Migration of trace elements from pyrite tailings in carbonate soils
Dorronsoro, C.; Martin, F.; Ortiz, I.; García, I.; Simón, M.;
Fernández, E.; Aguilar, J.; Fernández, J.
Dpto. Edafología. Facultad de Ciencias. Universidad de Granada. 18002
Granada. Spain.
As the result of a break in the retention wall of a pond containing the residues
of a pyrite mine in Aznalcóllar (Seville province, S. Spain) on 25
April 1998, 45 x 105 m3 of toxic water and tailings containing high concentrations
of heavy metals were spilled, affecting 45 km2 of land within the Agrio and
Guadiamar river basins. The concentration of heavy metals in the waters was
minimal (measured in µg kg-1; Simón et al. 1999), implying that
the soil pollution was caused exclusively by the tailings, which penetrated
irregularly through pores and cracks (Simón et al., 1999).
From the spill, the soils were covered by a layer of tailings (Figure
1) of variable thickness averaging 7 cm (López-Pamo et al., 1999).
When the tailings from a pyrite mine are exposed to oxygen and water, sulphides
oxidise to sulphates, the pH falls markedly due to the formation of sulphuric
acid, and the pollutants solubilize (Nordstrom, 1982; Förstner &
Wittmann, 1983, Nordstrom y Alpers, 1999; Alastuey et al., 1999).
In the carbonate soils the penetration of the liquid phase from the tailings
was strongly limited because the carbonates neutralized the acidity of the
solution, the oxidation of Fe2+ to Fe3+ proceeds rapidly (Singer & Stumm,
1968), iron precipitates and the calcium and sulphate ions form gypsum (Ritsema
& Groenenberg, 1993; Kashir & Yanful, 2000) precipitating most of
the heavy metals and trace elements. Gypsum formation in these soils is therefore
frequent both in the presence of carbonates as well as calcium from mineral
alteration or from calcium adsorbed by the exchange complex (Van Breemen,
1973). Thus, the mobility of heavy metals released in these processes is related
to pH and Eh, to the complex ion forms involved and to the presence of certain
soil components that favour adsorption (most commonly CaCO3, clays, organic
matter and oxy-hydroxides of iron, aluminium and manganese).
In some places in these soils, a thin layer of reddish-yellow soil (a few
mm thick) developed immediately underneath the tailings (Figure
1). This layer appeared a few weeks after the spill, the color being owed
to abundance of Fe in the tailings (Simón et al., 1999). Presumably,
this layer resulted from the impregnation of the soil by contaminating solutions
from the overlying layer of tailings.
The aim of the present work is to assess, in the reddish-yellow layer of these
soils (where the toxic spill exerted its most intense effects), the level
of pollution, the migration of the pollutant elements and the chemical consequences
of this pollution in the soil.
Three reddish-yellow layers, 4 mm thick each, were sampled on 20 June 1998
(57 days after the spill). Within these layers, the soil was sampled every
millimetre (0-1, 1-2, 2-3 and 3-4 mm), and the underlying soils were also
sampled at various depths (4-6, 13-15, 28-30 and 100-150 mm). In addition,
the layer of tailings covering the reddish-yellow layers was also sampled.
Furthermore, three adjacent soils unaffected by the spill (0-100 mm) were
used as the background.
In each sample, the particle-size distribution was determined by the pipette
method after elimination of organic matter with H2O2 and dispersion with sodium
hexametaphosphate (Loveland and Whalley, 1991). The pH was measured potentiometrically
in a 1:2.5 soil-water suspension. The CaCO3 equivalent was determined by a
manometric method (Williams, 1948). Total carbon was analysed by dry combustion
with a LECO instrument, and the organic carbon was determined by the difference
between total carbon and inorganic carbon from CaCO3. The cation-exchange
capacity (CEC) was determined with 1N Na-acetate at pH 8.2. Pills of soil
and lithium tetraborate (0.6:5.5) were prepared and the total content in Fe
was measured by X-ray fluorescence using a Philips PW-1404 instrument.
Samples of the tailings and soils, very finely ground (< 0.05 mm), were
digested in strong acids (HNO3 + HF + HCl). In each digested sample, 25 elements
were measured by ICP-MS with a PE SCIEX ELAN-5000A spectrometer. The accuracy
of the method was corroborated by analyses (6 replicates) of Standard Reference
Material: SRM 2711 (Simon et al., 1999). A Zeiss-950 scanning electron microscope
with a Tracor Northern 523 X-ray energy-scattering microanalyser (SEM-EDS)
was used to examine the morphology and analyse the composition of certain
minerals present in the first 6 mm of the soil. For X-ray diffraction, a Philips
PW-1710 instrument with CuKa radiation was used.
The climate of the study area is typically Mediterranean (hot, dry summers;
cold, wet winters; temperate autumns; and springs with variable rainfall).
The average annual rainfall is 630 mm, the average temperature 17.9 °C
and the potential evapotranspiration 975 mm.
