Geoderma 164 (2011) 232237

Contents lists available at ScienceDirect

Geoderma
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / g e o d e r m a

Mobility of Cr, Pb, Cd, Cu and Zn in a loamy sand soil: A comparative study
B. Fonseca , H. Figueiredo, J. Rodrigues, A. Queiroz, T. Tavares
IBB-Institute for Biotechnology and Bioengineering, Centre of Biological Engineering, University of Minho, 4710-057 Braga, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: Interest in soil contamination has been growing in recent years due to the ongoing degradation of soil
Received 13 July 2010 environments. Therefore, the development of remediation techniques and the study of contaminant sorption
Received in revised form 10 May 2011 and migration are areas of intense research.
Accepted 22 June 2011
In this study, the authors sought to evaluate the scenario of co-contamination of a loamy sand soil by multiple
Available online 16 July 2011
heavy metals. To that end, the sorption and transport of ve metalsCr, Pb, Cd, Cu and Znwas evaluated
Keywords:
using representative samples of a soil from the north of Portugal. The tests were conducted in batch and
Heavy metals continuous systems using single- and multiple-metal acid solutions to evaluate the effect of metal
Soils competition. In accordance with the type of assaybatch or continuousLangmuir or Convection Dispersion
Sorption Two-Site Nonequilibrium models were adjusted to explain the sorption/transport data. FTIR analyses were
Convectiondispersion performed on the nal samples of the continuous systems.
Equilibrium Generally, the results revealed good tting of the tested models for the metals in competitive and
noncompetitive scenarios, with the exception of Zn that was originally present in soil samples at higher
concentrations. As expected, the inuence of competition was observed in both batch and continuous
systems, but with different tendencies. The FTIR spectra also revealed a strong inuence of clay minerals and
organic matter on the sorption of the metals.
2011 Elsevier B.V. All rights reserved.

1. Introduction single- and multi-metal contamination, in order to obtain more realistic

results (Serrano et al., 2005). However, it is also important to perform
The release and disposal of heavy metals from anthropogenic these types of studies for different regions and soils, as the composition
activities have been responsible for the increasing concentrations of of the soil matrix may result in unexpected behavior.
these contaminants in soil environments. The high loading of metals in Some heavy metals such as cadmium (Cd), zinc (Zn) and copper
soils may affect the growth of plants and the health of animals, thereby (Cu) can be found in fertilizers used on agricultural lands (Tran et al.,
representing a signicant threat to public health (Berti and Jacobs, 1998; USEPA, 2009). In addition, Zn and Cu are also present in high
1996). Consequently, the development of effective strategies to manage concentrations, along with lead (Pb), in roadside soils (Miller et al.,
heavy metal pollution is of great importance (Adhikari and Singh, 2003) 1989). These four metals, together with chromium (Cr), are
but requires extensive knowledge of the sorption and transport frequently identified in wastes from several industrial activities
behaviors of heavy metals and of the diverse variables affecting these including electroplating, car manufacturing, and metallurgy (Covelo
processes. Several studies have been performed in order to establish the et al., 2008; Lau and Stenstrom, 2005; USEPA, 2009). Thus, these five
inuence of different parameters on heavy metal sorption/desorption metals can be readily found as co-contaminants in agricultural lands
(Appel and Ma, 2002; Fonseca et al., 2009b; Fontes et al., 2000; Hanna as well as near roads and/or automotive facilities. For this reason, a
et al., 2009; Lee et al., 2001; Liu et al., 2006; Sipos et al., 2008). Most of soil sample collected in a location of great agricultural activity near an
these studies primarily reported the results of batch tests, giving automotive facility was used to study the competitive and non-
detailed information on the sorption process but little on the transport competitive sorption and transport of Cr, Pb, Cd, Zn and Cu.
of the heavy metals. Therefore, because the simultaneous presence of Batch tests were undertaken using single- and multiple-metal
competing metals is known to affect sorption processes and leaching solutions with equimolar concentrations of the aforementioned heavy
potentials through soil profiles, this study sought to evaluate the metals in order to study their sorption equilibria. The Langmuir
retention of heavy metals using either batch or flow tests, simulating isotherm model was adjusted to the experimental data, allowing the
determination of the soil's maximum sorption capacity for each metal,
with and without competition. To evaluate the retention of each metal
Corresponding author at: Biological Engineering Department, University of Minho,
Campus de Gualtar, 4710-079 Braga, Portugal. Tel.: + 351 253 604 400; fax: + 351 253
in single- and multiple-metal ow systems, the respective solutions
678 986. were pumped through soil columns. Finally, the CXTFIT code was used
E-mail address: [email protected] (B. Fonseca). to fit the dimensionless two-site nonequilibrium convectiondispersion

