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A three-year field experiment was conducted in North-East Poland. Each year three sulfur fertilization rates in the form of sulphate (S-SO42–) and pure (S–S0) sulfur were applied: 40, 80, and 120 kg/ha. After the third year of the study, the application of sulfate and elemental sulfur decreased the zinc content of 0–40 and 40–80 cm soil layers, as compared with soil sampled before the experiment. Over the entire experimental period, sulfur fertilization had no significant effect on changes in the natural copper content of soil at a depth of 0–40 and 40–80 cm. Manganese concentrations remained at a similar level at a soil depth of 0–40 cm. The manganese content of the 40–80 cm soil layer was substantially lower than in the 0–40 cm horizon. An insignificant increase in the lead content of soil was observed. The applied doses of sulfate and elemental sulfur led to an increase in the cadmium content of soil depth of 0–40 cm. Sulfur fertilization contributed to a decrease in the nickel content of soil. The applied doses of sulfate and elemental sulfur exerted a stronger effect in the 0–40 cm soil layer than in the 40–80 cm horizon.
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PLANT SOIL ENVIRON., 58, 2012 (3): 135–140 135
The concentrations of soluble forms of heavy
metals in soil are mostly determined by their total
content and soil processes. Soil organic matter
and pH are the key factors affecting the content
and mobility of heavy metals in soil (Soliman
et al. 1992, Martinez and Motto 2000, Borůvka
and Drábek 2004, Šichorová et al. 2004). Another
important consideration is human activity which
contributes to soil contamination in some regions
of Poland, thus leading to changes in the natural
heavy metals content. In the 1980’s SO
2
emissions
in Poland were at about Gg/year, which provided
an average of 132.1 kg of SO
2
/ha during the year.
In 2006, SO
2
emissions were reduced to 1195 Gg/
year, i.e. 38.3 kg of SO
2
/ha CSO (2008).
According to many authors (Nederlof and
Riemsolijk 1995, Temminghoff et al. 1997), the
toxicity of heavy metals and their availability to
plants increase due to soil acidification caused by
sulfur deposition. In a study by Kayser et al. (2000),
the application of elemental sulfur and a decrease
in soil pH increased the solubility of heavy metals.
Some elements, including zinc and copper, pre-
cipitate as sulfides and sulfates, to produce forms
that are relatively immobile in the soil profile
(Kabata-Pendias and Pendias 1992). Cadmium, on
the other hand, can form inorganic ligands with
S-SO
4
2–
(McLaughlin et al. 1996).
Direct and residual effect of sulfur fertilization
on changes in the heavy metal content of soil has
to be taken into account in environmental analy-
ses in agricultural areas, including environmental
impact assessments and predictions.
The purpose of the present study was to deter-
mine the effect of fertilization with increasing rates
of sulfur applied in the form of sulphates and as
elemental sulfur on the natural content of heavy
metals in soil at the depth 0–40 cm and 40–80 cm.
MATERIAL AND METHODS
A three-year field experiment was conducted
from 2000 to 2002, in North-East Poland. The
The effect of different sulfur doses and forms on changes
of soil heavy metals
M. Skwierawska
1
, L. Zawartka
1
, A. Skwierawski
2
, A. Nogalska
1
1
Departament of Agricultural Chemistry and Environmental Protection, University
of Warmia and Mazury in Olsztyn, Olsztyn, Poland
2
Chair of Land Reclamation and Management, University of Warmia and Mazury
in Olsztyn, Olsztyn, Poland
ABSTRACT
A three-year field experiment was conducted in North-East Poland. Each year three sulfur fertilization rates in the
form of sulphate (S-SO
4
2–
) and pure (SS
0
) sulfur were applied: 40, 80, and 120 kg/ha. After the third year of the
study, the application of sulfate and elemental sulfur decreased the zinc content of 0–40 and 40–80 cm soil layers,
as compared with soil sampled before the experiment. Over the entire experimental period, sulfur fertilization had
no significant effect on changes in the natural copper content of soil at a depth of 0–40 and 40–80 cm. Manganese
concentrations remained at a similar level at a soil depth of 0–40 cm. e manganese content of the 40–80 cm soil
layer was substantially lower than in the 0–40 cm horizon. An insignificant increase in the lead content of soil was
observed. e applied doses of sulfate and elemental sulfur led to an increase in the cadmium content of soil depth
of 0–40 cm. Sulfur fertilization contributed to a decrease in the nickel content of soil. e applied doses of sulfate
and elemental sulfur exerted a stronger effect in the 0–40 cm soil layer than in the 40–80 cm horizon.
