3rd AMIREG International Conference (2009): Assessing the Footprint of 416

Resource Utilization and Hazardous Waste Management, Athens, Greece

Sorption of nickel and copper on agricultural soils impacted by mining

activities in the North West Province, South Africa

H. Tutu, E.M. Cukrowksa and L. Chimuka

Environmental Analytical Chemistry, School of Chemistry, University of the Witwatersrand, South
Africa

ABSTRACT ducers (for both precious metals and base met-

als) in the world. Mineral exploitation consti-
The South African economy has, for many
tutes a large part of the country’s gross domestic
years, been based on the production and export
product (GDP) and is one of the important
of minerals particularly precious metals and
sources of foreign exchange. However, envi-
base metals. The North West Province has sig-
ronmental contamination as result of mining ac-
nificant reserves of platinum group metals
tivities has raised concerns from various quar-
(PGMs) as well as base metals including Cr, Ni,
ters in South Africa. Environmental pollution by
Zn, Cu and V. There are a number of smelting
chemicals and heavy metals threatens the health
operations and open cast mines which have in
of millions of people and natural resources such
the past been linked to both water and air pollu-
as soil and water (Viljoen and Reimold, 1999).
tion. In the vicinity of most of these operations
Metal contamination is a serious concern be-
are agricultural plots which produce fruits and
cause, compared to other toxic pollutants, met-
vegetables. No study has documented the im-
als are unrelenting, non-biodegradable and
pacts of mining pollution on soils in the agricul-
harmful to the environment. Accumulation of
tural plots or the effects of agrochemicals (e.g.
heavy metals (HMs) in cultivated soils is a con-
CaCl2, ammonium phosphate and organic mat-
tinuing environmental problem in many parts of
ter) on the potential mobility of metal pollutants
the world. An increase in HM concentration can
deposited on the soils.
enhance uptake of toxic metals by crops and en-
The central aim of the study was to build a
ter the human food chain. Soil contains alumi-
baseline for assessing the potential mobility of
nosilicates, oxides and organic matters as its
Ni and Cu in agricultural soil. Both adsorption
major mineral groups. These soil mineral con-
and desorption experiments were performed to
trol adsorption, transformation and release be-
assess the retention potential of the soil. Ad-
haviour of chemical constituents to soil or water
sorption at different pH regimes and times was
solution through their surface electrochemical
assessed as well as the effects of agrochemicals
properties. Soils acidity strongly influences
on sorption processes. The results pointed to the
heavy metals solubility thus presenting a major
irreversibility of the adsorption process. How-
threat to surface and ground waters. The struc-
ever, this was affected by the presence of some
tures of most soil minerals have negative
agrochemicals thus spelling out some risk con-
charges which lead to attraction of metal ions
siderations for crops and groundwater under
and other cations. Retention of metals by soil
such conditions. Time dependence showed that
depends on factors such as:
kinetics played an important role in the adsorp-
tion process. - the nature of the mineral
- organic constituents
- the nature and concentration of the metal
1. INTRODUCTION
Mobility and bioavailability of heavy metal
South Africa is one of the leading mineral pro- pollutants in soil systems can be evaluated by
3rd AMIREG International Conference (2009): Assessing the Footprint of
Resource Utilization and Hazardous Waste Management, Athens, Greece
Figure 1: Mining operations (shown as white patches)
adjacent to agricultural plots in the Rustenburg area of the
North West Province.
sorption experiments. The sorption-desorption
phenomena are essential for partitioning be-
tween solid and dissolved phases in soils, heavy
metal movement in soils and consequently
heavy metal availability to plants (Covelo et al.,
2004; Echeverria et al., 1998; Evangelou, 1998;
Garcia - Sanchez, 1999; Goldberg, 1992; Gut-
tierrez and Fuentes, 1991; Jagdish et al., 1996;
Lehmann and Harter, 1984; McLaren et al.,
1986; Sevil and Bilge, 2007; Limousin et al.,
2007).
The adsorption of metals by soils and other
adsorbents can be described by various adsorp-
tion isotherms, for example: Langmuir,
Freundlich, Frumkin, Dubinin-Radushkevici,
Brunauer-Emmet-Teller (BET) and Redlich-
Peterson among others. Since adsorption iso-
therms do not automatically provide any infor-
mation about the reactions involved in the sorp-
tion phenomenon, different adsorption mecha-
nisms also tend to characterise the partitioning
of metals between the mobile phase and the
solid phase. This information is useful for risk
assessment studies.
This study was aimed at examining sorption
processes of Ni and Cu onto mining-impacted
agricultural soil using classical adsorption mod-
els based on the Freundlich and Langmuir equa-
tions. Adsorption behaviour of these heavy met-
als in the presence of various agrochemicals has
also been investigated.
417