0016-7061/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.geoderma.2011.06.016
 B. Fonseca et al. / Geoderma 164 (2011) 232237 233

equation to the breakthrough curves (Toride et al., 1995; van was determined by flame atomic absorption spectroscopy after the
Genuchten, 1981) in order to determine the retardation factor for preparation of the solutions.
each metal under the tested conditions. Functional groups present in the Preliminary studies showed that over the concentration range
soil that may have some role in the sorption process were identified by tested, Cr reached sorption equilibrium after 192 h, the longest
FTIR. equilibration time of the ve metals studied (Fonseca et al., 2009a;
Serrano et al., 2005; Usman, 2008; Vega et al., 2006). Therefore, all the
2. Material and methods batch equilibrium tests, including blanks, were undertaken in an
orbital mixer (Certomat S) for 192 h at room temperature (25 0.5
2.1. Soil characterization C) and at a shaking speed of 100 rpm. The polypropylene tubes
containing the soilsolution mixtures were then centrifuged at
Several representative soil samples of a loamy sand soil were 5000 rpm for 5 min, and an aliquot of the supernatant was collected
collected at Pvoa de Varzim, Oporto, Portugal (412515.58N and in pre-acidied sample tubes (2% HNO3). These samples were stored
84558.27O), homogenized and characterized as described else- at 4 C for future analysis by ame atomic absorption spectroscopy.
where (Fonseca et al., 2009a, 2009b). The particle distribution was The pH of the supernatant was measured and was always approxi-
determined by means of laser granulometry (Beckman-Coulter mod. mately 6 0.5.
LS230). The soil pH was determined according to US EPA method The concentration of metal adsorbed onto the soil at equilibrium
9045D (USEPA, 2004). The ammonium acetate (Hendershot et al., S/(mmol kg 1)was calculated as:
1993) and the Tinsley (Tinsley, 1950) methods were used to quantify
the cationic exchange capacity and the organic matter content of the SCi C V = W 1
soil, respectively. Moreover, the concentration of each elementCr,
Cd, Pb, Zn, and Cuwas determined by ame atomic absorption where C is the concentration of metal in the solution at equilibrium
(Varian SpectraAA-400), after microwave digestion (Aurora Instru- (mM); Ci is the initial concentration of metal in the liquid phase
ments MW600) with nitric acid using US EPA method 3051A (USEPA, (mM); V is the volume of metal solution (L) and W is the weight of the
2007). Iron and manganese oxides were determined by the soil sample (kg). The results were plotted in a graph of S versus C and
dithionitecitrate method (Mehra and Jackson, 1958). Finally, the the Langmuir isotherm model was fitted to data:
carbonate content and mineral composition were determined with a
Scheibler calcimeter and by X-ray diffraction analysis (Philips S = Smax bC = 1 + bC 2
PW3710), correspondingly. Table 1 summarizes the physical and
chemical characterization performed for the studied soil. Smax is the maximum mass of metal that can be sorbed by a given mass
of the sample (mg kg 1); b is a constant related to the binding
2.2. Batch experiments strength (L mg 1) (Fonseca et al., 2009a; Langmuir, 1918; Sparks,
1995).
Sorption isotherm assays for Cr, Pb, Cd, Zn and Cu, with either single
or mixed solutions, were performed using the batch equilibrium 2.3. Continuous flow experiments
technique. The experiments were conducted by adding 20 mL of each
metal solution or an equimolar solution of the five metals to 2 g of soil in All column experiments, including duplicates, were conducted at
50 mL polypropylene centrifuge tubes. The experiments were per- room temperature25 1 Cin acrylic columns 2.5 cm in diameter
formed using seven different solutions, prepared on a molar concen- by 25 cm deep. The packed soil in the columns had a mean bulk
tration basis, in order to prevent mass effects (Echeverria et al., 1998). density of (2.3 0.3) g cm 3 and a bed height of (22 1) cm. Single-
The heavy metal concentration range [0.05 mM0.48 mM] was selected metal solutions with 0.05 mM of each metalCr, Pb, Cd, Zn and Cu
considering the legislated limit for Pb, as this was the heaviest metal and also a mixed solution with equimolar concentrations of the five
tested. Except for the Cr solutions, which were prepared from potassium metals, each with a pH lower than 2, were passed through the
dichromate salt, the solutions were prepared using nitrate salts of the columns for approximately 35 h at an average ow rate of (15 0.2)
desired heavy metals in a background of 0.01 M of CaCl2. This mL min 1. To ensure saturation ow conditions and, consequently,
background was used to improve centrifugation and minimize cation the absence of immobile regions, the columns were operated in an
exchange (OECD, 2000). The solutions were acidied with concentrated upward ow mode (Papelis and Um, 1999). The samples were
HNO3 (65%), in order to avoid the precipitation of metal cations collected in 50 mL polypropylene tubes, and an aliquot was acidified
(pH 2). It should be noted that the initial concentration of every metal with 2% (v =v ) of concentrated HNO3 (65%) for nal analyses by flame
atomic absorption spectroscopy. The pH of the efuent samples was
also measured. The dimensionless two-site nonequilibrium convec-
Table 1 tiondispersion equation (TSM) was then tted to the obtained
Chemical and physical properties of soil. experimental breakthrough curves (C/C0 versus t) using the CXTFIT
Clay (%) 2.58 model (Toride et al., 1995), in order to determine the retardation
Silt (%) 23.06 factorRthe coefcient of partitioning between the equilibrium and
Sand (%) 74.36 nonequilibrium phasesand the mass transfer coefcient for
pH (H2O) 5.9 transfer between the two phases. The hydraulic parameters,
Cationic exchange capacity/(cmolc kg 1) 12.52
namely the dispersion coefcientD/(cm 2 h 1)and the pore
Organic matter content/(%) 3.5
[Feox]/(g kg 1) 3.82 water velocityv/(cm h 1)were determined independently for
[Mnox]/(g kg 1) 0.10 each column. Specically, the equilibrium convectiondispersion
[Cr]/(mmol kg 1) 0.17 equation (CDE) was tted to the breakthrough curves of a nonreactive
[Pb]/(mmol kg 1) 0.58
tracerCaCl2 (0.01 M). Consequently, a residence time of approxi-
[Zn]/(mmol kg 1) 4.21
[Cd]/(mmol kg 1) 0.01 mately 50 min was estimated for the ow experiments. The detailed
[Cu]/(mmol kg 1) 0.54 procedure has been described elsewhere by Fonseca et al. (2009b).
[CaCO3]/(mg kg 1) 0.0 After each displacement experiment, the soil bed was collected
Clay mineralsa Smectite, illite, kaolinite and homogenized, three samples of each column were digested
a
Average of clay minerals content: smectite (18%); illite (31%); kaolinite (41%). (Fonseca et al., 2009b; USEPA, 2007), and the metal concentration in
234 B. Fonseca et al. / Geoderma 164 (2011) 232237

