480
0.217
1.357
5.993
20.0
1.500
0.391
6.270
0.087
1.201
9.449

182
3 +
solution showed that very little exchangeable A1 existed
initially, however.
Tables 4-16 and 4-17 present concentrations of cations
in solution and exchange phases for Mg-topsoil columns which
received input HC1 solutions of pH 3.9 and 4.9,
respectively. Concentrations of cations in the solution
phase were in the order Al3 + > Na+ > Ca^+ > Mg^+ > K+, but
2+ 2+ 3+
for the exchange phase were in the order Mg > Ca > A1
> Na+ > K +. Abnormally high solution concentrations of
3+
Al were observed for both treatments. Comparison of
concentrations of cations in the exchange phase with values
in Table 4-4 for original exchangeable cations in Mg-topsoil
2+
showed that the concentration of Mg decreased but the
• 2+ ^ *f 3+ t
other cations such as Ca , K , Na and Al increased after
leaching with acid. This may be explained by decomposition
of the minerals due to the effect the input acid solutions.
A comparison of the CEC after leaching with the CEC of
initial pretreated topsoil showed a significant decrease but
if one compared the CEC that resulted after leaching with
the CEC of the original untreated topsoil (Table 4-5), good
agreement occured. A small decrease in CEC was found only
for the section of the soil column that received input acid
. 3+
solution. Large concentrations of exchangeable Al were
found at the end of the columns receiving input acid
solution.
Mixed subsoil. Tables 4-18 and 4-19 present
concentrations of cations in solution and exchange phases

183
Table 4-16 Concentrations of cations in solution
and exchange phases for Mg-topsoil after
leaching with pH 3.9 HCl solution
Depth
Ca
Mg
K
Na
A1
Sum
(cm)
mmole
(+) l'1
1.0
0.587
0.115
0.142
1.340
0.213
2.397
2.0
0.322
0.584
0.161
0.164
0.024
1.256
3.0
0.067
0.387
0.106
0.848
7.860
9.268
4.0
0.569
0.370
0.215
0.861
0.078
2.093
5.0
0.192
0.704
0.115
1.410
0.053
2.474
6.0
0.215
0.629
0.299
1.280
0.367
2.790
7.0
0.657
0.398
0.197
2.260
0.178
3.690
8.0
0.354
0.432
0.141
1.680
1.350
3.957
9.0
0.399
0.388
0.186
1.890
1.860
4.723
10.0
0.491
0.372
0.075
1.660
0.173
2.771
11.0
0.595
0.652
0.179
4.050
0.053
5.529
12.0
0.539
0.559
0.197
2.300
1.630
5.225
13.0
0.437
0.580
0.230
2.490
4.170
7.907
14.0
0.503
0.991
0.321
3.310
21.200
26.325
15.0
0.439
0.457
0.127
1.530
0.058
2.611
16.0
0.255
0.431
0.117
1.570
0.138
2.511
17.0
0.403
0.536
0.216
1.620
10.900
13.675
18.0
0.411
0.497
0.106
1.640
3.750
6.404
19.0
0.527
0.454
0.157
1.730
5.570
8.438
20.0
0.517
0.872
0.199
1.870
21.000
24.458
Depth
Ca
Mg
K
Na
A1
Sum
(cm)
phase
Kg 1
Hi JvL'Ildliy L.
1.0
1.320
0.473
0.230
0.391
6.772
9.186
2.0
2.880
4.110
0.281
0.478
1.001
8.750
3.0
2.060
7.200
0.153
0.435
0.767
10.615
5.0
2.540
8.640
0.326
0.467
0.890
12.863
7.0
1.950
9.260
0.166
0.348
0.801
12.525
10.0
1.850
9.460
0.198
0.304
0.767
12.579
13.0
1.920
9.460
0.185
0.348
0.745
12.658
16.0
2.160
8.840
0.166
0.283
0.645
12.094
18.0
1.980
10.100
0.205
0.337
0.601
13.223
20.0
2.210
10.700
0.230
0.500
0.556
14.196

184
Table 4-17 Concentrations of cations in solution
and exchange phases for Mg-topsoil after
leaching with pH 4.9 HCl solution
Depth
(cm)
Ca
Mg
i
K
Solution
Na
ph^se
Al
Sum
1.0
0.737
0.349 0.234'
1.740
2.080
5.140
2.0
0.413
0.494
0.150
2.350
11.700
15.107
3.0
0.626
0.415
0.183
1.550
1.410
4.184
4.0
0.596
0.329
0.230
2.000
3.740
6.895
5.0
0.631
0.698
0.357
2.070
1.670
5.426
6.0
0.701
0.434
0.363
2.490
2.860
6.848
7.0
0.180
0.681
0.225
1.680
32.600
35.366
8.0
0.695
0.527
0.358
1.970
10.600
14.150
9.0
0.293
0.528
0.178
1.940
13.600
16.539
10.0
0.607
0.372
0.166
1.380
2.740
5.265
11.0
0.418
0.588
0.160
1.720
11.900
14.786
12.0
1.000
0.666
0.577
3.990
0.183
6.416
13.0
0.363
0.553
0.302
2.440
8.480
12.138
14.0
0.152
0.502
0.175
1.100
17.700
19.629
15.0
0.134
0.543
0.187
1.280
17.300
19.444
16.0
0.087
0.605
0.171
0.848
19.600
21.311
17.0
0.120
0.647
0.310
1.520
22.800
25.397
18.0
0.031
0.518
0.213
1.210
17.100
19.072
19.0
0.132
0.592
0.190
1.270
21.900
24.084
20.0
0.134
0.513
0.189
0.751
12.900
14.487
Depth
(cm)
Ca
Mg
K
Na
phase
Al
Sum
Kg 1
1.0
2.070
5.550
0.416
0.500
2.335
10.871
3.0
1.920
8.640
0.160
0.391
0.956
12.067
5.0
1.710
8.840
0.141
0.304
0.923
11.918
7.0
1.860
8.840
0.294
0.446
0.767
12.207
9.0
1.630
9.460
0.147
0.228
0.812
12.277
11.0
1.670
9.050
0.115
0.239
0.689
11.763
14.0
1.720
9.460
0.160
0.370
0.634
12.344
16.0
1.770
9.670
0.173
0.359
0.712
12.684
18.0
1.770
8.640
0.365
0.489
0.623
11.887
20.0
1.970
10.100
0.294
0.565
0.656
13.585

