[article pii="nd" doctopic="oa" language="en" ccode="CAICYT"
status="1" version="4.0" type="ilus
gra" order="12" seccode="cds010"
sponsor="nd" stitle="Cienc. suelo" volid="33" issueno="2"
dateiso="20151200" fpage="0"
lpage="0" issn="1850-2067"]
[front][titlegrp][title language="en"]HEAVY METAL
BACKGROUND LEVELS IN RURAL SOILS: A CASE STUDY IN PAMPEAN SOILS (ARGENTINA)[/title][/titlegrp]
[authgrp][author
role="nd"][fname]NURIA [/fname][surname]
1 Facultad de
Agronomía, Universidad Nacional del Centro de
2 Facultad de Biologia, Depto.
Biologia Vegetal, Universidad de Barcelona (España),
Av. Diagonal 643, 08028 Barcelona (España)
*Autor de contacto: nuria@faa.unicen.edu.ar
Recibido: 29-09-14
Recibido con revisiones: 21-04-15
Aceptado: 05-06-15
[bibcom]ABSTRACT
[abstract
language="en"]Azul,
an agricultural county at the center of
Key words. [keygrp scheme="nd"][keyword type="m"
language="en"]Background, trace elements, soil
pollution, anthropic sources[/keyword][/keygrp].
NIVELES BASALES DE METALES PESADOS EN SUELOS RURALES: UN CASO EN SUELOS PAMPEANOS (ARGENTINA)
RESUMEN
[abstract language="es"]En este trabajo se proponen valores básales en el municipio de Azul (Argentina), una zona de uso agrícola-ganadero representativa en Sudamérica, como base para detectar e identificar la contaminación de los suelos a nivel regional. Se muestreó el horizonte superficial de cuarenta y dos suelos, se realizó una digestión ácida y, posteriormente se analizaron siete elementos (Cd, Co, Cr, Cu, Ni, Pb y Zn) con un espectrómetro de plasma de inducción acoplada (ICP-MS). Se comprobó la eficacia de tres pruebas estadísticas (4a-outlier test, iterative 2a-outlier test and calculated distribution function) para definir los valores de referencia. El límite superior de los niveles basales en mg kg-1 fueron: Cd 0,15, Co 10,8, Cr 22,1, Cu 39,2, Ni 13,7, Pb 11,8 y Zn 133,9. Una vez establecido los valores basales, se detectaron puntos con indicios de contaminación antrópica. El metal pesado que mostró anomalías en mayor número de muestras fue el Cd. Los horizontes superficiales de antiguos vertederos no controlados presentaron anomalías en Cd, Cr, Cu, Ni, Pb y Zn. Las anomalías detectadas en los suelos agrícolas podrían señalar una incipiente contaminación antrópica a nivel regional.[/abstract]
Palabras clave. [keygrp scheme="nd"][keyword type="m" language="es"]Niveles basales[/keyword], [keyword type="m" language="es"]elementos traza, contaminación de suelos, fuentes antrópicas[/keyword][/keygrp].[/bibcom][/front]
[body]INTRODUCTION
Soil is a
key natural resource which supports life and is a major pre-requisite for
sustainable development in terrestrial environments (Sultan and Shazili 2009). Knowledge of background values of heavy
metals in soils is necessarybefore a soil can be
declared to be contaminated. These values can be defined as the natural content
of heavy metals in soils without human influence (Salminen
& Gregorauskiene, 2000). The term
"geochemical baseline'' indicates the actual content of an element in a
surface environment at a given point in time, as defined by Salminen
and Gregorauskiene (2000) and considering the
entrance of these elements to soils by diffusion (Adriano, 2001). Therefore,
baseline values are not always true background levels (Mico
et al, 2007). In particular, baseline values in agricultural soils
correspond to total contents of heavy metals in soils not influenced by point
input due to local human activities (eg, industries)
but include diffuse or nonpoint input (e.g., atmospheric deposition,
fertilization) (Holmgren et al, 1993). The determination of background
values (as geogenic natural content), in contrast to
baseline values, is crucial when defining the extent of contamination in areas
where environmental legislation has not yet established intervention limits for
all environmental matrices (Albanese et al., 2007).