each sample was determined through flame atomic absorption interference of other substances, such as soluble organic matter, that
spectroscopy. These samples were also analyzed by transmission can compete with soil particles for the metal cations (Sposito, 1989).
FTIR (FTIR BOMEM MB 104) on pressed KBr pellets (100 mg of KBr Except for Cr, all the other equilibria were reached more slowly in the
and 1 mg of sample). Background correction for atmospheric air was case of competitive sorption (Figure 1) as the ions competed for
used for each spectrum. Spectra were obtained in the range 5004000 sorption sites (Markiewiez-Patkowska et al., 2005). Nevertheless, the
wavenumbers with a minimum of 10 scans and a resolution of higher sorption density of Cu may also be due to the formation of Cu
4 cm 1. Cr precipitates, since the soilsolution at the end of the experiment
had a pH of approximately 6 (Sun et al., 2006). This could also explain
3. Results and discussion the higher retention of Cr when in competition with Cu and other
metals (Yolcubal and Akyol, 2007).
3.1. Soil characterization As mentioned before, the experimental isotherm obtained for the
sorption of Pb in the absence of competition was a nearly vertical line
According to the data compiled in Table 1, it can be inferred that (Figure 1), revealing its total sorption and its high afnity for the soil
the studied soil is slightly acidic loamy sand. It has considerable despite the variation in the solution concentration. Given this
organic matter content, but low cationic exchange capacity and no observation and the values of the Langmuir afnity constantb
carbonate (Fonseca et al., 2009a). Kaolinite was found to be the determined for each metal in both systems (Table 2), a sorption trend
predominant mineral composing the clay fraction of the soil sample. can be defined as: Cr N Pb N Cd N Cu N Zn. This trend can be mainly
Finally, all the heavy metals were found in concentrations below the explained by the conventional hardsoft acidbase (HSAB) principle
national legislated limit for soils with pH between 5.5 and 7. and the nature of the ions studied. The hard ions are those with high
electronegativity, low polarizability and small ionic size. These ions
3.2. Batch experiments prefer hard ligands but form weak complexes with them. However,
the soft ions have greater afnity for soft sites and are more
Fig. 1 shows the isotherm curves obtained for each metal in strongly bounded (Ghosh and Biswas, 2003; Liu et al., 2006; Puls and
competitive (multiple-metal) and noncompetitive (single-metal) Bohn, 1988; Sparks, 1995). It should be noted that, at low pH values,
systems. Generally, the isotherm curves have the shape of an L- Cr 6+ exists mainly as an oxyanion, which is adsorbed at positively
curve isotherm, resulting from the relatively high afnity of the soil charged sites. In fact, the equilibrium pH values of the sorption
particles for the metal at low surface coverage, an afnity that experiments, including the blank, were between 5.5 and 6.5,
decreased as the surface became saturated (Echeverria et al., 1998; indicating the degree of protonation of the soil surface. Furthermore,
Sposito, 1989). For the noncompetitive sorption of Pb and the oxyanions are soft bases and, according to the Pearson concept, can
competitive sorption of Cr, the isotherms obtained took the form of react strongly with Lewis acid sites created by inner-sphere surface
nearly vertical lines, or H-type isotherms. These are usually produced complexation (Bailey et al., 1960; Banks et al., 2006; Fonseca et al.,
by inner-sphere surface complexation or by signicant van der Waals 2009b; Pearson, 1963; Sposito, 1989).
interactions in the adsorption process (Sposito, 1989). Finally, the As the working concentration range is very narrow in these studies,
curves obtained for the noncompetitive sorption of Cu and Zn the experimental maximum sorption capacities observed (Figure 1)
revealed an S-type curve. This is related to the low afnity between differ largely from the estimated values (Table 2), because the trend of
the soil particles and the metal at low concentrations due to the the isotherm curves for higher concentrations is unpredictable. However,

