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a,*
, C. Sarzanini a,
a
Department of Analytical Chemistry, University of Torino, Via Giuria 5, 10125 Torino, Italy
Department of Sciences and Advanced Technologies, University of East Piedmont, Spalto Marengo 33, 15100 Alessandria, Italy
c
Institute for Wood, Plant and Environment (I.P.L.A.), Corso Casale 476, 10132 Torino, Italy
Received 8 February 2002; received in revised form 18 June 2002; accepted 28 June 2002
Abstract
The distribution and speciation of heavy metals in ve agricultural soils of Piedmont Region (north-western Italy)
were investigated. Ten metals, namely Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Ti and Zn were considered. Analytical determinations were performed by atomic emission or atomic absorption spectroscopy after microwave sample dissolution in
acid solution. Total metal concentrations t in the typical concentration ranges for unpolluted soils, with the exception
of cadmium and lead content in some horizons. The eect of sampling depth on concentrations was discussed. Speciation studies were carried out by applying Tessiers procedure, which allows to subdivide the total metal content into
ve fractions, representing portions bound to dierent components of the soil. Moreover, the element labilities in two
soils were evaluated by extraction with EDTA. Correlations among the variables and/or similarities among the sampling points were identied by principal component analysis and hierarchical cluster analysis.
2002 Elsevier Science Ltd. All rights reserved.
Keywords: Metals; Speciation; Agricultural soils; Pattern recognition; Piedmont; Italy
1. Introduction
The concentrations of heavy metals in soils are associated with biological and geochemical cycles and are
inuenced by anthropogenic activities, such as agricultural practices, transport, industrial activities, waste
disposal (Lund, 1990). The knowledge of both the total
concentration and chemical speciation is necessary to
characterise the behaviour of heavy metals in soils. In
fact it is well known that metals are present in soils in
dierent chemical forms, which inuence their reactivity
and hence their mobility and bioavailability. Speciation
0045-6535/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 0 2 ) 0 0 3 5 2 - 1
546
2. Experimental
2.1. Sampling
Soil samples were collected in ve sites in Piedmont
Region (north-western Italy). The sites are located in the
small towns of Poirino (Province of Asti), Vigone (two
sites, hereafter called Vigone 1 and Vigone 2), S. Maurizio Canavese and Carmagnola (Province of Torino).
Table 1 shows their taxonomic classication (Soil Conservation Service USDA, 1984; Soil Survey Sta, 1990;
Soil Survey Sta, 1999).
All soils were used as permanent meadows, with the
exception of the one from Carmagnola, cultivated to
maize. Vigone soils have an alluvial origin, whereas the
Table 1
Soil identication and description
Code
Position
Soil phase
USDA taxonomy
Carmagnola
S. Maurizio Canavese
Poirino
V1
Vigone 1
V2
Vigone 2
547
Table 2
The general characteristics of the investigated soils
Soil parameter
Horizon
% silt
(0.0050.002 mm)
pH
%C
Organic matter
CEC
% clay
(<0.002 mm)
CAa
CBa
CCa
Ap
AC
C
14.8
3.5
6.1
43.1
66.1
48.9
8.5
7.0
6.7
7.9
8.1
8.0
1.16
0.55
0.39
2.00
0.95
0.67
10.1
8.50
5.20
MAa
MBa
MCa
Ao
Bw
Cr
36.7
52.2
77
56.5
37.9
14.8
6.8
9.9
8.2
5.9
6.6
6.5
2.11
0.69
0.06
3.64
1.19
0.10
14.0
9.20
9.20
PAa
PBa
PCa
Ap
Bg
BCg
45.6
49.6
45.1
51.4
30.4
29.1
3.0
12.9
15.4
6.7
6.5
6.8
1.92
0.07
0.08
3.31
0.12
0.14
17.2
11.5
8.20
V1Aa
V1Ba
V1Ca
V1Da
V1Ea
Ap
AB
Bw
BC
C1
47.8
45.6
46.7
54.4
68.3
43.8
42.4
31.9
28.8
23.3
8.4
12
21.4
16.8
8.4
6.0
6.6
6.7
6.9
6.7
0.82
0.23
1.41
0.40
9.45
8.51
V2Aa
V2Ba
V2Ca
V2Da
V2Ea
Ap
AB
Bg
BC
C
60.5
67.9
83.4
97.2
95.3
34.4
23.2
14.6
2.2
3.2
5.1
8.9
2.0
0.6
1.5
6.2
6.5
7.4
7.4
7.3
0.87
0.27
1.50
0.47
9.32
12.1
Carmagnola: CA (040 cm); CB (4090 cm); CC (90120 cm); S. Maurizio Canavese: MA (030 cm); MB (3060 cm); MC (6080
cm) Poirino: IA (020 cm); IB (2080 cm); IC (80160 cm) Vigone 1: V1A (030 cm); V1B (3050 cm); V1C (5070 cm); V1D (70120
cm); V1E (120160 cm) Vigone 2: V2A (035 cm); V2B (3575 cm); V2C (75120 cm); V2D (120175 cm); V2E (175195 cm).
