Journal of Environmental Protection, 2011, 2, 1076-1083
doi:10.4236/jep.2011.28124 Published Online October 2011 (http://www.scirp.org/journal/jep)
Metal Transport Parameters in Residual Soil with
an Undisturbed and Remolded Structure
Percolated by an Acid Solution
Eduardo Pavan Korf1, Antonio Thomé2, Nilo Cesar Consoli1, Rafael de Souza Tímbola2,
Gláucia Carine dos Santos1
1Department of Civil Engineering, Federal University of Rio Grande do Sul, Porto Alegre, Brazil; 2University of Passo Fundo, Passo
Fundo, Brazil.
Received July 18th, 2011; revised August 21st, 2011; accepted September 22nd, 2011.
ABSTRACT
There is no enough informa tion about metal transport parameters in residual so il. These soils are generally structured
and still there is no answer to what happens with the contaminant transport parameters when an acid solution with
metal percolates this material with different structure. The objective of this study was to determine the contaminant
transport parameters for Cd, Ni, Cu and Zn metals in an acid multispecies solution to a residual soil from south Brazil
with an undisturbed and remolded structure. Column tests were carried out to determine the Rd, kd, Dh transport pa-
rameters. It was possible conclude that the magnitude of the kd, Rd and Dh parameter did n ot vary sign ificantly with the
soil structure.
Keywords: Pollutant Transport, Column Equipment, Natural Attenuation, Dissolved Metals, Analytical Simulation
1. Introduction
Acidic and inorganic materials in residual water repre-
sent a common effluent from industrial activities such as
mining (coal and mineral deposits), electroplating, cast-
ing and the handling of chemical substances in general.
These effluents, if not well managed, may generate en-
vironmental pollution and have a negative impact on soil,
superficial and underground water and ecosystems [1-
11].
The metals when inserted in the environment may
cause serious damage to toxicity in exposed organisms,
because metals may be inserted in the food chain due to
their high mobility. [12] have claimed that contamination
by metals may lead to both acute and chronic high toxi-
city, persist in an environment, high mobility and accu-
mulate in organisms due to their liposolubility. Addi-
tionally, metal compounds, even in small amounts, may
be toxic to plants and animals [13,14].
Studies are needed to provide an understanding of the
control mechanisms of solution with metallic compounds
on the residual soil, mainly from south Brazil. Such
studies should be conducted with the objective of moni-
toring the contamination plumes migration and carried
out environmental models studies. Additional studies might
also accelerate immobilization and decontamination pro-
jects or suspend such procedures for verifying effective-
ness of natural attenuation processes [15].
The migration of pollutants to the subsurface is in-
fluenced by several factors that may determine the move-
ment of metal through the soil. These factors are de-
scribed by physical and biophysical-chemical processes,
which are represented by the theoretical model. The
physical process, in general, involves diffusion and me-
chanical dispersion phenomena, and one may be predo-
minant over the other. The summation of those two pro-
cesses is called hydrodynamic dispersion (Dh). This phe-
nomenon is characterized in the diffusive part by mo-
lecular diffusion coefficient (D*), which is represented
by the direct relationship between the coefficient diffu-
sion in free solution (Do) and a physical-chemical factor
called tortuosity (τ). In the dispersive part of transport,
the phenomena are represented by the mechanical dis-
persion (α) and the percolation speed (vs). The bio-
physicochemical processes are related to the physical,
chemical and biological interactions that may occur be-
tween the soil and the pollutant. In those processes, the
interaction between the environmental conditions, the