6 6
S/(mmol kg1)

S/(mmol kg1)

Cr Pb
4 4

2 2

0 0
0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0 0.5 1 1.5 2 2.5 3
3
C/(mmol L1) C/(mmol L1) x 10

6 6
S/(mmol kg1)

S/(mmol kg1)

Zn Cd
4 4

2 2

0 0
0 0.005 0.01 0.015 0.02 0 0.005 0.01 0.015 0.02 0.025 0.03
1) C/(mmol L1)
C/(mmol L
6
S/(mmol kg1)

Cu
4 Monometal
Monometal
2
Multimetal
0 Multimetal
0 1 2 3 4 5 6
3
C/(mmol L1) x 10

Fig. 1. Adsorption isotherms obtained for the tested metals in competitive and noncompetitive systems. Lines represent the adjusted Langmuir model. The error bars depict the
confidence interval for a level of condence of 95%.
 B. Fonseca et al. / Geoderma 164 (2011) 232237 235

Table 2 Table 3
Values of Langmuir and Sips equations parameters determined in the mono- and multi- Quality of fit and parameter estimates based on the two-site chemical nonequilibrium
metal batch systems, for each tested metal. The standard deviations were under 10%. convective dispersion equation, for mono- and multi-metal flow systems. The standard
deviations were under 10%.
Langmuir Mono-metal Multi-metal
Parameters Mono-metal Multi-metal
Cr
Smax 3.10 Cr
b 1364 R 107 502
r2 0.964 0.11 0.00
Pb 0.13 0.17
Smax 14.0 r2 0.924 0.73
b 183 Pb
r2 0.793 R 34 39
Zn 0.63 0.62
Smax 9879 17.0 0.01 0.02
b 0.04 21.0 r2 0.999 0.995
r2 0.831 0.971 Zn
Cd R 6
Smax 10 10 0.18
b 41 30 100
r2 0.988 0.991 r2 0.887 0.030
Cu Cd
Smax 9977 8531 R 27 13
b 0.1 0.1 0.99 0.72
r2 0.735 0.956 100 0.58
r2 0.987 0.996
Cu
R 49 198
it is clear from the experimental data (Figure 1) that all the metals at the 0.99 0.09
tested concentration range were totally sorbed in this soil, in either 60 0.03
noncompetitive or competitive scenarios. r2 0.998 0.993

3.3. Flow experiments

concentration much higher than 1 were obtained for this assay, with
In Fig. 2, the breakthrough curves obtained for each metal in more expression in the first 5 h before the breakthrough point of the
competitive and noncompetitive ow tests are shown. The respective other metals (Figure 1). The Zn cations can be easily exchanged when
adjusted two-site adsorption models are also presented. Generally, competing with other metal cations (Covelo et al., 2004). Therefore, it
the fit provided by the two-site adsorption model was good, as can be assumed that a fraction of the highly concentrated native Zn
demonstrated by the correlation coefficient values in Table 3. (Table 1) was washed out from the column, increasing its concentra-
However, the breakthrough curve of Zn in the competitive sorption tion in the effluent, especially before the saturation of the exchange-
experiment could not be fit using this model. Values of relative able surfaces.