548
549
Table 3
Total metal concentrations in considered soils, typical literature ranges and most common values, average abundance in the earths
crust (values in mg/kg unless otherwise stated)
Al
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Ti
Zn
CA
CB
CC
67 900
77 800
74 700
5.4
6.4
3.4
162
174
146
30
44
28
34 000
39 500
36 300
833
1080
899
102
141
132
215
291
229
3550
4160
3760
94
103
86
MA
MB
MC
73 500
72 600
57 900
4.9
4.3
2.1
588
562
598
34
28
30
46 100
44 600
41 800
1130
965
802
675
535
510
270
99
750
5520
5250
6150
104
73
73
PA
PB
PC
47 400
81 500
77 800
2.7
4.3
5.1
124
170
143
19
46
36
22 900
38 600
36 200
525
1050
900
32
126
94
141
181
149
3070
4270
3850
82
92
93
V1A
V1B
V1C
V1D
V1E
V1F
58 600
69 300
72 100
66 200
56 600
67 600
1.3
1.1
0.9
0.4
1.3
0.3
116
162
156
137
138
1580
24
27
36
34
30
34
31 600
24 400
42 500
40 600
63 700
33 800
585
670
1410
1030
1260
360
74
96
104
113
130
111
374
350
582
354
447
392
4210
4580
4280
3980
3800
4060
73
74
80
75
69
79
V2A
V2B
V2C
V2D
V2E
82 100
75 300
76 200
75 500
63 800
0.8
1.6
0.7
0.9
0.7
140
150
115
118
105
45
33
24
17
16
51 200
40 900
34 500
37 800
32 200
877
897
639
623
485
134
123
95
82
81
524
302
213
204
168
4100
3930
3690
3630
2710
135
81
71
61
57
0.012.0
51500
2250
7000
42 000
2750
2300
1900
0.11
70100
2030
20
10 000
1000
50
1030a
50
Typical
range
Common
value
a
These values are for rural soils. The common values for lead in urban soils are reported as 30100. Carmagnola: CA (040 cm); CB
(4090 cm); CC (90120 cm); S. Maurizio Canavese: MA (1020 cm); MB (4050 cm); MC (6080 cm); Poirino: IA (depth 515 cm); IB
(depth 4050 cm); IC (depth 100120 cm); Vigone 1: V1A (030 cm); V1B (3050 cm); V1C (5070 cm); V1D (70120 cm); V1E (120
160 cm); V1F (120160 cm); Vigone 2: V2A (035 cm); V2B (3575 cm); V2C (75120 cm); V2D (120175 cm); V2E (175195 cm).