Metal Transport Parameters in Residual Soil with an Undisturbed and Remolded Structure Percolated 1077
by an Acid Solution
pollutant and the porous media may cause the delay, ac-
celeration or degradation of pollution. The parameter that
governs these processes is the retardation factor (Rd)
which is directly co-related with the distribution coeffi-
cient (kd). All the contaminant transport parameters can
be determined through laboratory experiments such as
column tests, diffusion tests and batch tests. Also, they
can be estimated according to literature data and by cor-
relations or through retro-analysis with analytical or nu-
meric solutions [16-27,5,7]).
The objective of this study was to determine the con-
taminant transport parameters of for Cd, Ni, Cu and Zn
metals dissolved in a pH multispecies acid solution in a
residual soil with undisturbed and remolded structures.
Both soil structures were evaluated with the objective of
simulating, respectively, the condition of a natural barrier
in the field as well as a remolded condition that repre-
sents the artificial soil barrier to prevent the percolation
of an acidic and inorganic pollutant.
2. Experimental Program
2.1. Materials
2.1.1. Residu a l Soil
The soil utilized in the present research was a basaltic re-
sidual soil sampled from the Geotechnical Experimental
Site of the University of Passo Fundo, located in south-
ern Brazil.
According to [28] the pedological classification is a
Humic Oxisol. These soils are very deep, drained and
highly weathered, and they show a sequence of A-Bw-C
horizons, where Bw is a oxisol type. In this study was
used the Bw horizon only. These soils have very little
clay increase with depth, and there is a gradual transition
between the horizons. Because the soils were very
weathered, there is a dominance of kaolinite and iron
oxides, which gave the soil samples a low CEC (cation
exchange capacity), strong acidity and a low stock of
nutrients. Its red color indicates that the soil had a low
base saturation and high iron content [29].
Regarding of chemical characterization, the residual
soil used has an acidic pH (5.4), high clay content (68%),
low organic matter content (<0.8%) and low CEC (8.6
cmolc/dm³), which is typical of soils with the predomi-
nance of kaolinite clay mineral. The geotechnical char-
acterization, based on characterization tests, indicated
soil is clay and have high compressibility—CH [29].
The mineral characterization, related to the specific
superficial area (SSA—was 33.86 m2·g–1), indicated a
predominance of kaolinite clay, according to the range of
values proposed by [30,31].
2.1.2. Pollu t ant Solution
The pollutant solution contained metals dissolved in dis-
tilled water with pH 1.35. This value was used to repro-
duce the condition of high solubility, attempting to avoid
precipitation chemical reactions. The metals concentra-
tion in the pollutant solution used in column tests were
defined according to increasing the intervention value for
underground water from Company of Technology in
Environmental Sanitation—CETESB [32]. The interven-
tion value indicates the need of remediation actions for
the possible risks receptors [32].The increase this value
represents an extreme condition of contamination, re-
quiring monitoring or remediation measures. These va-
lues as well as the inserted concentration to different
metal used in this study are presents in Table 1.
2.2. Methods
2.2.1. Molding of the Test Samples
Each sample was taken from the field in its undisturbed
form from the B horizon of the soil (1.2 m depth). In the
laboratory, the cylindrical test samples (TS) were molded
with an undisturbed and remolded structure. The re-
molded test samples had approximately the same density
and natural moisture as the undisturbed samples. The
diameter of the test samples was 5 cm and the heights of
the samples were variable. Tabl es 2 and 3 show the phy-
sical properties for the test samples with undisturbed and
remolded structures, respectively.
2.2.2. Column Test
The column test reproduces the transport of a pollutant
through the soil and is used for determination of physical
Table 1. Concentration of metals inserted in the columns
tests.
Metal
CETESB
Intervention
(mg·L–1)
Increasing
Inserted
Concentration
(mg·L–1)
Ni <0.02 100 2
Cr <0.05 100 5
Pb <0.01 100 1
Cd <0.005 100 0.5
Zn <5 2 10
Cu <2 2.5 5
Mn <0.4 2 0.8
Table 2. Physical properties of the test samples with an
undisturbed struc ture.
Test
sample
Moisture
content
(%)*
Height
(cm)
Diameter
(cm)
Specific.
mass
(g·cm–3)*
Void
ratio Porosity
Void
volume
(cm3)
1 35.279.224.93 1.50 1.41 0.59102.74
2 32.506.405.17 1.43 1.46 0.5979.85
3 34.628.664.57 1.51 1.38 0.5882.38
*Moisture and density equivalent to molding field.