2. METHODS
2.1 Soil sampling
The soil samples were obtained from at 30 cm
depths in various locations on an agricultural
plot in the vicinity of mining operations (Fig. 1).
The samples were collected into polythene bags
and later dried at room temperature before siev-
ing through a 2 mm sieve.
2.2 Preparation of solutions
Artificial rainwater was used to prepare the
metal solutions, thus simulating the environ-
mental conditions in which the solutions would
likely be found in. Ideally, local rainwater
should have been collected for this purpose.
A mixture of 11.6 mg of NH4NO3 7.85 mg of
K2SO4, 1.31 mg of Na2SO4, 1.31 mg of
MgSO4.7H2O and 4.32 mg of CaCl2 were
placed in a 1000 ml volumetric flask (Huang
and Matzner, 2004). The flask was filled up to
the mark with de-ionised water.
Heavy metal solutions (both single-
component and multi-component) were pre-
pared by making 1000 mgl-1 stock solutions of
Ni(NO3)2.6H2O and Cu(NO3) from which serial
dilutions were done to obtain working solutions.
The representative agrochemicals, namely
chloride and sulphate were prepared from CaCl2
and (NH4)2SO4, respectively while fulvic acid
was extracted from a humic substances standard
which was used as surrogate for manure.
2.3 Adsorption experiments
10.0 g of each soil type was weighed into plastic
tubes. To each 50.0 ml of metal nitrate standard
was added and the contents were shaken for
16 h. The contents were centrifuged for 20 min
and the supernatant solution was analysed to
check how much metal had been absorbed.
Similar treatment of the soil was carried out us-
ing the agrochemical solutions.
The analysis of metals was carried out using
inductively coupled plasma-optical emission
spectroscopy (ICP-OES). All the sample con-
tainers were washed with soap, rinsed with tap
water, rinsed with 1 M HNO3 and then rinsed
with de-ionised water from a Milli-Q system
(Millipore, Bedford, MA. USA).
3rd AMIREG International Conference (2009): Assessing the Footprint of
Resource Utilization and Hazardous Waste Management, Athens, Greece
(a)
(b)
Figure 2: Plots of adsorption capacity (AC) vs initial con-
centration for single-component solutions of (a) Ni and
(b) Cu.
3. RESULTS AND DISCUSSION
The results of adsorption capacity against initial
concentration of heavy metals in single compo-
nent solutions are presented in Figure 2. A lin-
ear relation characterised adsorption capacity
and initial concentration. As initial concentra-
tion of the metals increased adsorption capacity
also increased.
The adsorption capacity for the single-
component solutions was fitted by the
Freundlich model (Fig. 3). This could imply
multi-layer adsorption rather than single-layer
adsorption. However, this is not a conclusive in-
ference as the Freundlich isotherm could be a
mixture of single-layer and multi-layer adsorp-
tion.
418
(a)
(b)
Figure 3: Freundlich isotherms for (a) Ni and (b) Cu in
single-component solutions.
The results for the adsorption of Ni in the
presence of sulphate are plotted in Figure 4. The
trend shows a slight decrease in adsorption ca-
pacity with increasing sulphate concentration.
This could in part be attributed to two possible
causes, namely: competitive adsorption involv-
ing NH4+ and the metal as well as the zero point
charge being reached (i.e. point of equality be-
tween the cation and anion exchange capacities)
on addition of sulphate.
Fulvic acid (FA) was used as a proxy for
humic substances family (fulvic acid, humic
acid and humin). The results of the effect of
fulvic acid on the adsorption of Cu are pre-
sented in Figure 5. The trend shows a decrease
in adsorption with increasing FA concentration.
This could be attributed to complexation of Cu
by FA, thus keeping it in solution and reducing
3rd AMIREG International Conference (2009): Assessing the Footprint of
Resource Utilization and Hazardous Waste Management, Athens, Greece
Figure 4: Adsorption of Ni in the presence of sulphate.
Figure 5: Adsorption of Cu in the presence of fulvic acid.
adsorption. However, the exact mechanism be-
hind this has to be ascertained.
4. CONCLUSION
In areas where mining activities are carried out,
there is a high risk of pollution of water sources,
air as well as the soil that fall within the imme-
diate vicinity. Adsorption and desorption study
is a common risk assessment tool which can be
employed to help understand the transport, fate
and bioavailability of heavy metals in soils. In
the study, adsorption capacity was found to in-
crease with initial concentration, implying that
the soil under study acted as an adsorbent for
both nickel and copper. Sulphate, which is one
of the agrochemicals used in the area, showed
little or insignificant influence on adsorption of
nickel and copper by the soil. Organic matter
419
(fulvic acid used as a proxy), on the other hand,
showed a significant influence on the adsorption
of these metals. Adsorption decreased with an
increasing concentration (percentage) of fulvic
acid. This was because the metals were com-
plexing with the fulvic acid and were kept in so-
lution. This resulted in the low adsorption of
nickel and copper at higher concentration of
fulvic acid.
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