185
for mixed subsoil columns that received input HCl solutions
of pH 3.9 and 4.9, respectively. Concentrations of cations
throughout the column for the solution phase were generally
in the order K+ > Na+ > Ca2+ > Mg2+ > Al3 + but, for the
+ 2+ 2+ 3+ +
exchange phase the order was K > Ca > Mg > Al > Na .
If one only examines the shallowest depth for the column
receiving the pH 3.9 input acid solution, the exchange-phase
3+ 2+ 2+ +
concentrations were in the order A1 > Ca > Mg > K >
Na+ and for pH treatment 4.9 in the order Ca2+ > Mg2 + > Al3 +
+ -f. , 2+ 2+
> K > Na . Concentrations of the basic cations Ca , Mg ,
*4" 3 •
K and Na were much less than the A1 concentration for
the pH 3.9 case. The pH 4.9 treatment had a reverse effect.
A comparison of concentrations on the exchange phase in
Tables 4-18 and 4-19 with values in Table 4-4 for the
original exchangeable cations in mixed subsoil showed that
. 2+ 2+ + +
concentrations of the basic cation Mg , Ca , K and Na
3+
were decreased but those Al remained fairly stable. The
base-cation saturation was remarkedly decreased by leaching.
Mixed topsoil. Tables 4-20 and 4-21 present
concentrations of cations in the solution and exchange
phases for mixed topsoil columns after receiving pH 3.9 and
4.9 input HCl solutions, respectively. Concentrations of
cations through the soil columns for the solution phase were
generally in the order Al3 + > Ca2+ > Mg2+ > K+ > Na+ for pH
treatment 3.9 and in the order Al3+ > Mg2+ > K+ > Ca2+ > Na+
for pH treatment 4.9. The exchange phase was in the order
Ca2+ > Al3+ > Mg2+ > K+ > Na+ for both treatments.

186
Table 4
Depth
(cm)
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
9.0
10.0
11.0
12.0
13.0
14.0
15.0
16.0
17.0
18.0
19.0
20.0
Depth
(cm)
1.0
2.0
3.0
5.0
7.0
9.0
12.0
15.0
18.0
20.0
18 Concentrations of cations in solution and
exchange phases for mixed-cation subsoil
after leaching with pH 3.9 HC1 solution
Ca Mg K Na Al Sum
Solution phase
mmole (+) L
0.050
0.016
0.142
0.178
0.017
0.403
0.082
0.037
0.151
0.165
0.011
0.446
0.085
0.062
0.205
0.167
0.011
0.530
0.062
0.058
0.129
0.100
0.011
0.360
0.040
0.021
0.288
0.139
0.000
0.487
0.032
0.016
0.260
0.115
0.006
0.429
0.015
0.025
0.285
0.133
0.013
0.471
0.027
0.021
0.326
0.148
0.022
0.544
0.060
0.037
0.365
0.202
0.006
0.669
0.000
0.000
2.530
0.154
0.000
2.684
0.078
0.035
0.523
0.334
0.060
1.029
0.057
0.021
0.386
0.243
0.050
0.757
0.035
0.016
0.362
0.189
0.000
0.602
0.015
0.012
0.365
0.165
0.000
0.557
0.042
0.020
0.375
0.219
0.033
0.689
0.023
0.005
0.324
0.236
0.014
0.602
0.012
0.015
0.301
0.130
0.007
0.464
0.027
0.010
0.335
0.157
0.027
0.555
0.033
0.015
0.275
0.193
0.020
0.536
0.045
0.020
0.410
0.237
0.060
0.772
Ca
Mg
K
Na
Al
Sum
2.990
0.716
0.491
0.222
8.117
12.536
4.640
3.040
1.010
0.183
0.912
9.785
5.240
3.130
1.370
0.191
1.007
10.938
4.940
2.960
3.500
0.196
0.845
12.441
4.690
2.710
4.450
0.174
0.790
12.814
4.790
2.630
5.650
0.191
0.899
14.160
4.790
2.140
6.270
0.200
0.723
14.123
4.140
2.330
6.040
0.226
0.801
13.537
4.890
2.410
6.500
0.217
0.634
14.651
4.240
2.350
6.340
0.252
0.656
13.838

187
Table 4-19 Concentrations of cations in solution and
exchange phases for mixed-cation subsoil
after leachingwith pH 4.9 HCl solution
Depth Ca Mg K Na A1 Sum
(cm) Solution phase
mmole (+) L
1.0
0.062
0.041
0.414
0.120
0.006
0.643
2.0
0.047
0.033
0.267
0.122
0.011
0.480
3.0
0.027
0.013
0.354
0.086
0.018
0.498
4.0
0.035
0.008
0.247
0.107
0.011
0.408
5.0
0.057
0.016
0.421
0.183
0.017
0.695
6.0
0.032
0.008
0.656
0.087
0.000
0.784
7.0
0.030
0.016
0.344
0.124
0.022
0.537
8.0
0.025
0.008
0.342
0.126
0.011
0.512
9.0
0.092
0.021
0.384
0.217
0.011
0.725
10.0
0.025
0.008
0.265
0.122
0.006
0.426
11.0
0.027
0.008
0.307
0.130
0.006
0.478
12.0
0.027
0.004
0.288
0.098
0.006
0.423
13.0
0.020
0.008
0.434
0.135
0.028
0.625
14.0
0.037
0.012
0.404
0.167
0.017
0.637
15.0
0.027
0.012
0.377
0.133
0.011
0.561
16.0
0.077
0.037
0.794
0.128
0.022
1.059
17.0
0.007
0.008
0.287
0.104
0.028
0.435
18.0
0.020
0.008
0.411
0.200
0.028
0.667
19.0
0.075
0.025
0.625
0.170
0.020
0.915
20.0
0.018
0.008
0.375
0.091
0.028
0.520
Depth
Ca
Mg
K
Na
A1
Sum
(cm)
Kg 1 ¡
1.0
3.590
3.620
1.430
0.313
2.635
11.588
3.0
4.540
2.960
3.480
0.196
1.190
12.366
5.0
4.490
2.630
4.550
0.200
0.956
12.826
7.0
4.690
2.300
4.940
0.196
1.012
13.138
9.0
4.040
2.570
5.350
0.200
0.878
13.038
11.0
3.940
2.500
5.550
0.183
0.756
12.929
14.0
4.040
2.390
5.830
0.130
0.812
13.202
16.0
4.190
2.330
6.060
0.191
0.701
13.472
18.0
4.090
2.220
5.940
0.235
0.689
13.174
20.0
4.240
2.100
6.640
0.243
0.767
13.990