550
Table 4
The percentages of the extracted metals in the rst fraction of
Tessiers speciation scheme
Al
Fe
Mn
Ti
CA
CB
CC
<0.001
<0.001
<0.001
<0.001
<0.001
<0.001
0.06
0.05
0.08
0.004
<0.004
0.005
MA
MB
MC
0.008
0.002
0.001
0.001
<0.001
<0.001
8.7
4.3
3.0
0.01
0.01
0.01
PA
PB
PC
0.004
<0.001
0.003
0.005
<0.001
<0.001
10.9
4.9
2.6
0.01
0.02
0.02
V1A
V1B
V1C
V1D
V1E
V1F
0.003
0.002
0.002
<0.001
0.001
0.001
0.004
0.001
0.002
<0.001
<0.001
0.002
1.6
0.2
0.06
0.09
0.02
0.06
<0.004
<0.003
<0.003
<0.004
<0.004
<0.004
V2A
V2B
V2C
V2D
V2E
<0.001
0.001
<0.001
<0.001
<0.001
0.001
0.003
0.003
0.002
0.003
0.05
0.03
0.02
0.01
0.03
<0.004
<0.004
<0.004
<0.004
<0.005
551
Table 5
The percentages of the extracted metals in the second fraction of Tessiers speciation scheme
Al
Cd
Cr
Cu
Fe
CA
CB
CC
0.03
0.04
0.02
3.30
3.61
10.12
<0.15
<0.14
<0.17
2.63
3.20
2.56
0.03
0.07
0.09
MA
MB
MC
0.05
0.03
0.04
2.10
<0.06
<0.12
0.22
0.08
0.06
3.71
1.73
1.73
PA
PB
PC
0.05
0.03
0.02
5.37
0.39
0.23
<0.20
<0.15
<0.17
V1A
V1B
V1C
V1D
V1E
V1F
0.01
0.01
0.01
0.01
0.01
0.01
0.02
0.06
0.07
0.13
0.02
0.08
V2A
V2B
V2C
V2D
V2E
0.03
0.06
0.02
0.05
0.06
0.02
<0.01
0.04
0.04
0.01
Mn
Ni
Pb
Ti
Zn
6.11
7.99
9.38
1.88
1.61
0.81
1.15
1.10
0.97
0.02
0.01
0.01
<0.01
<0.01
<0.01
0.04
0.02
0.02
4.21
2.92
2.16
0.61
0.58
0.44
4.19
0.49
0.07
0.01
<0.01
<0.01
2.11
0.39
0.21
2.67
0.86
1.26
0.11
0.02
0.01
19.24
3.98
2.13
3.25
0.82
0.77
2.23
0.62
2.52
0.01
0.01
0.01
4.34
0.21
0.20
<0.21
<0.15
<0.16
<0.18
<0.18
<0.02
7.58
2.78
2.16
1.26
1.32
1.56
0.01
0.01
0.01
0.05
0.01
0.01
0.98
0.51
0.20
0.26
0.21
1.34
1.89
1.21
1.18
2.83
1.62
0.44
0.742
0.482
0.112
0.452
0.152
0.452
<0.01
<0.01
<0.01
<0.01
0.01
<0.01
0.09
<0.01
<0.01
<0.01
<0.01
<0.01
<0.18
<0.17
0.63
<0.21
<0.24
0.70
1.41
1.60
2.21
1.41
0.09
0.14
0.05
0.13
0.16
5.71
3.76
2.30
0.85
4.35
0.99
3.04
2.51
2.76
2.79
0.342
0.392
0.582
0.422
0.512
0.02
0.02
0.01
0.01
0.01
<0.01
0.71
<0.01
<0.01
<0.01
Table 6
The percentages of the extracted metals in the third fraction of Tessiers speciation scheme
Al
Cd
Cr
Cu
Fe
CA
CB
CC
<0.01
<0.01
<0.01
2.48
1.59
<0.15
0.97
1.01
1.28
15.77
23.64
30.00
7.26
8.82
9.71
69.15
79.17
79.87
1.81
1.37
1.08
3.86
2.57
3.19
0.02
0.03
0.02
15.85
6.25
7.51
MA
MB
MC
1.09
1.39
1.88
0.47
<0.12
<0.24
1.87
2.35
1.67
8.44
7.36
7.17
13.76
15.64
15.85
35.04
43.83
33.17
24.00
23.55
24.90
4.26
3.96
0.41
0.03
0.05
0.04
30.10
7.47
7.18
PA
PB
PC
0.97
1.01
0.83
0.74
0.39
0.10
0.90
1.92
1.85
10.63
8.61
10.47
21.73
16.28
15.93
54.67
94.76
52.44
18.06
7.09
6.03
4.85
4.35
4.12
0.03
<0.01
0.01
31.10
7.71
6.85
V1A
V1B
V1C
V1D
V1E
V1F