Soil properties and main components
The soils that presented reddish-yellow layers were sandy carbonate with low
organic-matter content, moderate cation-exchange capacities, low pH and little
iron (approximately 3%; Table 1).
These layers presented the Munsell color 7.5YR6/8, while the rest of the soil
had the color 10YR6/3.
The oxidation of the sulphides in the tailings caused a sulphate rich-contaminant
solution (Stumm and Morgan, 1981) which on infiltration with rainwater strongly
acidified the soil. The infiltration of the acidic solution decarbonated and
acidified the reddish-yellow layer (the first 4 mm of the soil). The carbonate
content diminished in this layer by up to 85% with respect to the underlying
soil (Table 2). The iron within this
layer strongly increased (Table 2),
indicating a high degree of pollution. Also, from this Fe distribution, we
deduce that this metal was responsible for the reddish-yellow coloration.
The infiltration of the acidic solution led to hydrolysis of the finest mineral
particles, reducing the mean clay content by roughly 62% with respect to the
underlying soil. In addition, the organic-carbon content declined by 45% in
the reddish-yellow layer.
The X-ray diffractograms of the underlying soil indicate a mineralogy primarily
of quartz, feldspar, calcite and, in lesser quantity, dolomite (Figure
2). In the soil samples within the layer, abundant gypsum formed (Ritsema
& Groenenberg, 1993; Kashir & Yanful, 2000), while the peaks corresponding
to carbonates strongly decreased. In no case was pyrite detected, revealing
the complete lack of direct contamination by the tailings in the interior
of the layer (this fact was corroborated by electron microscopy).
The oriented aggregates of the clay fraction in the samples from the soil
underlying the reddish-yellow layer gave diffractograms showing illite, kaolinite,
smectite, interstratified complexes of chlorite/smectite, calcite and feldspars.
In the samples from the interior of this layer, the peaks become broader and
lower, indicating a generalized breakdown of minerals, both of the phyllosilicates
as well as of the carbonates (Figure 3).
The presence and alteration of the components present in the soil (fundamentally,
feldspars, micas and clays) boosted the capacity of acid neutralization and
retention of released metals. Identification of such mineral alteration is
not easy, the phyllosilicates and particularly smectites apparently being
the most active in neutralizing the acidity (Pons et al, 1982; van Breemen,
1980).
Electron microscopy of the reddish-yellow layer confirmed the presence of
gypsum (Miedema et al., 1974; Eswaran & Shoba, 1983) together with sulphates
that had highly diverse compositions (sometimes jarosite; Wagner et al., 1982;
Eswaran & Shoba, 1983) as well as Fe oxides and hydroxides in much lower
proportions (Figure 4). In carbonate
soils affected by acid solutions the presence of iron oxyhydroxide coatings
over calcite grains with substantial amounts of adsorbed Zn, Cu and Pb have
been described (Bertorino et al, 1995). Electron microscopy of these samples
also revealed that the S, Fe and Al constituted main elements, while Zn, Mn
and K were found in lesser concentrations. These results indicate that, in
addition to the precipitation as gypsum, sulphates may also be adsorbed by
various Fe and Al oxides and hydrous oxides, this being assumed to be the
primary mechanism for SO42- retention in a variety of soils (Parfitt &
Smart, 1978; Johnson & Todd, 1983; Singh, 1984). The Fe compounds were
more abundant in the upper part of the layer (0-3 mm), whereas the Al sulphates,
and at times with Zn, were concentrated in below (4-6 mm).
Elemental composition
A total of 25 trace elements were analysed (Table
2). According to the ANOVA, the values of the different layers of polluted
vs. non-polluted soils (values for the same non-polluted soils being similar
to those of Simon et al. 1999, Lopez-Pamo et al. 1999, and Cabrera et al.
1999) showed significant increases in Pb, Zn, As, Cu, Sb, Bi, Tl, Co, Cu and
In; therefore, only 10 elements were deemed pollutants.
The reddish-yellow layer showed high contents of heavy metals and associated
elements, with Zn and Cu presenting the highest concentrations. The Zn reached
values of 23090 mg kg-1, this being 2.8-fold higher than in the tailings (table
3) and 230-fold the content of uncontaminated soils (column UCS of Table
3). Meanwhile, Cu registered 11480 mg kg-1 in the reddish-yellow layer—that
is, 5.3-fold more than in the original tailings, and 446.7-fold greater than
in non-polluted soils.
The increase of the elements in the soils of the reddish-yellow layer can
be ascribed to the secondary oxidation of the sulphides from the tailings
(oxidative pollution), which, on changing to sulphates (Nordstrom, 1982) mobilized
trace elements (Rogowski et al., 1977; Caruccio and Geidel, 1978), these in
turn progressively penetrating the soil with the rainwater.