1 1
Cr Pb
C/C0

C/C0

0.5 0.5

0 0
0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35
t/h t/h

9 1.5
Zn Cd
6 1
C/C0

C/C0

3 0.5

0 0
0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35
t/h t/h

1.5
Cu
1 Monometal
C/C0

Monometal
0.5 Multimetal
Multimetal
0
0 5 10 15 20 25 30 35
t/h

Fig. 2. Experimental breakthrough curves obtained for each metal in competitive and noncompetitive scenarios. Lines represent the adjusted two-site model. The error bars depict
the confidence interval for a level of confidence of 95%.
236 B. Fonseca et al. / Geoderma 164 (2011) 232237

Examining the single-metal systems, it is evident that the highest 3.3.1. FTIR spectral analysis
retardation factorRwas obtained for Cr, whose affinity for the soil Fig. 4 shows the FTIR spectra obtained for an uncontaminated soil
was already shown to be the highest among the metals studied sample and from the single-metal contaminated and co-contaminated
(Table 3). Cr oxyanions were specically sorbed to sites with high soil samples collected from the soil bed columns. The bands of clay
dissociation constants, making them less vulnerable to leaching. minerals represented by the SiOH stretches at 3706 cm 1 and
However, the batch tests revealed that the other metals were sorbed 3622 cm 1 (kaolin) and the SiOSi stretch at 1030 cm 1 were
at less energetic sites, making them more susceptible to acid leaching. A slightly different from the spectra of the contaminated samples
trend in relative metal mobility under the conditions studied can be (Smidt and Meissl, 2007). The authors have reported similar results
defined as: Zn N Cd N PbN CuN Cr, which is slightly different from what previously, when studying the noncompetitive sorption of chromium,
would be expected after the analysis of the affinity constants (b) and attributed these to the sorption of metals at the edges of the clay
obtained in the batch tests (Table 2), although it is known that the minerals (Alvarez et al., 2004; Fonseca et al., 2009b). However, the
sorption and transportation of heavy metals in dynamic environments acidic character of the inlet solutions may have enhanced the
do not always occur under equilibrium conditions (Sposito, 1989). In dissolution of silicates, as these peaks decreased for the contaminated
fact, compared with Cd and Cu, the values of the partitioning coefficient sample. However, the peaks do not overlap, revealing the persistence
between the equilibrium and nonequilibrium phasesobtained for of these edges, even if they are less concentrated. There are two bands
Cr and Zn were significantly lower (Table 3). This suggests that the at approximately 2900 cm 1, attributed to the CH stretch of
sorption of these metals occurs instantaneously at equilibrium sites but aliphatic structures, and a band at approximately 1634 cm 1 that
is time-dependent at the remaining sites, with higher sorption energy change in all spectra (Carballo et al., 2008). However, the change is
(Toride et al., 1995). However, the values found for the mass transfer more evident in the cases of Pb and Cr. Pb forms strong complexes
coefficients ( N 1) suggest that not only Cd and Cu cations but also Zn with soil organic matter and can compete with most other metals for
cations are promptly sorbed at equilibrium sites. The results with sorption sites (Strawn and Sparks, 2000). Cr transport can also be
respect to Pb transport and sorption are less conclusive. The mass signicantly retarded by the presence of organic matter, as this
transfer coefficient points to a nonequilibrium process ( b 1), but the material has been reported to reduce Cr 6+ to Cr 3+ under acidic
value of reveals that a larger amount of these cations are sorbed at conditions or to complex chromium oxyanions, as mentioned
equilibrium sites than at nonequilibrium sites (Candela et al., 2007; previously (Banks et al., 2006; Jardine et al., 1999). In this particular
Seuntjens et al., 2001; van Genuchten, 1981). According to the batch case, the bands assigned at 1634 cm 1 and 1384 cm 1 may also be
experiment results, both Cr and Pb cations were retained at sites with related to the interactions with the free water and the organic matter
high sorption energies; therefore, sorption at nonequilibrium sites fractions (Haberhauer and Gerzabek, 1999). The bands at 692 cm 1
seems to be predominant, as this reaction is kinetically controlled. When and 797 cm 1 commonly associated with inorganic materials tended
in competition, the mass transfer coefcient did not vary signicantly to overlap for the contaminated samples, probably due to the
for Cr and Pb, as these metals seemed to be sorbed more specifically. By presence of heavy metal complexes (Du et al., 2007).
contrast, the value of this variable decreases for the Cd and Cu cations,
probably because competition stimulates the specic sorption of these 4. Conclusions
ions.
The values obtained for the retardation factorRestimated for Cr The batch and continuous tests showed that this type of soil
and Cu transport in the competitive system were much higher than the loamy sandhas a high affinity for all the tested metals but a different
values obtained for the other metals. This strengthens the aforemen- maximum sorption capacity for each one. An affinity trend was
tioned hypothesis of the precipitation of a CuCr solid in the column,
which is especially reasonable given that the pH of the efuent in the
rst 5 h was above 6 (Figure 3) due to the low acid-buffering capacity of
the soil (Fonseca et al., 2009b; Sun et al., 2006). It should be noted that
the hydroxides of the tested metals do not precipitate in the pH range at
which experiments were conducted (Cherry, 1982). Finally, as expected,
the Cd retardation factor decreased when Cd was in competition with
other cations for sorption sites (Markiewiez-Patkowska et al., 2005;
Serrano et al., 2005; Vega et al., 2006). Pb ions experienced a slightly
higher retardation in the competitive scenario, as this metal is adsorbed
specically on sites with high dissociation constants. As can be observed,
the curve correspondent to the competitive scenario in Fig. 2 grew more
slowly, suggesting increasing sorption density at high-energy sites
(Sposito, 1989; Strawn and Sparks, 2000).

