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2 AUTHORS:
Sabrina Novaes dos Santos-Araujo
Luis Alleoni
University of So Paulo
University of So Paulo
4 PUBLICATIONS 35 CITATIONS
SEE PROFILE
SEE PROFILE
Received: 20 August 2012 / Accepted: 18 December 2012 / Published online: 19 January 2013
# Springer Science+Business Media Dordrecht 2013
1 Introduction
Heavy metals occur naturally in soils, at concentrations that depend on the soil parent material, on the
processes by which the soil formed, and on the composition and proportion of the components of its solid
phase. Quantifying these concentrations is important
for studies of environmental pollution, and a key step
towards establishing soil quality reference values.
Environmental agencies require reference indicators in order to monitor environmental impacts and
determine pollution levels, as part of their mandate to
enforce environmental legislation. These indicators
are obtained by comparing concentrations of toxic
elements in soils with those observed in natural
(nonpolluted) soils, or with reference values.
To date, a number of studies have been carried out
to quantify natural concentrations and reference background values of heavy metals in Brazilian soils.
However, no studies have described natural concentrations of heavy metals in the soils of Mato Grosso
and Rondnia, Brazilian states in the southwestern
1430, Page 2 of 16
Table 1 Characteristics of macroregions in the states of Mato Grosso and Rondnia, southwestern Amazon region, Brazil
(Mello, 2007)
Region
Topography
Soil
Vegetation
Alto Xingu
Oxisols
Amia (1,7502,250)
Seasonal semi-deciduous
forest to open Amazon
forest
Paran Basin
Parecis Plateau
Entisols Aquent
Entisols
Ami (1,2502,000)
Am (1,5001,750)
Oxisols, Ultisols
Entisols
Northeastern
Mato Grosso
Amid (2,0002,500)
Cerrado to seasonal
semi-deciduous forest
Northern
Mato Grosso
Northern Rondnia
Predominately flat
Oxisols
Awi (2,0002,500)
Central Rondnia
Ultisols, Oxisols
Entisols, Alfisols
Am (1,5001,750)
Pantanal
a
The contents of available phosphorus and potassium were extracted with Mehlich-I (Mehlich 1953),
and calcium and magnesium were extracted with
1 M KCl (Anderson and Ingram 1992). Phosphorus
content was determined by colorimetry, Ca and Mg
were quantified in an atomic absorption spectrophotometer (AAS), and K in a flame photometer.
Exchangeable aluminum was removed with 1 moll1
KCl (Anderson and Ingram 1992), and determined by
titration with 0.025 moll1 NaOH. Total acidity (H +
Al) was extracted with a 1 M calcium acetate (pH7
buffered) solution and determined by titration with
0.025 M ammonium hydroxide.
pH was determined potentiometrically for suspensions of air-dried fine earth in 1 M KCl, H2O, and
0.01 M CaCl2 1:2.5 (Anderson and Ingram 1992). The
1430, Page 4 of 16
Fig. 1 Map of southwestern Amazonian Brazil, showing townships selected for soil sampling (RO Rondnia, MT Mato Grosso)
1430, Page 6 of 16
Table 2 Selected physical and
chemical attributes of soil samples from the states of Rondonia
and Mato Grosso, Brazil (n=19)
Variable
Mean
Minimum
Maximum
Standard Deviation
pH (H2O)
4.6
3.5
7.4
0.9
pH (0.01 M CaCl2)
4.3
3.2
7.2
0.9
pH (1 M KCl)
4.2
3.2
6.9
0.9
mmolc kg
CECe
19.0
2.3
96.4
17.9
CECt
55.4
17.8
158.0
29.0
%
V
24
0.2
99
26.9
46
0.1
98
34.6
g kg1
Org. C
CECe effective cation exchange
capacity, CECt totalcation exchange capacity, V base saturation, m saturation for aluminum
13.3
Sand
189
Silt
38
10
92
21
Clay
307
25
651
174
Certified soil
Cd
2709ac
0.3
84.7
DO65