Keywords: fertilizer; S-SO
4
2–
; S-elemental; available forms; zinc; copper; manganese; lead; cadmium; nickel;
interaction
136 PLANT SOIL ENVIRON., 58, 2012 (3): 135–140
village is distant from larger industrial plants
which emit sulfur compounds and lies far from
any big cities. The concentration of sulfur in the
soil was not caused by human activity.
The trial was set up on Dystric Cambisols (FAO),
of the granulometric composition of heavy loamy
sand. The initial soil had the following properties:
pH
KCl
= 5.30, mineral nitrogen 24.0, sulphate sulfur
4.10, available phosphorus 34.5 and potassium
110.0 mg/kg of soil. The annual rates of sulphate
sulfur (S-SO
4
2–
-S) and elemental sulfur (S
0
-S) were:
S
1
– 40, S
2
– 80 and S
3
– 120 kg/ha. Air-dry soil
was passed through a 1 mm mesh sieve. The soil
samples were used to determine soil pH in 1 mol
KCl (the ratio between soil and extraction 1:2.5);
total sulfur (Butters and Chenery 1959) and S-SO
4
2–
with the turbidimetric method (the ratio between
soil and extraction 1:3); N-NO
3
by colorimetry
using phenyl disulphonic acid (the ratio between
soil and extraction 1:5); N-NH
4
+
was determined
using the Nesslers reagent (the ratio between
soil and extraction 1:5); available phosphorus
and potassium was determined with the Enger
Riehms method (DL) – (the ratio between soil
and extraction 1:50) – (Panak 1997).
The permanent experiment was established in
a random block design and consisted of eight
fertilization treatments with four replications: (1)
unfertilized control; (2) NPK; (3) NPK + S
1
-SO
4
;
(4) NPK + S
2
-SO
4
; (5) NPK + S
3
-SO
4
; (6) NPK +
S
1
-S
0
; (7) NPK + S
2
-S
0
; (8) NPK + S
3
-S
0
.
Nitrogen in the form of ammonium nitrate or am-
monium sulphate, phosphorus in the form of triple
superphosphate, potassium in the form of potassium
salt of 60% or in the form of potassium sulphate,
sulfur in the form of potassium sulphate and am-
monium sulphate supplementation as well as in the
form of elemental sulfur. The NPK rates (Table 1)
depended on the crop species and soil fertility.
Soil samples were collected from each plot, at
0–40 and 40–80 cm depths, prior to the establish-
ment of the trials, after each harvest and before
sowing the consecutive crop. Air-dry soil was
passed through a 1 mm mesh sieve. The soil samg-
ples were used to determine the concentrations:
Zn, Cu, Mn, Pb, Cd, and Ni in soil (extractions
with 1 mol HCl/dm
3
, the ratio between soil and
extraction – 1:10) was determined by AAS method
using Schimadzu AA apparatus (model AA-6800,
Kyoto, Japan).
The results of the yields and chemical analysis of
soil were processed statistically with the analysis of
variance for a two-factor experiment in a random
block design, using the form of sulfur as factor a
and rate of sulfur as factor b. Additional statisti-
cal analyses were performed with the software
package Statistica 6.0 PL, to carry out analysis of
regression with the Duncans tests with an aim
of determining statistical differences between
sets of data.
RESULTS AND DISCUSSION
Soil pH. Results of soil reaction changes after
sulfur fertilization are presented in the publication
by Skwierawska et al. (2008a).
During the three years of the experiment, sul-
phate and elementary sulphur addition had a sig-
nificant effect on changes in the soil pH at the
depth of 0–40 cm. The rate of 120 kg S-SO
4
2–
/ha
and S-S
0
caused a significant decline in the soil
pH versus the control object. At the deeper layer
of soil (40–80 cm) the soil pH was in general more
even and lower than in the top soil layer in the
analogous objects.
Rate 120 kg S-SO
4
2–
/ha and S-S
0
depressed soil pH
in the 0–40 cm soil horizon. Acidification of soil
caused by S-SO
4
2–
became evident already in the
first year of the trials, while that produced by S-S
0
did not occur until the third year. The influence
of sulphur on soil pH at the depth of 40–80 cm
was irregular.