6
pH

0
0 20 40
t/h

Fig. 3. Variation of the effluent pH during the course of a competitive flow test. The Fig. 4. FTIR spectra of uncontaminated and contaminated soil samples collected from
experiment was performed in duplicate with a standard deviation of less than 10%. each column after the flow tests.
 B. Fonseca et al. / Geoderma 164 (2011) 232237 237

defined as: Cr N Pb N Cd N Cu N Zn, according to the respective Langmuir Ghosh, D.C., Biswas, R., 2003. Theoretical calculation of absolute radii of atoms and ions.
Part 2. The ionic radii. Int. J. Mol. Sci. 4, 379407.
constantb. Similarly, a trend of the maximum sorption capacities of Haberhauer, G., Gerzabek, M.H., 1999. Drift and transmission FT-IR spectroscopy of
the soilSmax valueswas described as: Cu Zn N Cd N Pb N Cr. The forest soils: an approach to determine decomposition processes of forest litter. Vib.
results of the ow tests showed that in dynamic systems, reactions Spectrosc. 19, 413417.
Hanna, K., Lassabatere, L., Bechet, B., 2009. Zinc and lead transfer in a contaminated
were not in equilibrium, and therefore, the trend of the retardation roadside soil: experimental study and modeling. J. Hazard. Mater. 161, 14991505.
factor was different: Zn N Cd N Pb N Cu N Cr. Hendershot, W.H., Lalande, H., Duquette, M., 1993. Ion exchange and exchangeable
Generally, in competitive situations, the heavy metals were less cations. In: Carter, M.R., Gregorich, E.G. (Eds.), Soil Sampling and Methods of
Analysis, pp. 197206.
strongly sorbed by soil, due to the competition for sorption sites. Jardine, P.M., Fendorf, S.E., Mayes, M.A., Larsen, I.L., Brooks, S.C., Bailey, W.B., 1999. Fate
However, Cr and Cu seemed to precipitate as a CuCr solid, due to the and transport of hexavalent chromium in undisturbed heterogeneous soil. Environ.
increase in the soil pH. Also, Zn is less effectively retained in ow Sci. Technol. 33, 29392944.
Langmuir, I., 1918. The adsorption of gases on plane surfaces of glass, mica and
systems, mainly due to the acid leaching of Zn ions, which were highly
platinum. J. Am. Chem. Soc. 40, 13611403.
concentrated in this soil. Lau, S.L., Stenstrom, M.K., 2005. Metals and PAHs adsorbed to street particles. Water
The existence of competition among heavy metals does not always Res. 39, 40834092.
reduce their retention in soil, depending on the concentration, pH and Lee, S.Z., Chang, L.Z., Chen, C.M., Yang, H.H., Hu, P.Y., 2001. The effect of hydration on
adsorption and desorption of heavy metals in soils Part A J. Environ. Sci. Health 36,
types of metals involved. Other processes besides adsorption may also 6374.
occur, thereby inuencing the selection of decontamination techniques. Liu, C.L., Chang, T.W., Wang, M.K., Huang, C.H., 2006. Transport of cadmium, nickel, and
zinc in Taoyuan red soil using one-dimensional convectivedispersive model.
Geoderma 131, 181189.
Role of the funding source Markiewiez-Patkowska, J., Hursthouse, A., Przybyla-Kij, H., 2005. The interaction of
heavy metals with urban soils: sorption behaviour of Cd, Cu, Cr, Pb and Zn with a
The PhD grants of Bruna Fonseca and Hugo Figueiredo and the typical mixed browneld deposit. Environ. Int. 31, 513521.
Mehra, O.P., Jackson, M.L., 1958. Iron oxide removal from soils and clays by a dithionite-
research grant of Joana Rodrigues were financially supported by citrate system buffered with sodium bicarbonate. Clays Clay Miner. 7, 317327.