Different
approaches have been used to establish the background levels of trace elements
in soils. Methods are usually classified into direct (empirical or geochemical)
or indirect (statistical) and both can be combined leading to integrated
methods (Dung et al, 2013). In direct methods, the background
concentrations are obtained from normal content reported in the literature or analysing samples representing pristine areas. Difficulties
arise when different soil types and extraction procedures are used. Furthermore,
the geochemical background changes regionally with the basic geology as well as
with the lithological and geochemical nature of the
bedrock. Different measurements at varying depths in the soil (vertical
comparison), such as a high content on surface horizons and a downward trend in
the profile, can confirm the hypothesis of an anthropic
accumulation. However, the comparison is effective only when the chemical
composition of the soil does not vary significantly with depth, and when there
are no intrasolum translocations, erosion processes,
truncation, colluviation or burial of the element
within the soil. An indirect method is the comparison between a given soil type
in an uncon-taminated site, and the same type of soil
at a site receiving anthropic inputs (horizontal
comparison) (Bini et al, 2011). Indirect
methods or statistical approaches consist in sampling a large number of sites
and involve using statistical tools and spatial analysis to separate, within a
data set, the background concentration from that related to anthropic
sources. Samples identified as polluted can be single ormultiple
outliers or a population itself. Considering the need to find a simple and
robust statistical test, three methods (4o-outlier test, iterative 2o-outlier
test and calculated distribution function) were used and discussed to establish
the reference or background levels. Naturally and anthropogenically-induced
processes not only lead to a widening of the range of the data collective
(larger standard deviations), but also to multi-modal distributions. Ideally,
each mode corresponds to a relevant process with its underlying normal
distribution (Matschullat et al, 2000). The
objective of the applied methods in this study is the elimination of potential
outliers from the data set. These outliers will have to be detected and
eliminated as fingerprints for processes disturbing the normal data
distribution (Matschullat et al., 2000). Therefore,
the resulting sub-collective (free from outliers) is defined as reflecting background
conditions.
Qualitative
and quantitative heavy metal content data from Argentine soils is scarce. Recently,
Roca et al. (2012) determined the background levels of several heavymetals in soils of Catamarca province, located in
north-western
Sustainability
of conventional agriculture is based on a high input of agrochemicals, such as
phosphate fertilizers.
Conventional
inorganic phosphorus fertilizers may cause an inadvertent addition of heavy
metals, which are contained as impurities. Giuffré de
López Camelo et al. (1997)
state that continuous fertilization of soils could increase the heavy metal
contents exceeding natural abundance in soils, and transfer of these metals to
the human food chain must not be overlooked. The topsoil layer is of particular
interest as degradation may occur due to atmospheric deposition or
anthropogenic activities (Aelion et al., 2008).
These concerns are very important in the Argentinian
agricultural system with a traditionally environment- friendly image with
relatively low agrochemical inputs. Other anthropic
land uses could be present in soils around residential areas or between cropped
lands and grazed grasslands as rubbish dumps, occupying small areas but with a
great impact on the environment. These mosaic of unauthorized rubbish dumps
increases the risk of soil pollution. Colangelo et
al. (2005) demonstrated contamination with Cd,
Cr, Pb and Zn in soils near a rubbish dump located in
This
study aims at (1) establishing background content levels for seven metals in
top soils of an agricultural area (Cd, Co, Cr, Cu,
Ni, Pb and Zn) using different statistical approaches
and (2) assessing the degree of surface soil pollution and identifying the
local sources of pollution.
MATERIAL
AND METHODS
Area
description and sample collection
The study
area is located in the municipal district of Azul,
The
native grasslands are organized in relatively extended, discrete patches
because of the smooth topography of the area, and Paspalum
quadrifarium L. grasslands, typical of moist
environments, are predominant from low areas to moderately high convexities. The
dominant species of the grass-legume mixed pasture are perennial rye-grass (Lolium perenne L.) and white
clover (Trifolium repens
L.), with minor coverage of red clover (Trifolium
pratense L.), bromegrass
(Bromus catharticus L.)
and tall fescue (Festuca arundinacea
S.).
Forty-two
plots from crop lands, grazed grassland and soils from Azul
Sierras were sampled. In each plot, eight subsamples of the A horizon were
taken and subsequently mixed. The area covered for the soil sample collection
was approximately 6615 km2 and ranged from 36°15' S to 37°21' S and
from 60°08' W to 59°05' W. The sampling sites are shown in Figure 1.