Cr
Cu
2709a
9.3
DO65
174.4
2709a
52.0
DO65
140.4
Certified valuea
(mg kg1)
Recovery
(determined)b (%)
Leach
recovery (%)
0.370.002
104
110
91.0
93
12.800.2
73
81
190.0
91.8
130.09.0
40
41
144.0
97
24.4
33.90.5
72
81
DO65
251.9
237.0
106
2709a
59.5
852
70
77
DO65
214.0
200.0
107
Pb
2709a
8.1
17.30.1
47
53
DO65
111.2
104.0
107
Zn
2709a
71.0
1034
69
77
DO65
314.4
341.0
107
Ni
Recovery level
(mg kg1)
2709a
Element
Co
7.1
953
35.1
271
4.4
654
Table 4 Heavy metal concentrations extracted by aqua regia and EPA 3051 in the surface layer (020 cm) of soils from Mato Grosso
and Rondnia, Brazil (n=19)
Aqua regia
Cd
Co
mg kg1
EPA 3051
Cr
Cu
Ni
Pb
Zn
Cd
Co
Cr
Cu
Ni
Pb
Zn
<0.05a
15.8
47.9
18.2
8.6
15.3
22.4
<0.05
20.3
39.4
16.5
1.3
8.1
Standard error
0.0
1.7
6.8
2.0
1.2
1.2
5.4
0.0
1.2
4.9
1.3
0.3
0.7
3.7
Median
0.0
14.1
39.7
15.4
7.8
15.1
13.2
0.0
18.3
31.2
14.3
0.4
7.5
0.6
Standard deviation
0.0
7.4
29.7
8.7
5.5
5.4
19.7
0.0
5.4
21.5
5.8
1.6
3.1
5.3
Variance
0.0
55.3
885.4
75.6
31.0
29.9
565.3
0.0
29.6
464.5
34.2
2.6
9.8
268.2
Minimum
<0.05
7.2
20.4
6.5
0.2
5.2
1.2
<0.05
16.6
19.2
9.7
0.0
2.7
0.0
Maximum
<0.05
38.9
142.1
32.9
24.3
25.8
100.9
<0.05
39.0
98.8
28.4
5.6
15.7
69.6
47
64
35
105
26
54
35
LC (%)b
Confidence level
46
62
126
6.8
38
238
Mean
Aqua Regia
EPA 3051
a
60
a
40
a
b
20
a
a
a
a
Pb
Zn
b
0
Co
Cr
Cu
Ni
1430, Page 8 of 16
DCF 1
r
DCF 2
SCC
PDR
SCC
PDR
Co
1.5
0.1
0.2
1.5
0.1
0.1
Cr
0.1
0.1
0.0
0.2
0.1
0.1
Cu
0.9
0.1
0.0
0.8
0.1
0.1
Ni
0.7
0.3
0.2
0.9
0.2
0.2
Pb
1.0
0.3
0.3
0.4
0.2
0.1
Zn
1.0
0.1
0.1
1.8
0.2
0.5
3.3 Correlations
Correlations between the heavy metal concentrations
in the 19 soil samples and the 34 physical and chemical attributes of those soils are presented in Table 6.
Metal concentrations extracted with AR, which had a
higher extraction power of the pseudo-total concentrations of heavy metals, were used in the correlations.
With the exception of Cr, there was generally a positive correlation between the concentrations of Co, Cu,
Ni, Pb, and Zn (Table 6). Biondi (2010) reported
similar results in a study of soils from Pernambuco,
Brazil, where Cu concentrations were positively correlated with concentrations of Zn (r=0.78; r=0.81),
Co (r=0.81; r=0.76), and Ni (r=0.73; r=0.71) in the
surface and subsurface horizons, respectively (p<
0.001). Co levels also showed positive correlations
with levels of Ni (r=0.72; r=0.77) and Mn (r=0.79;
r=0.92), revealing the geochemical affinity of these
metals.
The content of exchangeable Al only showed a significant correlation with Cr concentrations (0.38*).
Acidity (pH) only showed a significant positive correlation with Co and Zn (0.47*) concentrations and a
significant negative correlation with Cr (0.39*).
These coefficients were relatively low, probably due to
the extraction methodology, since the total concentrations were extracted in a strongly acidic medium, and
significant correlations with pH are more frequent when
considering available concentrations in the most common range of soil pH in agricultural soils (between 5.0
and 6.5). CECe was positively correlated with C content
0.624*
ns
0.469*
ns
ns
0.284*
MnO (SA)
Ki
Kr
Fe2O3(OXA)
0.502*
Fe2O3
ns
0.399*
0.619*
0.721*
0.710*
0.333*
0.341*
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
0.542*
0.401* ns
ns
0.405*
0.426*
ns
ns
ns
0.670*
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
0.705*
0.893*
ns
0.880*
ns
ns
0.805*
0.854*
1.00
0.874*
0.978*
ns
0.995*
ns
0.533*
0.829*
1.00
Ca
ns
0.347*
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
0.581*