188
Table 4-20 Concentrations of cations in solution and
exchange phases for mixed-cation topsoil
after leaching with pH 3.9 HCl solution
Depth
(cm)
Ca
Mg K
Na
Al
Sum
1.0
0.202
0.078
0.151
0.115
0.100
0.646
2.0
0.167
0.062
0.155
0.183
0.139
0.706
3.0
0.205
0.074
0.182
0.159
0.094
0.715
4.0
0.227
0.128
0.208
0.193
0.295
1.051
5.0
0.279
0.152
0.223
0.196
1.070
1.920
6.0
0.319
0.267
0.313
0.198
13.800
14.897
7.0
0.277
0.197
0.228
0.154
2.300
3.156
8.0
0.342
0.276
0.205
0.124
9.060
10.007
9.0
0.317
0.230
0.220
0.150
1.530
2.447
10.0
0.414
0.415
0.292
0.152
23.000
24.273
11.0
0.409
0.341
0.290
0.157
10.800
11.997
12.0
0.392
0.317
0.385
0.148
7.800
9.042
13.0
0.384
0.247
0.294
0.187
1.150
2.262
14.0
0.359
0.346
0.278
0.141
14.000
15.124
15.0
0.387
0.354
0.504
0.152
13.400
14.797
16.0
0.334
0.235
0.340
0.182
0.757
1.848
17.0
0.374
0.420
0.336
0.117
23.100
24.347
18.0
0.394
0.337
0.344
0.159
12.100
13.334
19.0
0.334
0.296
0.267
0.100
10.000
10.997
20.0
0.357
0.284
0.331
0.109
9.440
10.521
Depth Ca Mg K Na A1 Sum
(cm) Exchange phas|
1.0
3.340
mm
0.946
ole (+)
0.379
Kg ;
0.252
soil
4.770
9.687
3.0
4.040
0.872
0.358
0.239
2.320
7.829
6.0
5.440
1.650
0.489
0.226
2.210
10.015
8.0
5.290
1.890
0.650
0.217
2.430
10.477
10.0
5.490
1.890
0.650
0.209
2.420
10.659
12.0
5.640
2.040
0.744
0.174
2.160
10.758
14.0
6.040
2.020
0.837
0.226
2.350
11.473
17.0
6.040
2.000
0.929
0.130
2.040
11.139
18.0
6.790
2.050
1.030
0.109
1.630
11.609
20.0
6.420
2.130
1.150
0.109
1.460
11.269

189
Table 4-21 Concentrations of cations in solution and
exchange phases for mixed-cation topsoil
after leaching with pH 4.9 HC1 solution
Depth Ca Mg K Na Al Sum
(cm) Solution ph^se
mmole(+) L
1.0
0.413
0.173
0.138
0.170
11.300
12.194
2.0
0.382
0.111
0.137
0.096
0.600
1.326
3.0
0.497
0.459
0.305
0.136
41.800
43.197
4.0
0.491
0.326
0.295
0.146
20.800
22.058
5.0
0.281
0.420
0.325
0.073
30.500
31.599
6.0
0.272
0.485
0.353
0.067
32.600
33.777
7.0
0.311
0.474
0.427
0.162
38.500
39.874
8.0
0.252
0.403
0.321
0.089
31.400
32.465
9.0
0.217
0.276
0.257
0.150
17.300
18.200
10.0
0.254
0.378
0.257
0.074
3.270
4.233
11.0
0.245
0.119
0.283
0.122
1.350
2.119
12.0
0.232
0.218
0.217
0.080
10.200
10.947
13.0
0.249
0.385
0.272
0.055
33.100
34.061
14.0
0.202
0.292
0.223
0.089
29.800
30.606
15.0
0.309
0.601
0.389
0.083
64.400
65.782
16.0
0.225
0.257
0.315
0.123
16.300
17.220
17.0
0.263
0.449
0.364
0.086
33.100
34.262
18.0
0.269
0.548
0.413
0.112
66.000
67.342
19.0
0.344
0.563
0.328
0.112
69.300
70.647
20.0
0.326
0.360
0.431
0.271
18.900
20.288
Depth
(cm)
Ca
Mg
K
Na
Al
Sum
Kg
2.0
5.140
1.760
0.647
0.217
3.847
11.611
3.0
6.040
1.910
0.729
0.200
2.913
11.792
6.0
5.190
1.790
0.998
0.209
2.780
10.967
8.0
5.990
1.970
1.110
0.200
2.769
12.039
10.0
5.840
1.790
1.040
0.191
2.680
11.541
12.0
5.240
1.810
1.030
0.235
2.713
11.028
13.0
4.740
1.720
0.941
0.130
2.646
10.177
16.0
5.040
1.710
1.120
0.226
2.402
10.498
18.0
4.690
1.780
1.190
0.209
2.858
10.727
19.0
6.190
1.950
1.220
0.217
2.558
12.135

190
3 +
Concentrations of Al in the solution phase were relatively
high for both treatments. If one examined only the
shallowest depth (at the end of the column receiving acid
input solution), cation concentrations in the exchange phase
were in the order Ca2+ > Al2+ > Mg2+ > K+ > Na+ for pH
treatment 4.9 and in the order Al2+ > Ca2+ > Mg2+ > K+ > Na+
3+
for pH treatment 3.9. Higher A1 concentrations but lower
. 2+ 2+ + +
concentrations of the basic cations Ca , Mg , K , and Na
were found at the input end of the soil column for the pH
3.9 case.
Charge Balance Using All Major Cations for Treated and
Mixed Soil Columns
The charge balance of all major cations for pretreated
and mixed topsoil and subsoil are given in Tables 4-22
through 4-27. The theoretical charge balance of major
cations in each soil column can be described by the
following relationship
Total H+ (mmole(+)) added + Exchangeable cations (mmole(+))
(includes exchangeable H+)
initially present on soil
exchange sites
= Total H+ (mmole(+)) and cations (mmole(+))
exported from the soil column
+ Exchangeable cations (mmole(+)) (includes H+ ions)
remaining in the soil column. [4-3]
Details for the calculation procedure are the same as
stated in chapter three. In the following text the