Determination
of metal content
To
determine the heavy metal content, approximately
Figure 1. Map of the Azul region showing the location of the sampled points.
Figura 1. Mapa de la
región de Azul con la localización de los puntos de muestreo.
Statistical
analysis
The
background values were calculated using the 4o-outlier test, iterative
2o-outlier test and calculated distribution function (Matschullat
et al., 2000). This calculation required the elimination of potential
outliers from the data set and the calculation of the mean and standard
deviation of the remaining subset. The normal range of a sample was defined by
the upper values assessed by the mean +2o, which means that 97% of the samples
were below this value. Only this type of data includes sufficient information
about the natural scatter of the background values (Matschullat
et al., 2000).
The
contamination degree of heavy metals in soils was assessed with the geoaccumulation index (Igeo)
introduced by Muller (1969), taking into account the upper limit of background
concentration determined as described before. The method has been widely
employed in European trace metal studies since the late 1960s. It is also
employed in pollution assessment of heavy metals in urban soils, urban road
dust and agricultural soils from
significance. The heavy metal distribution by soil use was tested
by applying ANOVA. In addition, data were compared using covariance analysis
(ANCOVA), with the organic carbon (OC) percentage and pH as the covariate (p
< 0.05) (Neter et al., 1990). Pearson
product moment correlation coefficients were calculated to examine the
relations among the variables and PCA to explain most of the variance in the
data while reducing the number of variables to a few uncorrelated components.
RESULTS
AND DISCUSSION
Background
determination
Table 1
shows the mean and median values of the original data set, the results from the
fitted distribution (2a), the 4a-outlier test and the calculated distribution. The
standard deviation (a) is given, as is the number "n" of single
values within the collective/sub-collective and the relative loss of individual
data points after respective fitting (data representation). Finally, the
calculated upper limit (mean+2a) of the natural background content is given. Distributions
are disturbed and skewed towards higher values. Lower values should, therefore,
be free from anthropic influences. This, of course,
is only partly true, because any kind of anthropogenically
induced depletion, e.g., via acidification processes in soils, is being
neglected here (Matschullat et al, 2000). The
upper limits of the background content differ mainlybetween
the iterative 2a-technique and the calculated distribution with respect to the
4a-technique. The iterative 2a-technique and the calculated distribution are
better at reducing the background upper limit than the 4a-outlier test, with
exception for Co (Fig. 2). It should be noted, however, that the values
obtained from the 4a-technique by Roca et al. (2012) in Catamarca soils
do not differ with respect to the iterative 2a-technique and the calculated
distribution. The most plausible calculation of the geogenic
background in the soils of the Humid Pampean Region
was tested using the iterative 2a-technique and the calculated distribution. Therefore,
the ranges obtained by the calculated distribution are chosen as background
values. The upper limit of background values were expressed in mg kg-1:
Cd 0.15, Co 10.8, Cr 22.1, Cu 39.2, Ni 13.7, Pb 11.8 and Zn 133.9. The soils have been predominantly
influenced by natural element dispersion and accumulation processes, but there are
a few points with an anthropic influence. The top
soils of the eastern Pampas (Lavado et al. 2004)
have content and dispersion values of heavy metals (in mg kg-1: Cd 0.92, Co 31.8, Cr 13.6, Cu 14.5, Ni 5.5, Pb 23.6 and Zn 50.0) that are similar to non-contaminated
soils in other parts of the world, with Cd, Co and Pb seeming greater than that in our study.
Table 1.
Statistical parameters for the top soil data set (mg kg4 and *u.g kg4) from the Azul
region, and their variation according to three statistical tests to determine a
natural background level.