Zinc. Changes in the natural heavy metal content
of soil fertilized with sulfate and elemental sulfur
at a dose of 40, 80, and 120 kg/ha were studied over
a three-year period (Table 2). Before the experi-
ment, zinc concentrations ranged from 15.65 to
17.00 mg/kg in the 0–40 cm soil layer, and from
5.80 to 7.60 mg/kg in the 40–80 cm horizon.
At the end of the experiment, zinc concentra-
tions in the 0–40 cm soil layer ranged from 2.92
to 3.99 mg/kg, irrespective of sulfur doses, and
they were generally considerably lower than in
the corresponding treatments in the first and
second year of the study. This could be due to in-
creased bioavailability of zinc. Kayser et al. (2001)
demonstrated that the application of elemental
sulfur increased zinc solubility in the soil and
Table 1. NPK rates applied in the trials
Crops Year
N P K
(kg/ha)
Head cabbage 2000 200.0 52.5 180.0
Common onion 2001 160.0 60.0 183.0
Spring barley 2002 90.0 80.0 111.0
-
PLANT SOIL ENVIRON., 58, 2012 (3): 135–140 137
utilization by plants. Kaya et al. (2009) reported
that the application of sulfur and sulfur-containing
waste resulted in decrease in soil pH, but it also
increased the concentrations of nutrients available
to plants, such as Zn, Cu and Mn. Different results
were obtained by Abdou et al. (2011) who did not
observe an increase in zinc availability to plants
as a result of elemental sulfur fertilization. In the
present study, zinc concentrations were lower
in the 40–80 cm soil layer than in the 0–40 cm
horizon, and they were significantly affected only
by sulfur form. Elemental sulfur contributed to a
higher decrease in zinc levels in the soil.
Copper. Before the experiment, the copper con-
tent of the 0–40 cm soil layer remained at a stable
level in all treatments (Table 2). Copper concen-
trations tended to increase in the treatment with
a single dose of elemental sulfur. In the 40–80 cm
horizon, copper content ranged from 1.00 to
1.26 mg/kg soil.
In the first year of the study, sulfur fertiliza-
tion had no significant effect on changes in the
copper content of soil. In the second year, cop-
per concentrations increased in the 0–40 cm soil
layer, relative to the NPK treatment, in particular
after sulfate application. This could result from
changes in soil pH. Sulfur decreases soil pH and
increases the solubility, availability and mobility
of heavy metals (Tichý et al. 1997, Seidel et al.
1998, Kayser et al. 2000, Martinez et al. 2000, Cui
Table 2. Effect of different rates and forms of sulphur on heavy metals content in the soil layers at 0–40 and
40–80 cm depths, before and after experiment (mg/kg soil)
Treatments
Before experiment After experiment
Zn Cu Mn Pb Cd Ni Zn Cu Mn Pb Cd Ni
Horizon 0–40 cm
0 17.00 1.80 89.00 5.26 0.080 1.34 2.92 1.72 85.75 5.50 0.096 0.367
NPK 16.18 1.90 106.25 5.00 0.085 0.89 2.95 1.63 88.66 5.59 0.119 0.592
NPK + S
1
-SO
4
2–
16.61 1.90 109.00 5.43 0.080 0.68 3.16 1.57 107.41 5.99 0.132 0.505
NPK + S
2
-SO
4
2–
15.65 1.80 101.74 5.16 0.089 1.35 3.44 1.78 91.32 4.66 0.105 0.556
NPK + S
3
-SO
4
2–
16.15 1.76 106.32 5.55 0.077 1.45 3.94 1.56 93.44 5.95 0.116 0.501
NPK + S
1
-S
_0
15.89 2.00 101.89 4.78 0.069 0.83 3.69 1.53 93.19 6.11 0.120 0.539
NPK + S
2
-S-
0
16.12 1.50 101.15 4.91 0.089 1.09 3.30 1.58 90.16 5.81 0.093 0.470
NPK + S
3
-S-
0
15.82 1.60 99.74 4.29 0.096 1.00 3.99 1.72 91.80 6.05 0.119 0.516
LSD
0.05
a n.s. n.s. n.s. n.s. n.s. n.s. 0.2754 n.s. n.s. 0.295 n.s n.s.
b n.s. n.s. n.s. n.s. n.s. 0.2191 n.s. n.s. 6.776 n.s. n.s. 0.0974
a × b n.s. 0.299 n.s. n.s. n.s. 0.3098 n.s. n.s. 9.583 0.591 0.0274 n.s.