Fundao para a Cincia e Tecnologia, Ministrio da Cincia e Miller, D.M., Sumner, M.E., Miller, W.P., 1989. A comparison of batch-generated and
Tecnologia, Portugal and Fundo Social Europeu (FSE). ow-generated anion adsorption-isotherms. Soil Sci. Soc. Am. J. 53, 373380.
OECD, 2000. OECD Guideline 106. Guideline for the testing of chemicals: Adsorption-
desorption using a batch equilibrium method.
Acknowledgments Papelis, C., Um, W., 1999. Anion and cation transport in zeolitized tuffs from the Nevada
test site: effects of ion type, pH, and ionic strength. In: Selim, H.M., Sparks, D.L.
(Eds.), Heavy Metals Release in Soils. Lewis Publisher, Boca Raton, pp. 3154.
The authors wish to acknowledge the support of Professor Pedro
Pearson, R.G., 1963. Hard and soft acids and bases. J. Am. Chem. Soc. 85, 35333539.
Proena from the Department of Earth Sciences, Sedimentology Puls, R.W., Bohn, H.L., 1988. Sorption of cadmium, nickel, and zinc by kaolinite and
Laboratory, of Coimbra's University, who performed the physical montmorillonite suspensions. Soil Sci. Soc. Am. J. 52, 12891292.
and chemical characterization of the soil. Serrano, S., Garrido, F., Campbell, C.G., Garcia-Gonzalez, M.T., 2005. Competitive
sorption of cadmium and lead in acid soils of Central Spain. Geoderma 124, 91104.
Seuntjens, P., Tirez, K., Simunek, J., van Genuchten, M.T., Cornelis, C., Geuzens, P., 2001.
References Aging effects on cadmium transport in undisturbed contaminated sandy soil
columns. J. Environ. Qual. 30, 10401050.
Adhikari, T., Singh, M.V., 2003. Sorption characteristics of lead and cadmium in some Sipos, P., Nmeth, T., Kis, V.K., Mohai, I., 2008. Sorption of copper, zinc and lead on soil
soils of India. Geoderma 114, 8192. mineral phases. Chemosphere 73, 461469.
Alvarez, R., Evans, L.A., Milham, P.J., Wilson, M.A., 2004. Effects of humic material on the Smidt, E., Meissl, K., 2007. The applicability of Fourier transform infrared (FT-IR)
precipitation of calcium phosphate. Geoderma 118, 245260. spectroscopy in waste management. Waste Manage. 27, 268276.
Appel, C., Ma, L., 2002. Concentration, pH, and surface charge effects on cadmium and Sparks, D.L., 1995. Environmental Soil Chemistry. Academic Press, San Diego.
lead sorption in three tropical soils. J. Environ. Qual. 31, 581589. Sposito, G., 1989. The Chemistry of Soils. Oxford University Press, Inc., New York.
Bailey, N., Carrington, A., Lott, K.A.K., Symons, M.C.R., 1960. Structure and reactivity of Strawn, D.G., Sparks, D.L., 2000. Effects of soil organic matter on the kinetics and
the oxyanions of transition metals. Acidities and spectra of protonated oxyanions. mechanisms of Pb(II) sorption and desorption in soil. Soil Sci. Soc. Am. J. 64,
J. Chem. Soc. 290297. 144156.
Banks, M.K., Schwab, A.P., Henderson, C., 2006. Leaching and reduction of chromium in Sun, J.M., Zhu, W.T., Huang, J.C., 2006. Characterization of primary precipitate
soil as affected by soil organic content and plants. Chemosphere 62, 255264. composition formed during co-removal of Cr(VI) with Cu(II) in synthetic
Berti, W.R., Jacobs, L.W., 1996. Chemistry and phytotoxicity of soil trace elements from wastewater. Environ. Sci. Pollut. Res. 13, 379385.
repeated sewage sludge applications. J. Environ. Qual. 25, 10251032. Tinsley, J., 1950. The determination of organic carbon in soils by dichromate mixture.