Depth distribution of the pollution
The distribution in depth of the10 pollutant elements is presented in Figure
5, showing:
i) The highest concentrations were consistently within the first 6 mm.
ii) Substantial concentrations were invariably found in the upper 15 mm.
iii) Below a certain depth (6 mm for As, Pb, Bi Tl, Cu and Sb; and 15 mm for
Zn, Co, Cd and In) the concentration in pollutant elements reached values
similar to those of uncontaminated soils.
iv) Nevertheless, Zn, Cu, Sb, Tl and Cd showed small but significant accumulations
at 100-150 mm.
Although all the elements dissolved in the acidic solution tended to accumulate
in the first 15 mm of the soil, clear differences appeared. Thus Zn, Cu, Cd
and Co, the most mobile elements, showed similar distributions, with concentrations
increasing from the upper zone (0-1 mm) downwards, reaching the highest values
near where the reddish-yellow layer met the underlying soil (4 mm). The Zn
and Cu became less soluble where the soil pH was higher, reaching their highest
precipitation values at pH 6.8 at 4 mm in depth. For the deepest zones, with
pH values exceeding 7.6, concentrations fell drastically. The Cd and Co reached
their highest accumulation at 4-6 mm, just below the reddish-yellow layer,
and thus proved more mobile than Fe. The concentration in Co decreased to
values lower than background in the uppermost part of the layer (0-3mm), indicating
that at pH <6.4 this element dissolved and infiltrated the underlying soil
(Figure 5).
For As, Pb, In, Tl, Bi and Sb, the concentrations declined intensely from
the upper part (0-1 mm) downwards, being less mobile than Fe. The Pb, As and
Bi did not reach the lower limit of the reddish-yellow layer, while the In
and the Sb remained partially soluble at 15 mm in depth, with a pH of 7.9.
These results coincide with other authors: For sample, Plant and Raiswell
(1983) indicated that in oxidizing acidic environments, the relative mobility
of Zn, Cd, Co and Cu is considered high or moderately high, while that of
Pb is low. Under neutral to basic conditions, relative mobility is considered
low or very low for all of the elements.
Also, regarding the variations of heavy metals in depth, Martin and Bullock
(1994) observed that in an acidic environment, Pb concentrations reached maximum
values within the first cm, whereas Zn, Cd and Cu reached higher values at
3 cm in depth. The concentrations of all of these metals diminished rapidly
with depth, at 30 cm approaching background values.
With respect to the relative mobility of Fe, Simms et al (2000) studied the
distribution of total Zn, and Fe, among other parameters, inside experimental
columns filled with oxidized as well as unoxidized tailings, observing that
the highest Fe concentrations were reached at a shallower depth than were
those of Zn. The pH of the oxidized zone was slightly lower than 6.0.In this
sense, the mobility of Pb is less than of Fe in strongly acid media (Lindsay,
1981).
Migration index
To evaluate the degree of mobility of the different pollutants, we calculated
a migration index (MI) from the following equation, for the upper 0-30 mm
(main zone of accumulation):
7
MI = ∑ (P / TP) d
n=1
where n represents the layers sampled, P is the pollution of each element
in each layer sampled, TP is the sum of the pollution of each element of all
layers sampled, and d the depth (mm) of the lower limit of each layer sampled.
The value of this index would range from 1 (if the element accumulated entirely
in the first 1 mm) to 30 (if the element accumulated entirely between 28 and
30 mm). The sequence of greater to lesser mobility would be (MI value in parenthesis):
Co (6.0) > Cd (4.3) > Zn (4.0) >Tl (3.6) >Sb (3.5) >Cu (3.2)
>Pb (2.2) >In (1.9) >Bi (1.9) >As (1.8)
For the same spill, comparable results were reported by Vidal et al. (1999)
three months after the accident, with the exception of Tl, which these authors
include among the elements of low mobility. This appears to indicate that
Tl can decrease in mobility over time.
By ANOVA, we verified that all the MI values were highly significant (p<0.001)
and by Duncan test we divided the MI values into 3 subsets. Elements with
high mobility were Co, Cd and Zn; with moderate mobility, Tl, Sb and Cu; with
low mobility, Pb, In, Bi and As.
The infiltration into the soil of the acid solution formed by oxidation of
pyrite tailings gave rise to weathering of the carbonates, acidification,
and hydrolysis of the phyllosilicate particles (more intense the finer the
particle size), but only in the first 4 mm of the soil. The SO42- ions present
in the acidic solution precipitated at this depth, forming gypsum, iron and
aluminium sulphates and complex sulphates. The Fe3+ ions also precipitated
at this depth, apparently, adsorbing a large part of the pollutants dissolved
in the acidic solution. Most of these pollutants did not appreciably penetrate
beyond 15 mm in depth, and large accumulations were found only in the first
6 mm.
For this type of toxic spill, our results indicate that in carbonate soils
under a Mediterranean climate (and under study conditions), the pollutants
tend to accumulate in the upper 0-15 mm of the soil, without contaminating
the subsoil or groundwater.
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