191
Table 4-22
Charge balance
Ca-topsoil
of cations for columns of
Ca
-topsoil
pH 3.9
(mmole(+) )
„ 2+
.. 2+
, 3 +
H
Ca
Mg
K
Na
Al
Initial cations
4.163
0.007
0.036
0.000
0.783
Total input
0.284
Final
#
0.075
0.060
0.017
0.169
0.004
solution
phase
Final
#
3.682
0.017
0.103
0.116
0.518
exchange
phase
Total
0.004
4.060
0.016
0.024
0.100
0.116
output in
effluent
Ca
-topsoil
pH 4.9
(mmole(+))
2+
, 3 +
H
Ca
Mg
K
Na
Al
Initial cations
4.240
0.007
0.036
0.000
0.800
Total input
0.029
Final
#
0.070
0.012
0.029
0.059
0.002
solution
phase
Final
#
3.810
0.022
0.093
0.095
2.000
exchange
phase
Total
0.003
2.120
0.042
0.019
0.023
0.193
output in
effluent
#: undetermined

192
Table 4-23 Charge balance of cations for columns of
K-topsoil
K-topsoil pH 3.9 (mmole(+))
H+
Ca2+
Mg2 +
K+
Na+
Al3 +
Initial cations
0.219
0.030
6.272
0.109
2.115
Total input 0.348
Final #
0.036
0.117
0.075
0.121
0.009
solution phase
Final #
0.335
0.048
0.893
0.081
2.210
exchange phase
Total 0.009
0.001
0.001
5.144
0.042
2.910
output in effluent
K-topsoil pH 4.9 (mmole(+))
H+
Ca2+
Mg2+
K+
Na+
Al3+
Initial cations
Total input 0.029
0.217
0.029
6.233
0.108
2.102
Final #
solution phase
0.026
0.078
0.069
0.068
0.002
Final #
exchange phase
0.275
0.040
0.990
0.077
0.584
Total 0.008
outputin effluent
0.233
0.044
5.167
0.098
2.518
#: undetermined

193
Table 4-24 Charge balance
Mg-topsoil
of cations for columns of
Mg-
•topsoil
pH 3.9 (mmole(+))
„ 2+
2 +
+
, 3 +
H
Ca
Mg
K
Na
A1
Initial cations
0.326
4.241
0.072
0.109
0.181
Total input 0.277
Final #
0.030
0.043
0.016
0.145
0.330
solution phase
Final #
0.756
2.836
0.776
0.141
0.491
exchange phase
Total 0.001
0.033
9.840
0.022
0.021
0.739
output in effluent
Mg-
topsoil
pH 4.9 (mmole(+))
2+
H
Ca
Mg
K
Na
A1
Initial cations
0.326
4.241
0.072
0.109
0.181
Total input 0.025
Final #
0.033
0.044
0.020
0.146
1.341
solution phase
Final #
0.656
0.320
0.082
0.141
0.330
exchange phase
Total 0.001
0.035
4.128
0.040
0.017
0.849
output in effluent
# : undetermined

194
Table 4-25 Charge balance of cations for columns of
Ca-subsoil
Ca
-subsoil
pH 3.9 (mmole(+))
H+
Ca2+
M 2+
Mg
K+
Na+
Al3 +
Initial cations
17.900
0.033
0.066
0.000
0.066
Total input 0.271
Final #
0.050
0.006
0.020
0.126
0.058
solution phase
Final #
3.580
0.011
0.088
0.086
0.321
exchange phase
Total 0.003
14.926
0.029
0.026
0.023
0.012
output in effluent
Ca-
-subsoil
pH 4.9 (mmole(+))
„ 2+
+
H
Ca
Mg
K
Na
A1
Initial cations
17.900
0.033
0.066
0.000
0.066
Total input 0.024
Final #
0.060
0.006
0.016
0.162
0.026
solution phase
Final #
3.500
0.016
0.061
0.100
0.124
exchange phase
Total 0.003
14.167
0.020
0.045
0.038
0.071
output in effluent
#: undetermined

195
Table 4-26
Charge balance
K-subsoil
of cations for columns of
K-
â– subsoil
pH 3.9
(mmole(+))
„ 2+
+
, 3 +
H
Ca
Mg
K
Na
Al
Initial cations
0.430
0.031
15.421
0.123
0.215
Total input
0.271
Final
#
0.050
0.008
0.051
0.207
0.002
solution phase
Final
#
0.372
0.021
3.721
0.208
0.450
exchange phase
Total
0.009
0.151
0.030
11.140
0.030
0.015
output in
effluent
K-subsoil pH
4.9 (mmole(+))
„ 2+
.. 2 +
, 3 +
H
Ca
Mg
K
Na
Al
Initial cations
0.424
0.030
15.199
0.121
0.212
Total input
0.026
Final
#
0.044
0.006
0.042
0.176
0.001
solution phase
Final
#
0.393
0.026
4.208
0.214
0.303
exchange phase
Total
0.008
0.082
0.019
6.872
0.021
0.010
output in effluent
#: undetermined

196
Table 4-27 Charge balance of cations for columns of
Mg-subsoil
Mg
f-subsoil
pH 3.9
(mmole(+))
„ 2+
„ 2+
, 3 +
H
Ca
Mg
K
Na
Al
Initial cations
0.093
30.164
0.093
0.006
0.436
Total input 0.125
Final #
0.044
0.013
0.015
0.148
0.001
solution phase
Final #
0.237
2.518
0.077
0.099
0.725
exchange phase
Total 0.021
0.041
22.959
0.043
0.041
0.062
output in effluent
Mg
-subsoil
pH 4.9
(mmole(+))
2+
. 3 +
H
Ca
Mg
K
Na
Al
Initial cations
0.094
30.380
0.094
0.063
0.044
Total input 0.026
Final #
0.037
0.010
0.020
0.108
0.029
solution phase
Final #
0.263
2.956
0.075
0.111
0.602
exchange phase
Total 0.01
0.154
22.438
0.035
0.039
0.035
output in effluent
#: undetermined