Tabla 1. Parámetros
estadísticos para los suelos superficiales (mg kg-1 and *u.g kg-1) de la región
de Azul. Variación que se observan según los tres estudios estadísticos
aplicados para determinar los valores de referencia.
|
|
*Cd |
Co |
Cr |
Cu |
Ni |
Pb |
Zn |
|
Mean |
406.1 |
7.1 |
18.1 |
40.4 |
11.2 |
17.6 |
124.6 |
Original data |
Median |
101.4 |
7.1 |
14.9 |
23.0 |
8.4 |
9.2 |
74.9 |
set |
Standard deviation |
1267.7 |
1.9 |
17.4 |
68.7 |
10.7 |
29.3 |
256.1 |
|
Number n |
42 |
42 |
42 |
42 |
42 |
42 |
42 |
|
Mean |
234.6 |
7.1 |
15.7 |
32.4 |
9.9 |
14.0 |
87.7 |
|
Median |
100.9 |
7.1 |
14.8 |
23.0 |
8.4 |
9.2 |
73.4 |
4a-outlier |
Standard deviation |
617.5 |
1.9 |
7.0 |
45.6 |
7.1 |
18.1 |
92.4 |
test |
Number n |
41 |
42 |
41 |
41 |
41 |
41 |
41 |
|
Loss (%) |
2.4 |
0 |
2.4 |
2.4 |
2.4 |
2.4 |
2.4 |
|
Upper limit |
1469.7 |
11.0 |
29.7 |
123.7 |
24.1 |
50.2 |
272.4 |
|
Mean |
91.5 |
7.1 |
14.2 |
20.1 |
7.4 |
8.9 |
67.6 |
|
Median |
88.0 |
7.1 |
13.9 |
20.2 |
7.7 |
9.0 |
67.6 |
2a-method |
Standard deviation |
22.7 |
2.0 |
3.1 |
6.5 |
2.2 |
1.1 |
21.5 |
Number n |
28 |
42 |
38 |
34 |
34 |
33 |
37 |
|
|
Loss (%) |
33.3 |
0 |
9.5 |
19.0 |
19.0 |
21.4 |
11.9 |
|
Upper limit |
136.8 |
10.9 |
20.5 |
33.1 |
11.7 |
11.1 |
110.5 |
|
Mean |
101.9 |
7.0 |
14.9 |
23.1 |
8.2 |
9.3 |
78.7 |
Calculated distribution |
Median |
101.9 |
7.0 |
14.9 |
23.1 |
8.2 |
9.3 |
78.7 |
Standard deviation |
25.1 |
1.9 |
3.6 |
8.0 |
2.8 |
1.3 |
27.6 |
|
Number n |
42 |
42 |
42 |
42 |
42 |
42 |
42 |
|
|
Upper limit |
152.0 |
10.8 |
22.1 |
39.2 |
13.7 |
11.8 |
133.9 |
Pollution
assessment
Once the
background upper limits were established, a few points with anthropic
signs were observed (Fig. 2). The heavy metal showing the greatest number of
samples with enrichment anomalies was Cd. The
greatest enrichment anomalies in Cd, Cr, Cu, Ni, Pb and Zn were also detected in the top soil of sampled
point numbers 14 and 15 (Fig. 2).
Multivariate
statistics were applied to extract quantitative information about the origin
and relationship of potentially toxic elements in soils (Boruvka
et al., 2005). Correlation matrices are presented in Table
main components were selected; they accounted for more than 88% of the total
variation. The components were rotated using Varimax
rotation. The loadings on the first component were large for Cd, Cr, Cu, Ni, Pb and Zn
contents in top soils. The second component had large loadings for
According
to the Igeo ranking cited by Muller
(1969), the level of pollution in the upper top soil of 2, 3, 40 and 42 points
were non-significant. The Igeo values for
the metals in soils with significant level of pollution are presented in Figure
The other
polluted area is located around a municipal dump with a composting plant at Tapalque town (N° 19, 20 and 21), close to the boundary of Azul's municipal district. The I for Cd,
Cu and Pb indicates slight
to moderate geo contamination. However, pollution is probably due to an earlier
unregulated storage system at the rubbish dump, and now the municipal treatment
dump has a better organized storage system. Garcia et al. (2011), after
over 10 years of accumulation of residues in dumps studied near Madrid,
reported low or moderate Cu, Ni, Zn and Pb contents
in the surrounding rubbish dump area.
In
general, agricultural and grassland soils with anthropic
signs appear to be the least contaminated soils in Cd
and Ni (slightly to moderately contaminated). The
diffuse contamination due to anthropic sources was
relevant to two natural grassland soils (39 and 41 points). These included
flooding events, where material rich in heavy metals may be carried from an
upstream source and be re-deposited on flooded land further downstream. Moreover,
the soils remain wet for long periods with a phreatic
level close to the soil surface. This suggests more influence from anthropic activities than other natural grassland soils in
a back slope position.