Metal Transport Parameters in Residual Soil with an Undisturbed and Remolded Structure Percolated 1078
by an Acid Solution
Table 3. Physical properties of test samples with a r e molded
structure.
Test
sample
Moisture
content
(%)*
Height
(cm)
Diameter
(cm)
Specific.
mass
(g·cm–3)*
Void
ratio Porosity
Void
volume
(cm3)
4 11.44 5 1.58 1.27 0.56 125.67
5 9.64 5 1.56 1.29 0.56 106.70
6
34.62
7.96 5 1.55 1.38 0.57 88.82
*Moisture and density equivalent to molding field.
and physical-chemical transport parameters. The test was
conducted with equipment produced according to the
[29]. The test consisted of two steps; the first stage the
distilled water was percolated until flow steady state,
where the hydraulic conductivity was determined. In the
second stage was percolated the pollutant solution. For
each soil structure, three test samples were tested simul-
taneously.
After percolating the pollutant solution through the
soil, the liquid was collected in different percolated vo-
lume and tested times. The metal concentration in each
collected samples was determined through analysis with
an atomic absorption spectrophotometer.
After determining metal present in the percolated ef-
fluent from the test samples, it was possible to obtain the
breakthrough curves for each test and metal pollutant.
The breakthrough curve gives the number of percolated
pores (percolated volume/void volume—Vperc/Vv) or
the percolation time (T) along the x axis, and the pollut-
ant relative concentration (percolated effluent concentra-
tion/initial concentration—C/Co) is given along the y
axis.
Tables 4 and 5 show the hydraulic characteristics of
each test sample for the undisturbed and remolded struc-
tures, respectively.
2.2.3. Deter mi n at ion of Trans po rt Parame t er s
Reference [33] developed a one-dimensional analytical
solution (1D) for the flow in homogenous and saturated
soils using both initial and boundary conditions: C (x, 0)
= 0 for x ≥ 0; C (0, t) = Co for t ≥ 0; C (∞, t)/ (t) = 0 for
t ≥ 0. The Equation (1) shows the analytical solution for
a reactive solute for the occurrence of delay biophysical-
chemical processes. In the equation, C/Co is the ratio be-
tween measured percolated effluent concentration and
the initial concentration, erfc is a function of the supple-
mentary error, Rd is the delay factor, L is the one-di-
mensional flow distance given by the height of the test
sample, vs is the percolation speed, t is the time of the
test, and Dh is the hydrodynamic dispersion coefficient.
To determine the Dh parameter, a theoretical curve
was adjusted at experimental transport curve (break-
Table 4. Hydraulic characteristics of test samples with un-
disturbed structure .
Test k (cm·s–1) vs (cm·s–1)
1 5.90 × 10–04 7.66 × 10–03
2 3.70 × 10–04 6.92 × 10–03
3 1.40 × 10–04 3.24 × 10–03
Table 5. Hydraulic characteristics of test samples with
remolded structure.
Test k (cm·s–1) vs (cm·s–1)
4 8.07 × 10–05 2.78 × 10–03
5 1.42 × 10–04 2.92 × 10–03
6 2.76 × 10–04 6.77 × 10–03
through) from column test by the Ogata and Banks solu-
tion Equation (1). To generate a theoretical curve, the
C/Co values were found by establishing different time
ranges (t), the height of the test sample (or the flow dis-
tance along x (L)), the percolation speed (vs) and the
parameters Rd. The Rd parameter was obtained from a
method given by [18], which defines the area above the
transport curve as a value corresponding to Rd.


0
dssd s
h
hd hd
Cx,t
C
RL-vtvLRL+vt 1
= erfc+experfc
2D
2DRt 2DRt


 



 

 



 


(1)
The kd coefficient was obtained using a linear rela-
tionship between the mass absorbed by a unit of solid
mass and the concentration of the substance in the solu-
tion when the soil is saturated, which was determined
after equilibrium was reached. The parameter kd was
determined according to Equation (2), where: Rd is the
delay factor, ρs is the specific soil dry mass, and n is the
porosity of the test sample [23].
d
d
s
R-1
k= n
ρ (2)
3. Results
3.1. Column Tests
Figures 1 to 4 show some results of columns tests with
the adjustments performed for the analysis of the trans-
port parameters for the residual soil. Only was showed
the best adjustments results for each soil structure and
tested metal. However, these results are representative of
all tests, once the results were similar for each treatment.
C opyright © 2011 SciRes. JEP