197
terminology of "input" and "output" refers to the left- and
right- hand sides of equation [4-3], respectively.
Treated Topsoil. Tables 4-22 through 4-24 present the
charge balance of Ca-topsoil, K-topsoil and Mg-topsoil,
respectively. Inputs were 5.272 and 5.112 mmole(+) and
outputs were 8.893 and 8.590 mmole(+) for Ca-topsoil that
received treatment pH 3.9 and 4.9 HCl solutions,
respectively. Therefore, very large charge-balance errors,
of + 69 and + 68%, were observed for Ca-topsoil for
treatments of pH 3.9 and 4.9, respectively. From Table 4-22
2+
the sum of concentrations of Ca in the exchange phase and
. . . 2+
effluent exceeded the initial quantities of Ca in the
Ca-topsoil, indicating that soil minerals underwent
dissolution during leaching with the HCl solutions. Inputs
were 9.353 and 8.718 mmole(+) and outputs were 12.031 and
10.275 mmole(+) for K-topsoil that received pH 3.9 and 4.9
HCl solutions, respectively. Charge-balance errors for
K-topsoil were + 29 and + 15% for the pH 3.9 and 4.9
treatments, respectively. Inputs were 5.206 and 4.954
mmole(+), and outputs were 15.734 and 8.183 mmole(+) for
Mg-topsoil that received pH 3.9 and 4.9 HCl solutions,
respectively. Charge-balance errors were + 202 and + 8% for
treatments of pH 3.9 and 4.9 respectively. The extremely
large error observed for the pH 3.9 treatment with
Mg-topsoil can possibly be explained by the effect of
. 2+
mineral dissolution, since concentrations of Mg in the
exchange phase and effluent were 3-fold greater than the

198
initial quantities for Mg-topsoil. For all of the
pretreated topsoil, quantities of all cations leached were
not directly proportional to the H+ concentration of the
applied solution, but larger quantities of major cations
were leached from columns receiving pH 3.9 HC1 than for pH
4.9 HC1. For example, for Ca-topsoil that received pH 3.9
HCl, 4.06 mole(+) of Ca^+ were leached but only 2.12
mmole(+) were leached when pH 4.9 HCl was applied. Mineral
dissolution was implied from concentrations of cations in
the leachate and on exchange sites. For example for
Ca-topsoil, K+ and Na+ were initially 0.036 and 0.0 mmole(+)
in the exchange phase but became 0.103 and 0.116 mmole(+)
after leaching with pH 3.9 HCl. Similar results were
observed for all treated topsoil columns of all cations
species examined. The increase of exchangeable-cation
3+
concentration was most dramatic for Al . Output from the
treated topsoil was observed to be greater than input, and
the resulting positive-charge-balance errors can be
attributed to the dissolution or decomposition of
interlayer-hydroxy vermiculite, as well as to other mineral¬
weathering processes in this soil.
Treated subsoil. Tables 4-25 through 4-27 present the
charge balance for Ca-subsoil, K-subsoil and Mg-subsoil,
respectively. Inputs were 18.336 and 18.089 mmole(+) and
outputs were 19.473 and 18.418 mmole(+) for Ca-subsoil that
received pH 3.9 and 4.9 HCl solutions, respectively.
Ca-subsoil gave charge-balance errors of + 6 and + 2 % for

199
pH 3.9 and 4.9 HCl solutions, respectively. Inputs were
16.491 and 16.012 mmole(+) and outputs were 16.465 and
12.425 mmole(+) for K-subsoil receiving pH 3.9 and 4.9 HCl
solutions, respectively. K-subsoil thus gave + 4 and + 22 %
charge-balance errors for treatments of pH 3.9 and 4.9,
respectively. Inputs were 30.917 and 30.701 mmole(+), and
outputs were 27.020 and 26.931 mmole(+) for Mg-subsoil that
received pH 3.9 and 4.9 HCl solutions, respectively.
Mg-subsoil thus gave - 13 and - 12% charge-balance errors
for treatments of pH 3.9 and 4.9, respectively. For all of
the pretreated subsoil, quantities of cations leached were
not directly proportional to H+ concentration of the applied
HCl solution for the major saturating cation. For example
for K-subsoil that received pH 3.9 solution, 11.140 mmole(+)
of K+ was leached, but only 6.872 mmole(+) was leached when
pH 4.9 acid was applied. The leaching of other cations was
also less than proportional to the applied solution pH. The
result of mineral dissolution was evident from the
concentrations of cations in the leachate and an exchange
phases, but was not as much as for the topsoil. For
+ 3+
Mg-subsoil, for example, concentrations of Na and A1
initially on the exchange sites were 0.006 and 0.436
mmole(+) but, after leaching with pH 3.9 HCl solution, these
concentrations became 0.041 and 0.725 mmole(+),
respectively. For all of the treated Cecil subsoil columns
the outputs were much less than were inputs, and negative
charge-balance errors occurred. This can be explained by

200
the red-orange color of the treated Cecil subsoil, which is
due to substantial amounts of Fe oxides. pH-Dependent sites
for these oxides tend to develop a negatively charged
surface at moderate to high pH (pH > 5.0). The stable pH
readings for the samples of effluent and of soil solution
were near 6.5. Therefore, some of the exchangeable cations
were adsorbed for charge-balance purpose, resulting in a
decrease in the quantity of exchangeable cations or cations
exported.
Mixed soil. Tables 4-28 and 4-29 present the charge
balance for mixed subsoil and topsoil, respectively.
Inputs were 8.161 and 7.841 mmole(+) and outputs were 11.576
and 12.656 mmole(+) for mixed topsoil that received pH 3.9
and 4.9 HCl solution, respectively. Charge-balance errors
for mixed topsoil were + 42 and + 61% for treatments pH 3.9
and 4.9, respectively. The large charge-balance error was
explained by mineral dissolution. Inputs were 24.825 and
24.582 mmole(+) and outputs were 26.889 and 30.360 ramole(+)
for mixed subsoil that received pH 3.9 and 4.9 acid,
respectively. Charge-balance errors for mixed subsoil were
8% and 23% for treatments of pH 3.9 and 4.9, respectively.
Mixed soils obtained by mixing the three pretreated soils in
2+
a 1: 1: 1 weight ratio resulted in Mg domination of
exchange sites. Concentrations of cations in the leachate
2+ 2+
were also dominated by Mg . Thus leaching losses of Mg
were greater than for all other cations. Total
concentrations of each cation in the effluent were not