In
addition to those warning signs, significant differences were also observed in
all heavy metal contents, except for Pb, when using
two types of land use: cultivated soil or grazed grassland (Table 4). Dongmei et al. (2011) also reported that land
utilization is one of the important factors which affect the heavy metal
contents of regional soil. For instance, all heavy metals were present at
greater levels in
cultivated top soil. When analysed by ANCOVA, with
organic carbon content as the covariate and land use as a factor, the effect of
the organic carbon was only significant for Cd and
Cu. However, the differences between the various land use soils were still
significant for all metals. When pH was used as the covariate, its effect was
also significant for Cu and Co. However, the differences between the two land
uses were still significant. Therefore, the organic carbon and pH, two
important factors which affect the heavy metal contents and distribution, could
not explain the greater levels in cultivated top soil. As some fertilizers and
pesticides contain heavy metals such as Cd, Pb, and Zn (Kabata-Pendias and Murkherjee, 2007), the continuous application of these
agrochemicals and other soil amendments potentially exacerbates the
accumulation of heavy metals in agricultural soil (Huang & Jin, 2007). The
most widely recognised contamination of inorganic fertilisers is associated with Cd
present in the rock phosphate feedstock of all phosphate fertiliser
materials (Nicholson et al., 2003). Wei and Yang (2010) also reported
that the sources of Cd in agricultural soils in
Table 4.
Descriptive statistics of the heavy metal content (mg kg-1 and u.g kg-1), organic carbon and pH in land use groups
(cultivated soil n = 10 and grazed grassland n = 20). For any given element
within a column, values followed by the same letter do not differ at p = 0.05.
Tabla 4. Estadística
descriptiva del contenido de metales pesados (mg kg-1 and *u.g kg-1), carbono
orgánico y pH según los usos del suelo (suelos cultivados n = 11 y pasturas n =
21). Para cada elemento dentro de la columna, valores seguidos por la misma
letra no difieren a p= 0,05.
|
|
Mean |
Standard Deviation |
Minimum |
Maximum |
Cd |
Cultivated soil |
|
37.14 |
72.50 |
192.70 |
Grazed grassland |
88.04 b |
23.39 |
54.90 |
131.00 |
|
Co |
Cultivated soil Grazed grassland |
|
1.37 1.75 |
6.10 2.50 |
10.90 9.80 |
Cr |
Cultivated soil Grazed grassland |
|
5.59 2.52 |
11.70 9.00 |
33.70 18.10 |
Cu |
Cultivated soil Grazed grassland |
|
4.20 5.16 |
15.30 10.10 |
32.10 26.40 |
Ni |
Cultivated soil Grazed grassland |
|
5.04 1.72 |
6.00 4.50 |
25.30 9.40 |
Pb |
Cultivated soil Grazed grassland |
|
0.88 1.16 |
8.10 6.00 |
10.90 10.70 |
Zn |
Cultivated soil Grazed grassland |
|
19.26 18.24 |
39.80 34.80 |
103.80 93.00 |
C |
Cultivated soil Grazed grassland |
|
0.57 0.78 |
2.01 1.29 |
3.82 4.43 |
pH |
Cultivated soil Grazed grassland |
|
0.28 1.19 |
5.40 5.20 |
6.40 8.99 |
CONCLUSIONS
The
background values were in mg kg-1: Cd
0.15, Co 10.8, Cr 22.1, Cu 39.2, Ni 13.7, Pb 11.8 and
Zn 133.9. The studied soils were predominantly influenced by natural element
dispersion and accumulation processes but there are a few points with an anthropic influence. In general, Co appears to be the least
contaminant element in all top soils. The greatest soil pollution with Cd, Cr, Cu, Ni, Pb and Zn was
detected in the grassland top soil due to an unauthorized rubbish dump. The
other polluted area, located around a municipal composting plant on the
boundary between Azul and Tapalqué,
was probably due to a historic uncontrolled storage system. The slight diffuse
enrichment of crop lands could be due to an incipient anthropic
contamination. [/body]
[back]ACKNOWLEDGEMENTS
The authors thank Mr. D. Ballarena, Mr. M.
Schwab and Ms. G. Ponce from the Facultad de Agronomía of the Universidad Nacional
del Centro de la provincia de Buenos Aires for their
assistance in this study.
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