1.50
1.37
1.37
1.38
1.68
1.25
1.05
0.76
0.84
3.60
9.47
1.28
3.54
6.05
7.69
9.42
4.69
0.49
14.62
14.78
17.42
17.44
19.13
26.56
10.81
16.57
9.13
10.19
6.61
8.88
64.61
87.46
44.47
36.21
97.70
28.33
9.53
10.52
11.30
17.61
28.54
11.89
2.04
1.45
0.82
0.41
0.54
0.66
0.02
0.03
0.01
0.01
<0.01
0.01
15.21
7.46
7.50
7.92
10.93
11.53
V2A
V2B
V2C
V2D
V2E
0.37
0.45
0.52
0.54
0.13
0.96
1.16
2.86
3.17
1.39
1.74
1.79
2.30
1.47
3.05
2.29
8.82
16.13
15.82
21.38
3.41
5.11
6.42
4.95
7.02
11.52
36.68
46.79
28.73
31.55
3.51
7.03
9.28
8.10
9.11
0.12
0.31
0.56
0.34
0.33
0.02
0.01
0.04
0.02
0.06
3.31
3.41
2.61
1.37
5.30
Mn
Ni
Pb
Ti
Zn
(Lund, 1990). Bioavailable concentrations are probably more correlated to the eect of milder extractants
such as neutral salts (Hani, 1990; Rauret, 1998). The
552
Table 7
The percentages of the extracted metals in the fourth fraction of Tessiers speciation scheme
Al
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Ti
Zn
CA
CB
CC
0.97
0.85
0.70
<0.09
<0.08
<0.15
1.64
1.33
1.18
28.57
9.95
10.00
0.74
0.45
0.30
7.19
11.67
7.09
1.04
0.77
0.50
1.07
0.88
0.81
0.08
0.04
0.05
0.42
0.43
0.33
MA
MB
MC
1.04
0.51
0.43
<0.10
<0.12
<0.24
3.79
2.90
2.16
17.41
3.02
3.77
0.28
0.03
0.04
4.96
2.55
1.42
<0.07
<0.09
<0.10
0.43
<0.50
<0.07
0.03
0.03
0.08
3.10
<0.01
<0.01
PA
PB
PC
1.18
0.26
0.24
<0.18
<0.12
<0.10
7.81
2.33
1.28
24.47
1.12
<0.35
0.92
0.05
0.02
12.97
17.14
9.77
<1.56
<0.40
<0.53
0.58
0.63
0.57
0.02
<0.01
0.03
4.16
<0.01
<0.01
V1A
V1B
V1C
V1D
V1E
V1F
0.66
0.39
0.63
0.62
0.27
0.42
<0.38
<0.44
<0.53
<1.38
<0.38
<1.46
5.68
3.31
2.97
3.35
2.19
0.14
11.21
1.63
1.59
2.13
<0.42
0.77
0.01
<0.01
<0.01
<0.01
0.01
0.01
3.50
0.82
0.19
0.36
0.05
0.14
2.80
1.99
2.35
2.89
1.87
2.01
<0.13
<0.14
<0.09
<0.14
<0.11
<0.13
0.18
0.05
0.01
<0.01
0.04
0.05
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
V2A
V2B
V2C
V2D
V2E
0.10
0.07
0.07
0.05
0.10
9.27
7.13
29.22
80.04
35.51
2.39
0.78
0.86
<0.42
0.94
3.53
1.08
<0.52
<0.73
<0.78
0.06
0.03
0.14
0.11
0.27
1.08
0.61
0.42
0.60
0.14
1.66
2.18
1.67
0.80
1.30
<0.09
<0.17
0.34
<0.24
<0.30
0.03
0.06
0.21
0.21
0.24
1.28
0.96
0.39
<0.01
<0.01
Table 8
The percentages of the extracted metals in the fth fraction of Tessiers speciation scheme
Al
Cd
Cr
Cu
Fe
Mn
Ni
Pb
Ti
Zn
CA
CB
CC
99.00
99.11
99.27
98.05
98.26
96.60
99.09
99.21
99.16
52.99
63.09
57.25
91.97
90.65
89.91
17.49
1.13
3.59
95.26
96.25
97.61
97.97
98.48
98.34
99.88
99.92
99.92
83.72
93.32
92.16
MA
MB
MC
97.81
98.07
97.65
99.11
99.94
99.97
98.04
98.22
98.70
70.29
87.73
87.32
85.92
84.31
84.09
47.03
46.43
60.21
75.39
75.86
74.65
97.04
98.49
99.84