201
Table 4-28 Charge balance of cations for columns of
mixed-cation subsoil
Mixed-cation subsoil
pH 3.9
(mmole(+))
„ 2+
.. 2 +
, 3 +
H
Ca
Mg
K
Na
A1
Initial cations
8.544
10.233
5.360
0.162
0.260
Total input 0.267
Final #
0.004
0.002
0.040
0.017
0.002
solution phase
Final #
1.473
0.793
1.352
0.067
0.500
exchange phase
Total 0.008
9.900
8.970
3.720
0.028
0.017
output in effluent
Mixed-cation subsoil
pH 4.9
(mmole(+))
+
„ 2+
„ 2+
H
Ca
Mg
K
Na
A1
Initial cations
8.544
10.233
5.360
0.162
0.260
Total input 0.024
Final #
0.003
0.002
0.039
0.013
0.002
solution phase
Final #
1.360
0.832
1.617
0.068
0.338
exchange phase
Total 0.007
8.183
8.000
4.640
0.036
0.020
output in effluent
#: undetermined

202
Table 4-29 Charge balance of cations for columns of
mixed-cation topsoil
Mixed
topsoil
pH 3.9
(mmole(+))
H+
ca2+
M 2+
Mg
K+
Na+
Al3 +
Initial cations
1.894
2.413
2.265
0.222
1.114
Total input 0.253
Final #
0.026
0.020
0.022
0.012
0.607
solution phase
Final #
2.025
0.650
0.268
0.070
0.883
exchange phase
Total 0.03
1.357
2.147
2.058
0.029
1.372
output in effluent
Mixed topsoil
pH 4.9
(mmole(+))
„ 2 +
, 3 +
H
Ca
Mg
K
Na
Al
Initial cations
1.871
2.385
2.238
0.220
1.101
Total input 0.026
Final #
0.024
0.029
0.024
0.009
2.282
solution phase
Final #
1.985
0.667
0.368
0.075
1.033
exchange phase
Total 0.033
1.548
2.030
1.905
0.023
0.621
output in effluent
#: undetermined

203
proportional to the H+ concentration of the applied solution
for the mixed soil, but the application of pH 3.9 acid
solution did increase the quantities of cations leached
compared to the case where pH 4.9 solution was applied.
Base saturation of cations was apparently decreased by acid
application to the soil columns.
Conclusions
The clay content of treated subsoil was 2.7-fold
greater than for treated topsoil, but organic matter content
was 1.6-fold greater for the topsoil than for the subsoil.
Exchange sites of pretreated Cecil subsoil gave
equivalent fractions of 95 and 99 % saturation with respect
+ + 2+
to the major cation of saturation (K , Ca , or Mg ) in the
cases of where exchangeable Al^+ was considered or not in
the calculation of cation exchange capacity. For pretreated
Cecil topsoil, however, equivalent fractions totalled 85 and
95% saturation with respect to the major cation of
+ 2+ 2+
saturation (K , Ca , or Mg ). Leaching of Cecil soil with
unbuffered salt solution resulted in an increase in the
cation exchange capacity of the soil.
All of the first few samples of effluent from soil
columns that received HCl solutions were observed to have
low pH but high concentrations of cations. This observation
could be explained by the replacement efficiency of H+ for
the cation-saturated sites as well as by a salt effect.
Soil chemically pretreated with a given cation was observed
to be more sensitive to the pH effect of the input solution

204
than untreated soil. Concentrations of the major saturating
cation in the column effluent usually were not proportional
to the H+ concentration of the applied input solution,
though concentrations of major cations were usually higher
in the effluent from columns receiving pH 3.9 solution as
compared to columns receiving pH 4.9 solution. Cation
concentrations in the solution and exchange phases of soil
columns were in general as expected, with cation
concentrations in the solution phase being in the order Na+
■f* 2+ 2+ • •
> K > Mg > Ca , whereas concentrations in the exchange
3+ 2+ 2+ + +
phase were in the order A1 > Ca > Mg > K > Na .
Exceptions to these orders, however, were observed for some
columns.
Although pretreatment of the soil eliminated much
uncertainty with respect to chemical analysis, observed
charge balances were larger between inputs and outputs for
all of the pretreated and mixed soils. As HCl acid
solutions were applied to the columns, several complicated
soil chemical reactions occurred between the pH-independent
exchange sites as well as between newly formed exchange
sites and pH-dependent charge-surface sites. Further
investigation of the effects of acid upon Cecil soil is
needed in the future, in order to understand the mechanism
and dissolution rate of interlayer vermiculite upon acid
application. Addition of neutral salt during chemical
treatment of the soil increased the exchange capacity of the
soil, and subsequent application of HCl acid solution to the

205
treated soil tended to accelerate the leaching loss of
2+ 2+
nutrient cations (Ca , Mg ) and induced the transformation
of nonexchangeable A1 to exchangeable Al^ + .
Acid deposition tended to adversely effect Cecil soil
by decreasing its fertility status. Therefore, under forest
conditions, fertilizer and lime application might be needed
2+ 2+
in the future to replace Ca and Mg leached from Cecil
soil if prolonged acid precipitation occurs.