ns
ns
ns
ns
ns
ns
ns
ns
ns
0.519*
ns
ns
ns
0.364* ns
ns
ns
ns
0.380* 0.400*
ns
ns
ns
ns
0.520*
0.444*
0.513*
ns
0.760*
0.402*
ns
0.07
0.15
ns
0.339*
0.484*
0.716*
0.589*
0.536*
ns
0.19
0.649*
ns
0.692*
ns
0.428*
ns
ns
ns
ns
ns
0.725* ns
0.924*
0.768*
0.09
0.824*
ns
0.490* ns
0.432*
ns
0.464*
1.00
ns
ns
ns
ns
ns
1.00
pH
0.628* ns
0.672*
0.834*
0.648*
0.520*
Sand
0.636*
0.333*
0.42
0.383*
ns
0.636*
ns
ns
ns
0.490*
ns
0.357*
0.23
ns
0.354* ns
ns
0.507*
0.377*
0.475*
ns
ns
1.00
ns
0.488*
0.695*
ns
ns
0.500*
ns
ns
0.398* 0.518*
ns
ns
ns
0.377*
0.387*
ns
0.478*
0.525*
ns
ns
pH
Silt
0.681*
0.524*
0.388*
0.322*
ns
0.337* ns
ns
ns
ns
ns
ns
1.00
Cu
0.511*
0,.563*
ns
0.339*
ns
ns
ns
0.524*
0.310*
0.748*
0.450*
0.557*
ns
0.668*
1.00
Co
0.390* 0.478*
ns
ns
1.00
Cr
0.320* 0.450*
ns
0.308*
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
0.628*
0.705*
ns
1.00
Pb
Clay
0.488*
ns
ns
Al2O3(OXA)
(CBD)
ns
Mn2O3(OXA) 0.790*
0.343*
ns
ns
ns
0.322*
0.425*
0.387*
ns
0.282*
ns
TiO2 (SA)
ns
CECt
ns
Fe2O3 (SA)
ns
SB
ns
0.573*
ns
H + Al
ns
ns
ns
Al
ns
0.524*
ns
Mg
ns
SiO2 (SA)
0.550*
Ca
ns
Al2O3 (SA)
0.499*
ns
ns
0.444*
ns
ns
ns
pH
ns
CO
0.476*
pH
0.780*
0.366* ns
0.718*
Cu
ns
ns
0.857*
Co
0.540*
ns
Cr
ns
1.00
0.485*
0.609*
Pb
CECe
0.559*
Ni
Ni
1.00
Zn
Zn
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
0.828*
0.815*
0.846*
ns
0.875*
ns
0.528*
1.00
Mg
ns
ns
ns
ns
ns
ns
ns
ns
0.600*
0.364*
0.327*
ns
0.463*
ns
ns
ns
0.358*
ns
ns
ns
ns
ns
0.329*
ns
ns
ns
ns
ns
ns
ns
ns
0.717*
0.494*
ns
0.368*
0.632*
ns
ns
1.00
ns
0.584*
H + Al
0.535*
1.00
Al
ns
0.474*
1.00
CECt
ns
ns
ns
ns
ns
0.554*
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
ns
0.421*
ns
0.540*
ns
ns
ns
ns
ns
ns
ns
ns
ns
0.456*
0.735* ns
0.880*
0.982*
ns
1.00
SB
ns
ns
ns
ns
ns
0.537*
ns
ns
ns
ns
ns
ns
ns
ns
0.407*
0.650*
0.829*
1.00
CECe
Table 6 Pearson correlation matrix between natural levels of heavy metals (aqua regia method) and soil attributes, with significant values (p<0.01) marked with an asterisk (*)
1430, Page 10 of 16
Water Air Soil Pollut (2013) 224:1430
ns
ns
ns
ns
ns
ns
0.338* ns
ns
ns
ns
ns
ns
0.340* ns
Fe2O3 (SA)
TiO2( (SA)
MnO (SA)
Ki
Kr
Fe2O3(OXA)
1.00
ns
ns
ns
ns
Fe2O3(CBD)
Clay
Silt
Sand
ns
ns
ns
ns
0.491*
0.737*
0.662*
ns
ns
0.525*
0.747*
0.875*
ns
ns
0.462*
ns
0.530*
0.507*
ns
ns
0.714*
ns
0.485*
ns
ns
1.00
TiO2
(SA)
0.467* ns
0.552*
0.579*
1.00
Fe2O3
(SA)
0.480* ns
ns
0.507*
0.61*
1.00
Al2O3
(SA)
0.370*
0.349*
ns
ns
0.475*
ns
ns
ns
1.00
MnO
(SA)
0.732*
0.782*
0.660*
ns
ns
0.480*
ns
ns
0.383*
0.336*
0.671*
0.562*
1.00
SiO2
(SA)
ns
ns
ns
ns
ns
ns
ns
ns
1.00
Ki
ns
ns
0.519*
0.356*
ns
ns
ns
ns
1.00
Mn2O
0.314* 0.522*
(OXA)
ns
0.448*
ns
1.00
Fe2O3
0.594*
ns
ns
ns
ns
1.00
Kr
SA sulfuric acid attack, OXA ammonium oxalate, CBD sodium citratebicarbonatedithionite, ns not significant
ns
ns
ns
ns
ns
ns
Al2O3(OXA)
ns
0.464* ns
ns
ns
ns
Mn2O3(OXA) 0.644*
ns
ns
ns
ns
Al2O3 (SA)
ns
ns
ns
ns
SiO2 (SA)
0.841* 1.00
CO
CO
1.00
Table 6 (continued)
3(OXA)
(OXA)
0.539*
0.339*
0.545*
ns
1.00
Al2O3
(CBD)
0.694*
0.525*
0.692*
1.00
Fe2O3
1.00
Silt
Sand
0.700*
1.00
Clay
1430, Page 12 of 16
Fig. 4 Principal components analysis of variables
related to physical and
chemical properties of soils
from Mato Grosso and
Rondnia, Brazil, for
extractions performed with
aqua regia (a) and EPA 3051
(b)
(a)
(b)
sand, P, Ca, Al saturation, total, free, and amorphous Fe2O3, amorphous Al2O3 and Mn2O3 and
total TiO2 for the EPA 3051 method, plus Ki and
4 Conclusions
1430, Page 14 of 16
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