Metal Transport Parameters in Residual Soil with an Undisturbed and Remolded Structure Percolated
by an Acid Solution
1079
Figure 1. Column test results and adjustment analysis for cadmium metal (a) undisturbed; (b) remolded structure.
Figure 2. Column test results and adjustment analysis for nickel metal (a) undisturbed; (b) rem olde d str uc ture .
Figure 3. Column test results and adjustment analysis for zinc metal (a) undisturbed; (b) remolded structure.

Metal Transport Parameters in Residual Soil with an Undisturbed and Remolded Structure Percolated 1080
by an Acid Solution
Figure 4. Column test results and adjustment analysis for copper metal (a) undisturbed; (b) remolded str uctur e .
3.2. Contaminant Transport Parameters
Tables 6-9 show the contaminant transport parameters
obtained for the tested metals with undisturbed and re-
molded structures at a pH of 1.35. Variance Analysis for
treatments for Kd, Rd and Dh showed no significant dif-
ference between the structures to the metals: Cd, Ni, Cu
and Zn. Although the Ni metal have presented p = 0.049,
this value is very close to 0.05, which does not reveal
significant differences with confidence ( = 0.05). The
tables also show the average value, standard deviation
and coefficient of variation for the values of kd and Rd
and Dh of each metal.
4. Discussion
Concerning the magnitude of parameters kd and Rd there
are no significant influence of the change of structure for
the metals Cd, Ni, Cu, Zn. The similarity between the kd
and Rd values related to the structure don’t agree with the
finding of [34,35], who have reported that the distur-
bance of a remolded structure influences the pollutants
mobility in soils. The authors have not related the pH,
but this may be true for higher values of pH, which can
decrease metals mobility in solution. In this study, the
similar behavior found with different structures must be
due to high mobility of metals in acidic pH (1.35), which
possibly may have favored the transport in both struc-
tures.
Reference [36] simulated the concentration of a con-
taminating solution at pH 4.5 and 5 mg·L–1, which is
close to most of the concentrations employed in the pre-
sent study in soil with 90.6 % kaolinite and 21 % clay.
They obtained kd values for Cd (4.9 cm3·g–1), Ni (9.5
cm3·g–1), Cu (15.0 cm3·g–1), Zn (6.5 cm3·g–1). The values
reported by [36] are similar to the ones found in the pre-
Table 6. Transport parameters obtained for cadmium metal.
Structure TS Rd k
d (cm3·g–1) Dh (cm2·s–1)
TS1 5.00 2.09 1.50 × 10–2
TS2 5.50 2.45 1.50 × 10–2 Undisturbed
TS3 7.00 3.10 6.67 × 10–3
TS4 3.64 1.26 1.17 × 10–2
TS5 6.52 2.66 8.33 × 10–3 Remolded
TS6 5.00 1.98 1.67 × 10–2
p 0.490 0.311 0.996
Average 5.44 2.26 1.22 × 10–2
Standard Deviation 1.20 0.63 4.04 × 10–3
Coefficient of variation
(%) 22.09 28.09 33.05
*p value of variance analysis.
Table 7. Transport parameters obtained for nickel metal.
Structure TS Rd k
d (cm3·g–1) Dh (cm2·s–1)
TS1 6.70 2.98 6.67 × 10–3
TS2 9.00 4.36 1.00 × 10–2 Undisturbed
TS3 ** 7.23 1.17 × 10–2
TS4 3.00 0.96 6.67 × 10–3
TS5 4.44 1.66 8.33 × 10–3 Remolded
TS6 5.01 1.99 5.00 × 10–2
p 0.049 0.046 0.520
Average 5.63 3.20 1.56 × 10–2
Standard Deviation 2.30 2.30 1.70 × 10–2
Coefficient of variation (%)40.91 72.00 109.14
*The parameter could not be obtained.
C opyright © 2011 SciRes. JEP