CHAPTER V
SUMMARY AND CONCLUSIONS
Summary
Cecil (Typic Hapludult) soil was used in investigations
of cation movement during steady displacement of electrolyte
solution and of cation leaching during application of acid
solutions under constant-flux conditions. Cecil soil was
characterized as a highly weathered soil. The principal
clay minerals in topsoil (0-30 cm depth) and subsoil (30-60
cm depth) were interstratified or interlayered vermiculite,
kaolinite, and quartz. Gibbsite was found only in the
subsoil. Topsoil and subsoil textures were classified as
sandy loam and sandy clay loam, respectively. Organic
matter (O.M) contents for topsoil and subsoil were 1.60 and
1.04%, respectively.
Studies of cation transport were conducted using
columns filled with water-saturated Cecil topsoil or
subsoil. Using a steady liquid flux of 1 cm h soil
2+
columns were initially saturated with Ca , using 0.005 M
CaC^, and then miscibly displaced by 0.005 M MgC^
solution. After displacing 4.5 and 3.6 pore volumes of
MgCl2 solution for topsoil and subsoil columns,
respectively, the flow was terminated. Soil columns were
equilibrated overnight, before dissection into sections the
next day. Cations in the solution and exchange phases were
206

207
separated by a centrifuge method. In the solution and
exchange phases, distributions of cation species and CEC
3 +
varied with depth m the columns. A1 comprised about 25
and 50% of the total exchangeable cations in subsoil and
topsoil columns, respectively. The large aluminum contents
of the Cecil soil are possibly due to dissolution of
interlayered vermiculite (M+ (Mg,Fe)3 (S^,A1)4 01Q (OH)2),
and of hydrous Al oxides.
2+ . 2+
The Mg exchange isotherm curve for the binary Mg ->
2+
Ca reaction was concave in shape and indicated that
exchange sites in both the topsoil and subsoil preferred
2+ 2+
Ca over Mg . Average magnitudes of selectivity
coefficients for the topsoil and subsoil were 0.225 and
0.798, respectively. Hydrodynamic dispersion coefficients
obtained from experimental Cl breakthrough curves were 1.85
-4 -4 2-1
x 10 and 3.03 x 10 m h , respectively, for subsoil and
topsoil columns.
A computer model was developed for predicting the
transport and exchange of two cation species in Cecil soil
columns. The model is based upon a Galerkin finite-element
numerical solution of the convective-dispersive partial
differential equation. The governing equation describes
one-dimensional transport and binary exchange of cations
under steady water flow through soil. The exchange term in
the transport equation is treated as an explicit function of
total solution concentration, cation exchange capacity,
valence and cation concentrations in the solution phase.

208
The use of cubic spline functions as shape functions enabled
employment of a Galerkin finite-element formulation over the
spatial and time domain. The resulting ordinary
differential equations were solved by a method based on
backward differentiation formulation (Gear, 1969).
Verification of the numerical model was performed using
an analytical model for nonreactive solute transport during
miscible displacement, where the retardation factor (R) is
assumed to be unity. Verification was also performed for
the case of non-preferential ion exchange with a selectivity
coefficient equal to unity and cation-transport retardation
R = 1 + [(a CT)/(0 CT)].
Sensitivity analyses for dispersion coefficient,
volumetric water content, bulk density, selectivity
coefficient and cation exchange capacity parameters were
performed for the numerical model with respect to the
experimental data from the columns of Cecil soil.
Sensitivity analysis showed cation exchange capacity to be
the most critical parameter in the model. Relatively small
values of CEC gave the best simulations for measured cation-
concentration distributions with depth in the solution and
exchange phases. Use of CEC values obtained from 1 M NH^OAc
extraction resulted in discrepancies between observed and
predicted cation distributions within the columns.
Leaching of soil cations was investigated during
displacement of acid solutions under constant liquid flux
through columns of initially air-dry Cecil topsoil and

209
subsoil. Samples of Cecil topsoil and subsoil were treated
with electrolyte solutions in order to saturate exchange
+ 2+ 2+
sites with a single (K , Ca , or Mg ) cation (treated
soil). Mixed soils were obtained by mixing equal masses of
K+-, Ca2+-, and Mg^+- saturated soils. Packed soil columns
used in these experiments were 10-cm long for nontreated
soil, and 20-cm long for treated and mixed soils. Dilute
aqueous HC1 solutions of pH 3.9 or 4.9 were applied at 1.0
cm h-1 Darcy flux to separate air-dry soil columns, until
approximately 30 pore volumes of effluent had been
collected. Initially, liquid flow into the soil was
transient as the wetting front moved through the unsaturated
soil, and effluent outflow did not occur until the wetting
front had reached the end of the column. Steady flow
occurred after a short transition period.
For all columns, regardless of applied-solution pH,
initial samples of effluent were characterized by low pH and
2+ 2+ + +
high concentrations of basic (Ca , Mg , K , Na ) and
3+
acidic (Al ) cation species. These observations were
attributed primarily to miscible displacement of soil
solution originally present within small pores, and
secondarily to the combined effects of removal of
exchangeable cations by ion exchange with H+ ions, and
release of cations by mineral hydrolysis, as the acid
wetting front penetrated the initially air-dry soil column.
With increasing volume of column effluent, cation
concentrations dramatically decreased and pH increased up to

210
about 5 pore volumes of effluent for nontreated soil, 3 pore
volumes for treated soil, and 3.5 pore volumes for mixed
soils. Between 5 to 30 pore volumes, effluent pH was in the
range of 6.0 - 6.5, but cation concentrations decreased in a
gradual manner. The H+ ions were obviously removed from the
soil solution at a fairly constant rate during the last 25
pore volumes of effluent as exchangeable cations were
leached from the soil.
During application of pH 3.9 and 4.9 HCl solutions, the
total quantities of basic cation eluted in effluent were
0.286 and 0.238 mmole(+), respectively, from columns of
nontreated topsoil; 0.395 and 0.306 mmole(+), respectively,
from nontreated subsoil; 4.204 and 2.207 mmole(+),
respectively, from Ca-topsoil; 5.697 and 5.55 mmole(+),
respectively, from K-topsoil; 9.917 and 4.221 mmole(+),
respectively, from Mg-topsoil; 15.007 and 14.273 mmole(+),
respectively, from Ca-subsoil; 11.360 and 7.002 mmole(+),
respectively, from K-subsoil; 23.105 and 22.676 mmole(+),
respectively, from Mg-subsoil; 22.626 and 21.066 mmole(+),
respectively, from mixed subsoil; and 5.621 and 5.519
mmole(+), respectively, from mixed topsoil. Also, during
application of pH 3.9 and 4.9 HCl solutions, total
quantities of aluminum were 0.110 and 0.017 mmole(+),
respectively, from nontreated topsoil; 0.001 and 0.001
mmole(+), respectively, from nontreated subsoil; 0.116 and
0.193 mmole(+), respectively, from Ca-topsoil; 2.910 and
2.518 mmole(+), respectively, from K-topsoil; 0.739 and