99.93
99.90
99.86
64.70
92.13
92.61
PA
PB
PC
97.79
98.71
98.90
97.93
99.71
99.86
97.05
98.54
98.92
62.05
89.38
88.15
77.24
83.65
84.03
2.27
1.28
33.03
78.50
92.04
93.16
97.44
98.13
97.59
99.94
99.97
99.93
60.40
92.08
92.95
V1A
V1B
V1C
V1D
V1E
V1F
97.82
98.23
97.99
97.99
98.04
98.33
99.62
99.67
99.67
98.44
96.77
99.39
96.87
96.85
96.42
95.71
97.67
99.78
66.47
80.73
78.74
79.05
79.25
71.01
89.17
83.42
90.86
89.75
93.37
91.10
29.27
10.96
55.08
63.07
2.02
70.13
85.78
86.28
85.17
76.66
67.97
85.66
99.31
99.50
99.70
99.84
99.79
99.75
99.80
99.92
99.97
99.97
99.94
99.94
84.70
92.53
92.49
92.07
89.06
88.46
V2A
V2B
V2C
V2D
V2E
99.48
99.41
99.39
99.35
99.71
96.58
97.24
89.29
72.25
87.70
98.58
99.10
98.74
99.32
98.67
93.44
88.63
81.63
81.01
76.68
96.43
94.71
93.39
94.80
92.54
81.64
58.92
50.46
69.81
63.94
93.84
87.75
86.54
88.34
86.80
99.94
99.85
99.70
99.86
99.85
99.92
99.91
99.73
99.75
99.69
95.40
94.92
97.00
98.61
94.68
LakanenErvi
o procedure is usually applied only to
soils that have a pH value lower than 6.5. Anyway, it
was used also for two samples from Vigone 1 with a
553
Table 9
The percentages of metals extracted with EDTA
Al
Cr
Cu
Fe
Mn
Ni
Pb
V1A
V1B
V1C
V1D
V1E
V1F
0.15
0.15
0.08
0.10
0.08
0.07
0.20
0.07
0.12
0.10
0.13
0.01
16.12
4.22
2.54
1.74
1.96
1.06
1.20
0.75
0.25
0.38
0.17
0.21
63.59
31.79
9.99
18.74
33.09
7.81
6.39
5.76
1.94
2.21
5.48
0.50
1.17
0.93
0.54
0.99
0.54
0.84
0.10
0.07
0.05
0.03
0.02
0.02
4.84
0.98
0.76
0.59
1.05
0.41
V2A
V2B
V2C
V2D
V2E
0.12
0.09
0.04
0.02
0.03
0.25
0.10
0.06
0.04
0.09
9.09
5.76
2.92
1.45
3.79
0.65
0.52
0.22
0.11
0.28
42.99
8.53
6.59
6.90
39.79
3.35
2.06
0.53
0.62
4.38
0.78
0.97
1.05
0.65
1.52
0.04
0.04
0.01
<0.01
0.01
3.47
1.94
0.97
0.47
0.68
leaching test with water because EDTA is a strong ligand that is able to react not only with the more mobile
forms of the metal, but also with those more strongly
bound to organic or inorganic soil constituents. In fact
the percentages of the extracted metals found with this
procedure are comparable to those obtained in the
third and fourth fraction of the Tessiers procedure. The
order of extractability was Mn > Cu > Ni > Zn > Pb >
Fe > Cr > Al > Ti and does not seem to be tightly related to the values of the formation constants with
EDTA, which decrease in the order Fe(III) > Cu >
Ni > Pb > Zn > Al > FeII > Mn (Sillen and Martell,
1979). Extractability is probably dependent on the
chemical form of the metal in soil and therefore to its
mobility. The extracted percentages range from 0.017
to 68.59 in Vigone 1 soil and from 0.007 to 39.79 in
Vigone 2.