Horizon 40–80 cm
0 6.72 1.20 41.64 2.11 0.037 0.80 1.94 0.767 40.02 2.18 0.013 0.178
NPK 6.51 1.00 41.32 3.52 0.036 1.13 2.32 1.157 32.27 2.89 0.029 0.413
NPK + S
1
-SO
4
2–
6.12 1.11 45.87 2.41 0.038 1.35 2.08 0.764 41.31 3.14 0.033 0.306
NPK + S
2
-SO
4
2–
5.99 1.15 43.75 2.84 0.039 1.09 1.75 0.713 28.96 3.18 0.021 0.290
NPK + S
3
-SO
4
2–
5.80 1.20 46.30 2.78 0.032 1.01 1.69 0.891 41.53 2.38 0.030 0.265
NPK + S
1
-S
_0
7.50 1.26 33.86 2.52 0.036 1.30 1.57 1.130 35.45 2.62 0.039 0.433
NPK + S
2
-S-
0
6.30 1.04 39.80 1.64 0.035 0.98 1.79 0.708 29.80 2.65 0.017 0.162
NPK + S
3
-S-
0
7.60 1.00 39.45 2.30 0.031 1.01 1.65 0.761 26.07 3.14 0.021 0.178
LSD
0.05
a n.s. n.s. n.s. n.s. n.s. n.s. 0.210 n.s. n.s. n.s. n.s. n.s.
b n.s. n.s. n.s. n.s. n.s. n.s. n.s. n.s. 7.9925 0.572 n.s. n.s.
a × b n.s. n.s. n.s. n.s. n.s. n.s. n.s. n.s. n.s. n.s. n.s. n.s.
a – form of sulphur; b – dose of sulphur; a × b – interaction, n.s. – no significant difference
138 PLANT SOIL ENVIRON., 58, 2012 (3): 135–140
et al. 2004). In a study by Takáč et al. (2009), the
content of mobile copper forms in the soil was
not significantly affected by soil pH.
In the third year of the study, at the end of the
experiment, copper concentrations in the 0–40 cm
soil layer were comparable, regardless of sulfur
forms and doses. A decrease in copper content
was noted, compared with soil samples collected
before the experiment. A similar trend was ob-
served in the 40–80 cm horizon, which could be
due to copper uptake by plants (Skwierawska et al.
2008b). Kaya et al. (2009) reported that increased
application of sulfur and sulfur-containing waste
led to a significant increase in the average copper
content of plants. In the present study, over the
entire experimental period, sulfur fertilization
had no significant effect on changes in the copper
content of soil at a depth of 0–40 and 40–80 cm.
Manganese. One of the adverse effects of sulfur
contamination is an increase in manganese solu-
bility and the mobilization of heavy metals from
both natural and anthropogenic sources (James
and Riha 1984). Before the experiment, the man-
ganese content of both soil horizons remained
stable (Table 2). Manganese concentrations were
substantially lower in the 40–80 cm horizon than
in the top layer.
In the autumn, after the third year of the study,
the manganese content of the 0–40 cm soil layer
ranged from 85.75 to 107.41 mg/kg. Form of sulfur
had no effect on changes in manganese concentra-
tions in the soil. The application of 40 kg sulfur
contributed to an increase in manganese content,
compared with higher sulfur doses. Sulfate and
elemental sulfur fertilization increased manganese
concentrations in the soil, in comparison with the
control treatments. The manganese content of the
40–80 cm horizon was considerably lower than
in the surface layer, and it was not significantly
affected by sulfur form. Manganese depletion was
observed, relative to the corresponding treat-
ments before the experiment. In a study by Erdal
et al. (2004), the application of elemental sulfur in
combination with nitrogen fertilizers substantially
increased the bioavailability soil heavy metals, in
particular manganese. Lošák et al. (2011) describe
that individual nitrogen fertilization did not reduce
the content of manganese in the plant or grain of
maize. According to Abdou et al. (2011), sulfur
fertilization has a minor effect on manganese
availability.