211
mmole(+), respectively, from Mg-topsoil; 0.012 and 0.071
mmole(+), respectively, from Ca-subsoil; 0.062 and 0.035
mmole(+), respectively, from Mg-subsoil; 0.015 and 0.010
mmole(+), respectively, from K-subsoil; 1.372 and 0.621
mmole(+) from mixed topsoil; and 0.017 and 0.020
mmole(+)respectively, from mixed subsoil. Therefore, the
total leaching of basic cations in the effluent from the
soil columns that received ten-fold different H+
concentrations differed by less than two-fold, indicating
that, in addition to ion exchange, chemical reactions such
as acid dissolution of soil minerals were important during
. . 3+
the leaching process. Higher concentrations of Al were
observed in column effluent from nontreated topsoil than
3+
from nontreated subsoil, but the concentrations of Al were
very low for all chemically pretreated and mixed subsoil
columns.
Distributions of cation concentrations on the exchange
sites revealed that, during displacement of pH 3.9 acid
solutions through the soil columns, base saturation
decreased from 52 to 11% for nontreated topsoil; from 68 to
29% for nontreated subsoil; from 99 to 27% for K-subsoil;
from 99 to 10% for Mg-subsoil; from 99 to 21% for
Ca-subsoil; from 85 to 79% for Ca-topsoil; from 76 to 15%
for K-topsoil; from 96 to 24% for Mg-topsoil; from 99 to 15%
for mixed subsoil, and from 86 to 38% for mixed topsoil.
During the period of pH 4.9 acid solution application, base
saturation decreased from 52 to 12 % for nontreated topsoil;

212
from 68 to 35% for nontreated subsoil; from 99 to 31% for
K-subsoil; from 99 to 11% for Mg-subsoil; from 99 to 21% for
Ca-subsoil; from 85 to 80% for Ca-topsoil; from 76 to 16%
for K-topsoil, 96 to 91% for Mg-topsoil, 99 to 16 % for
mixed subsoil; from 86 to 40% for mixed topsoil. As
expected, the distribution of cations on soil exchange sites
followed the order Al3+ > Mg^+ > Ca^+ > Mg^+ > K+ = Na+,
. + + 24-
while for the solution phase the order was Na > K » Ca >
2+ 3 +
Mg > A1 The most significant response to input HC1
solution occurred at the receiving end of the soil columns,
3+
where larger values of exchangeable Al were observed.
Base saturation drastically decreased for columns of soil
which received pH 3.9 input acid solution. Columns of soil
which were chemically pretreated showed a greater decrease
in base saturation than did nontreated soil.
Conclusions
In general, the numerical model for binary cation
transport during steady liquid flow agreed very well with
analytical solutions for simple cases. Experiments were
performed to generate data for evaluating the predictive
capacity of the numerical model. During steady liquid flow
through water-saturated columns of Ca-saturated Cecil
topsoil and subsoil, aqueous MgC^ solutions were displaced
through the columns. When the overall measured CEC values
in the column were used as the input for the model,
simulated results overestimated the distributions of cation
concentrations in the columns. When the measured sum of

213
dominant basic cations was used as input CEC for the model,
however, the numerical simulation result gave a reasonable
prediction of the experimental data. The model proposed in
this study was shown to approximate the cation transport and
exchange processes during one-dimensional steady
displacement through columns of Cecil soil.
A ten-fold difference in H+ concentrations of HC1
solutions applied at constant flux to columns of nontreated,
treated, and mixed Cecil soil resulted in a less than
proportional difference in quantities of cations removed in
the effluent. This difference was noted from H+ and cations
added and recovered as a result of H+ interactions with and
dissolution of soil minerals. Therefore, further
investigation of effects of acid upon Cecil soil is needed
to determine dissolution rates for interlayered vermiculite
as well as for Al hydrous oxide, and for gibbsite.
Leaching of cations during acid application to Cecil
soil columns under laboratory condition presents an extreme
case compared to field conditions when periodic wetting and
drying of soil during rainfall events limit cation exchange
and transport with the water, and where cations released by
the dynamic weathering of soil minerals tends to offset
cation-leaching losses. The most deleterious effects of
acid deposition on the soil would be those cases where the
soil is of low CEC and of medium to high base saturation.
For most acid agricultural soils where lime and
fertilizer are applied with relatively high frequency, the

214
effects of acid deposition are likely to go unnoticed.
However, for certain forest soils, periodical fertilizer
application may be needed in the future to minimize adverse
effects of acid deposition upon soil fertility.

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BIOGRAPHICAL SKETCH
Ko-Hui Liu was born on November 5, 1951, in Taichung,
Taiwan, Republic of China. After graduating from high
school she entered National Chung-Hsing University,
Taichung, Taiwan, where she received her Bachelor of Science
degree in 1974. She then taught high school in the city of
Taipei. In the fall of 1979 she enrolled as a graduate
student in the Department of Soil Science at the University
of Florida. After receiving her Master of Science degree in
1982, she remained to perform graduate study toward the
Ph.D. degree.
She is married to Ming-Hsinug Chen. She is a member of
Gamma Sigma Delta, the Honor Society of Agriculture, and is
also an associate member of Sigma Xi.
221

I certify that I have read this study and that in ray
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the deqree of Doctor of Philosophy.
Professor of Soil Sci
I certify that I have read this study and that in ray
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the deqree of Doctor of Philosophy.
R. D. Rhue
Associate Professor
of Soil Science
I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the deqree of Doctor of Philosophy.
¿AÚcu*l
E. A. Hanlon
Assistant Professor
of Soil Science
I certify that I have read this study and that in ray
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the deqree of Doctor of Philosophy.
C. C. Hsu
Professor of
Enqineerinq Sciences

I certify that I have read this study and that in my
opinion it conforms to acceptable standards of scholarly
presentation and is fully adequate, in scope and quality, as
a dissertation for the degree of Doctor of Philosophy.
^7^ 7^ 'TWc 7^-
W. W. McFee
Professor of Soil Science
This dissertation was submitted to the Graduate Faculty of
the College of Agriculture and to the Graduate School and
was accepted as partial fulfillment of the requirements
for the degree of Doctor of Philosophy.
August, 1987
lege of Agriculture
Dean, Graduate School

UNIVERSITY OF FLORIDA
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