Candela, L., varez-Benedi, J., de Melo, M.T.C., Rao, P.S.C., 2007. Laboratory studies on IV International Congress of Soil Science, pp. 161164.
glyphosate transport in soils of the Maresme area near Barcelona, Spain: transport Toride, N., Leij, F.J., van Genuchten, M.T., 1995. The CXTFIT code for estimating transport
model parameter estimation. Geoderma 140, 816. parameters from laboratory or eld tracer experiments. U.S. Salinity Laboratory.
Carballo, T., Gil, M.V., Gomez, X., Gonzalez-Andres, F., Moran, A., 2008. Characterization U.S. Department of Agriculture, Riverside, California.
of different compost extracts using Fourier-transform infrared spectroscopy (FTIR) Tran, Y.T., Bajracharya, K., Barry, D.A., 1998. Anomalous cadmium adsorption in ow
and thermal analysis. Biodegradation 19, 815830. interruption experiments. Geoderma 84, 169184.
Cherry, K.F., 1982. Plating Waste Treatment. Ann Arbor Science, Michigan. USEPA, 2004. Soil and Waste pH. Environmental Protection Agency, United States of
Covelo, E.F., Andrade, M.L., Vega, F.A., 2004. Heavy metal adsorption by humic America.
umbrisols: selectivity sequences and competitive sorption kinetics. J. Colloid USEPA, 2007. Microwave Assisted Acid Digestion of Sediments, Sludges, Soils, and Oils.
Interface Sci. 280, 18. Environmental Protection Agency, United States of America.
Covelo, E.F., Vega, F.A., Andrade, M.L., 2008. Sorption and desorption of Cd, Cr, Cu, Ni, Pb USEPA, 2009. In: Cameron, R.E. (Ed.), Guide to Site and Soil Description for Hazardous
and Zn by a bric histosol and its organo-mineral fraction. J. Hazard. Mater. 159, Waste Site Characterization. Environmental Protection Agency, United States of
342347. America.
Du, C.W., Linker, R., Shaviv, A., 2007. Characterization of soils using photoacoustic mid- Usman, A.R.A., 2008. The relative adsorption selectivities of Pb, Cu, Zn, Cd and Ni by soils
infrared spectroscopy. Appl. Spectrosc. 61, 10631067. developed on shale in New Valley, Egypt. Geoderma 144, 334343.
Echeverria, J.C., Morera, M.T., Mazkiaran, C., Garrido, J.J., 1998. Competitive sorption of van Genuchten, M.T., 1981. Non Equilibrium Transport Parameters from Miscible
heavy metal by soils. Isotherms and fractional factorial experiments. Environ. Displacement Experiments. U.S. Salinity Laboratory, U.S. Department of Agricul-
Pollut. 101, 275284. ture, Riverside, California.
Fonseca, B., Maio, H., Quintelas, C., Teixeira, A., Tavares, T., 2009a. Retention of Cr(VI) Vega, F.A., Covelo, E.F., Andrade, M.L., 2006. Competitive sorption and desorption of
and Pb(II) on a loamy sand soil: kinetics, equilibria and breakthrough. Chem. Eng. J. heavy metals in mine soils: inuence of mine soil characteristics. J. Colloid Interface
152, 212219. Sci. 298, 582592.
Fonseca, B., Teixeira, A., Figueiredo, H., Tavares, T., 2009b. Modelling of the Cr(VI) Yolcubal, I., Akyol, N.H., 2007. Retention and transport of hexavalent chromium in
transport in typical soils of the North of Portugal. J. Hazard. Mater. 167, 756762. calcareous karst soils. Turk. J. Earth Sci. 16, 363379.
Fontes, M.P.F., de Matos, A.T., da Costa, L.M., Neves, J.C.L., 2000. Competitive adsorption
of zinc, cadmium, copper, and lead in three highly-weathered Brazilian soils.
Commun. Soil Sci. Plant Anal. 31, 29392958.