Ti
Zn
554
correlated or not related to metal concentrations, probably because such metals are mainly bound to the soil
matrix and are present in the exchangeable form only in
very low percentages, as shown by the results obtained
with Tessiers speciation protocol.
3.4.2. Tessiers fractions
In the plot of PC1 vs. PC2 obtained from the percentages of extracted metals in the rst fraction (Fig.
2a), it is possible to note one group formed by S.
Maurizio Canavese and Poirino soils, sample MA being
distinguished from the others because it is characterised
by a lower pH value. The samples from Carmagnola are
also close to each other. Vigone 1 and Vigone 2 samples
are partially overlapped.
Fig. 2b shows the results of PCA for the data obtained in the second step of Tessiers extraction. It is
possible to identify the following groups: (i) MB, MC
and PB, PC samples, with sample MC partially apart
because of its higher sand content; the topsoils from S.
Maurizio Canavese and Poirino, i.e. samples MA and
PA, clearly dier from the corresponding subsoils; (ii) all
horizons of Vigone 1, (iii) all horizons of Vigone 2, (iv)
all horizons of Carmagnola soil. It is evident that the
samples of the rst two groups are characterised by high
percentages of clay and low percentages of extracted Al,
Fe and Mn; the samples from Carmagnola are distinguished from the others because they have the lowest
555
Fig. 4. Percentage of the extracted metals in the fourth extraction of Tessiers procedure: (a) combined plot of scores and
loadings on PC1PC2, and (b) dendrogram obtained by cluster
analysis.
the dendrograms; as an example the dendrogram relative to the fourth fraction is reported in Fig. 4b.
PCA was also performed with all variables. As expected, CEC was found to be strongly correlated to the
percentages of Mn, Al, Fe extracted in the rst fraction,
corresponding to exchangeable metals. On the other
hand, this variable was anticorrelated to the metal percentages in the fth fraction, i.e. to the species more
strongly bound to the soil matrix.
556
Acknowledgements
We thank the Ministero dellUniversit
a e della Ricerca Scientica e Tecnologica (MURST, Rome, COFIN
2000) and the Italian National Research Council
(C.N.R., Rome) for nancial support.
References
4. Conclusions
Total metal concentrations in the ve investigated
agricultural soils t in the typical ranges for unpolluted
soils, with the exception of lead and cadmium in some of
the sites. The concentrations in Vigone 2 samples decreased with increasing depth, whereas a surface depletion was observed for Carmagnola and Poirino.
Of course the results of this study apply to only a
limited zone of the considered areas, because of the
restricted number of samples, and cannot be directly
extended to the whole sites. The main goal of the
investigation was understanding metal mobility and
distribution also in connection with main soil characteristics.
For this reason metal speciation and mobility were
studied with Tessiers sequential extraction procedure.
The highest percentages of metals were found to be
strongly bound to soil matrix, i.e. in a form not readily
available for introduction into the food chain. Extractability in EDTA was investigated in Vigone 1 and Vigone 2 soils: in all cases metals were found to be more
readily available from topsoil than from subsoil. The
chemometric study enabled us to evidence similarities or
dierences among the ve soils and correlations or anticorrelations among variables that were not clearly visible from an examination of the analytical data in the
tables. For instance, samples from the same site showed
a similar behaviour toward extraction in Tessiers protocol, and soil pH was found to be anticorrelated to the
percentages of metals extracted by EDTA, owing to the
higher element mobility at low pHs.
557
Tessier, A., Campbell, P., Bisson, M., 1979. Sequential extraction procedure for the speciation of particulate trace metals.
Anal. Chem. 51, 844851.
Tessier, A., Campbell, P., Bisson, M., 1980. Trace metal speciation in the Yamaska and St. Francois Rivers (Quebec).
Can. J. Earth Sci. 17, 90105.