Metal Transport Parameters in Residual Soil with an Undisturbed and Remolded Structure Percolated 1081
by an Acid Solution
Table 8. Transport parameters obtained for copper metal.
Structure TS Rd k
d (cm3·g–1) Dh (cm2·s–1)
TS1 5.50 2.35 1.00 × 10–2
TS2 7.97 3.80 3.33 × 10–2
Undisturbed
TS3 ** 6.20 6.67 × 10–3
TS4 6.52 2.64 1.17 × 10–2
TS5 8.49 3.62 1.67 × 10–3
Remolded
TS6 7.29 3.12 3.33 × 10–2
p 0.5900.940 0.710
Average 7.15 3.62 1.61 × 10–2
Standard Deviation 1.18 1.38 1.38 × 10–2
Coefficient of variation (%) 16.5538.08 85.37
*The parameter could not be obtained.
Table 9. Transport parameters obtained for zinc metal.
Structure TS Rd k
d (cm3·g–1) Dh (cm2·s–1)
TS1 2.500.78 1.50 × 10–2
TS2 3.501.36 1.50 × 10–2 Undisturbed
TS3 7.003.10 6.67 × 10–3
TS4 3.111.01 3.33 × 10–3
TS5 4.471.68 8.33 × 10–3 Remolded
TS6 4.291.63 4.17 × 10–2
p 0.8000.690 0.670
Average 4.151.59 1.50 × 10–2
Standard Deviation 1.580.82 1.39 × 10–2
Coefficient of variation (%) 38.1051.26 92.49
sent study. [37] studied metals mobility in oxisol with
72% clay and kaolinite 70.9% and obtained Rd values of
1.34, 1.46 and 3.88 for Zn, Cd and Cu, respectively.
These values are lower than the values obtained in this
study. This is due the different structures and mineral
formation for soil used.
With respect to the metal retention sequence, which
was observed through the average parameters kd and Rd,
the following prevalence order was observed: Cu > Ni >
Cd > Zn. The affinity order obtained by [38], from re-
sidual oxisol in the state of São Paulo, Brazil, had a
similar behavior for Cu and Zn metals. [5] claimed that
Cu metal have reduced mobility in soil as compared to
Zn, Ni and Cd metals, which was confirmed by the re-
sults of this study. Relative to the kaolinite clay mineral,
which was predominant in the studied soil, [19] found
the following preference series for pH values of 3.5 to 6:
Pb > Ca > Cu > Mg > Zn > Cd. Similar results were ob-
tained for the Cu and Zn metals in the current study.
Vega et al. (2006) [36] obtained similar preference series,
which only had opposite behavior between Cd and Zn.
[37] obtained equivalent preference series in the study of
Zn, Cd and Cu metals.
The results for parameter Dh, according to Tables 6-9,
range from 10–3 to 10–2 cm2·s–1 and, according to analysis
of variance, no difference was found between the struc-
tures tested. [25] obtained Dh values for Cd in the hori-
zon B oxisol, resulting in an average value of 2.81 × 10–4
cm2·s–1. [20], obtained Dh values for zinc in clayey soil
used in compacted landfill barriers with average value of
1.78 × 10–4 cm2·s–1. [39], obtained Dh values that ranged
from 2.25 × 10–5 cm2·s–1 to 8.15 × 10–5 cm2·s–1 for a soil
from a urban solid waste landfill, and they studied the
presence of Cd, Cu and Zn metals. The values obtained
by those authors were lower than the values in the pre-
sent study, which could be explained by the difference in
structures and mineral formation and direct influence of
the low kd and Rd values, which also reduced the Dh val-
ues, which have been obtained through these parameters.
5. Conclusions
In this work was studied the contaminant transport pa-
rameters to a clay residual soil from south Brazil with
different structures (undisturbed and remolded) when
percolated with an acid solution (pH = 1.35). The fol-
lowing conclusions can be made:
- The kd, Rd and Dh magnitude did not vary signifi-
cantly with soil structure, thus, it is possible conclude
that the soil structure did not influence the contaminant
transport parameters for this residual soil;
- The metal retention sequence was Cu > Ni > Cd >
Zn.
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