Over a three-year period, manganese concentra-
tions in the 0–40 cm soil layer remained stable, but
were lower than in soil samples collected before the
experiment. The only exception was the treatment
fertilized with 40 kg S-SO
4
2–
-S, where manganese
content was higher than in the other treatments.
This trend was maintained throughout the study.
In the 40–80 cm layer, manganese concentrations
were considerably lower than in the 0–40 cm hori-
zon. The highest manganese content was observed
in the treatment with a triple sulfate dose whose
effect was noticeable over the entire experimental
period. This could result from change in soil pH
from acidic to highly acidic (Skwierawska et al.
2008a), which increased the content of readily
available manganese.
Lead. Before the experiment, the lead content
of soil samples collected at a depth of 0–40 cm
and 40–80 cm was similar (Table 2).
In the second year of the study, sulfur fertilization
had no significant effect on changes in the lead
content of both sampled horizons (0–40 cm and
40–80 cm). The lead content of the 40–80 cm soil
layer was considerably lower than in the 0–40 cm
horizon, in the corresponding treatments. Similar
results were obtained by Šichorová et al. (2004),
in the cited study, lead concentrations decreased
with increasing soil depth.
At the end of the experiment, the lead content of
the 0–40 cm horizon ranged from 4.66 to 6.11 mg/
kg soil, and it was significantly affected by sulfur
form. A minor increase in lead concentrations was
observed. Terelak et al. (1996) found that sulfur-
contaminated soils are characterized by increased
bioavailability and accumulation of Mn, Cd, and Pb
in crops. Similar findings were reported by Holoah
et al. (2010) – increasing doses of elemental sulfur
caused a significant increase in lead content and
uptake by plants. In our study, lead concentrations
were lower in the 40–80 cm layer than in the 0–40 cm
horizon, and they were significantly affected only
by sulfur dose.
Cadmium. Cadmium is one of the most toxic and
mobile metallic elements (Basta et al. 2005, Zhao
and Masaihiko 2007). Before the experiment, the
cadmium content of both sampled soil horizons
(0–40 cm and 40–80 cm) was comparable, but it
was slightly lower in the deeper layer than in the
topsoil (Table 2). Similar trends were observed
in the first and second year of the study, when
neither sulfur form nor dose exerted a significant
effect on changes in cadmium concentrations in
the soil. The effect of sulfur was noted as late as
in the third year. At the end of the experiment,
the cadmium content of the 0–40 cm soil layer
increased in treatments fertilized with sulfur, in
particular at a dose of 40 kg S. Changes in the
PLANT SOIL ENVIRON., 58, 2012 (3): 135–140 139
natural cadmium content of soil, observed during
a three-year period, were irregular. No distinct
trends were noted in response to sulfate and el-
emental sulfur fertilization. As demonstrated by
McLaughlin et al. (1998), an increase in Na
2
SO
4
doses is followed by an increase in the concentra-
tions of active cadmium forms in the soil solution.
Such an increase was also noted by Kayser et al.
(2001) as a result of elemental sulfur application.
Nickel. Before the experiment, the nickel content
of the 0–40 cm soil layer varied widely, from 0.68
to 1.45 mg/kg. In the first year of the study, the
nickel content of the 0–40 cm horizon increased
with increasing sulfate doses (Table 2). Sulfate
sulfur exerted a stronger effect than elemental
sulfur. The experimental factors had no significant
influence on changes in nickel concentrations in
the 40–80 cm soil layer.
At the end of the experiment, the nickel content
of the 0–40 cm soil layer ranged from 0.367 to
0.592 mg/kg. Nickel depletion was observed, in
comparison with the previous two years, probably
due to increased nickel uptake by plants. Our results
corroborate the findings of Holah et al. (2010).
Sulfur fertilization had no significant influence on
changes in nickel concentrations in the 40–80 cm
horizon. However, a steady decrease in the nickel
content of soil was noted, compared with the cor-
responding treatments in the past two years.
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Received on November 2, 2011
Corresponding author:
Dr. Ing. Małgorzata Skwierawska, University of Warmia and Mazury in Olsztyn, Department of Agricultural
Chemistry and Environmental Protection, ul. Oczapowskiego 8, 10-718 Olsztyn, Poland
e-mail: malgorzata.skwierawska@uwm.edu.pl
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