Estuarine, Coastal and Shelf Science 88 (2010) 71e83

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Estuarine, Coastal and Shelf Science

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Analysis of the spatial variation of heavy metals in the Guadiana Estuary

sediments (SW Iberian Peninsula) based on GIS-mapping techniques
J. Delgado a, *, J.M. Nieto a, T. Boski b
a
Department of Geology, University of Huelva, 21071 Huelva, Spain
b
Centre for Marine and Environmental Research, University of Algarve, 8005-139 Faro, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: This work reveals the usefulness of the GIS (Geographic Information Systems) mapping techniques to
Received 3 November 2009 show the distribution of pollutants along an estuarine environment, as the nal stage of a thorough
Accepted 9 March 2010 study. In the case of study, the environmental quality of the sediments in the Guadiana river estuary was
Available online 24 March 2010
determined by means of a complete geochemical characterization consisting on the calculation of
enrichment factors for the most important metals and metalloids (compared with the local background
Keywords:
of non-contaminated sediments). The obtained results were depicted in enrichment distribution maps
geochemistry
which evidenced a distribution of the elements in two groups: Group-I, elements with natural origin (Al,
enrichment factor
source contamination
Fe, Mn, Co, and Cr) distributed homogeneously along the basin, and Group-II, elements associated to
GIS-analysis technique anthropic origin (As, Cd, Cu, Pb, Ni and Zn) with clear punctual sources besides a high concentration all
Guadiana Estuary over the estuary. The enrichment factors for the elements of Group-II are indicative of the existence of
Iberian Pyrite Belt a noticeable diffuse historical mining pollution associated with the acid mine drainage generated in the
internal zones of the basin, which could overlap minor pollution inputs from other human activities. The
obtained results lead us to a reconsideration of the traditionally thought unpolluted environment when
it was compared to nearby estuaries.
2010 Elsevier Ltd. All rights reserved.

1. Introduction metallogenic polymetallic massive sulphide provinces in the world,

Estuaries are sedimentary environments of uvialemarine
interaction where an important biomass exchange takes place. As
a result, they are environments that favour the accumulation of
potentially contaminant elements (Sanger et al., 1999; Ridgway and
Shimmield, 2002; Spencer et al., 2003). In this sense, the water and
the elements discharged into the estuary by the rivers and the sea
will determine, according to their physicochemical features, the
environmental quality of the referred environment.
Taking into account that environmental pollution varies greatly
with time and location (Van Alsenoy et al., 1993), and that these
systems undergo strong anthropogenic pressure (urban, mining,
industrial.) instead of their natural and human importance (Prez
et al., 1991; Birch, 1996), it seems necessary to evaluate how these
impacts will affect to the system quality.
The Guadiana river estuary is located almost completely in the
Central Domain of the South Portuguese Zone (Fig. 1), crossing the
materials of the Iberian Pyrite Belt (FPI), one of the most important
* Corresponding author.
E-mail addresses: joaquin.delgado@dgeo.uhu.es (J. Delgado), jmnieto@dgeo.uhu.
es (J.M. Nieto), tboski@ualg.pt (T. Boski).
with original massive sulphide reserves exceeding 1700 million
tonnes (Sez et al., 1999). Associated with the exploitation of these
sulphide deposits, a very contaminant acid leachate with high
concentrations of metals and metalloids such as Fe, Cu, Zn, Pb, Cd,
Mn, As, etc. and sulphates (SO2
4 ) is originated. This, called acid mine
drainage (AMD) is usually added to the river network. These leach-
ates are responsible of the environmental pollution and water quality
degradation in the southern limit of the Guadiana River basin and,
consequently, of the marshlands on its mouth (Delgado et al., 2009).
Unlike the nearby Tinto and Odiel rivers, Guadiana River also
receives the acidic discharge from important mines on the Portu-
guese (So Domingo mine) and Spanish margins (Herreras mine),
as well as several upstreams pollutants from different sources, due
to its long course.
The spatial evaluation and visualization of pollutants is impor-
tant to better understand how the sources of risk, the receptors and
the exposure pathways are distributed in the space (Bien et al.,
2004; Poggio and Vrs caj, 2009). This is the reason of the recent
interest of using GIS techniques in studies of distribution of envi-
ronmental pollution (i.e. Mate j
cek et al., 2006; Zhou et al., 2007).
However, these techniques are not successful by themselves, they
must be applied after a proper investigation of the environment.

0272-7714/$ e see front matter 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ecss.2010.03.011
72 J. Delgado et al. / Estuarine, Coastal and Shelf Science 88 (2010) 71e83
Fig. 1. Regional setting of the Guadiana River Basin.
In this sense, an exhaustive geochemical study was developed
in the area, considering as references geochemical backgrounds for
metals and metalloid the ones determined by Delgado et al.
(2008), given that in previous works about the contamination in
the area (i.e. Ruiz, 2001), this background values were not properly
determined.
The aims of this work are: (1) The characterization of the
Guadiana estuary environmental quality in terms of trace metal
content, based on the specic local geochemical backgrounds
established by the authors for the river basin (2) the evaluation of
the possible incidence that some processes associated to human
activities, such as the acid mine drainage, or urban efuents, could
produce in this environment, (3) the establishment of zones with
high values of potentially contaminant elements. In order to fulll
these objectives, the possibility of integrating the result of the study
in a GIS based system was suggested.
2. Regional setting
Guadiana River is one of the most important rivers of the Iberian
Peninsula whose total length is 810 km, of which the last 200 km
make a natural border between Portugal and Spain.
Geologically the drainage basin of 67,000 km2 is heterogeneous.
Due to the deep (80 m) incision of the Carboniferous shale and
greywacke substratum, the accumulation of the sediments within
the area of the present estuary started very early, ca 13,000 cali-
brated years BP (Boski et al., 2008). Until 7500 cal BP, the sea level
rise of ca 7 mm/yr led to the fast accumulation of mainly clayey
sediments. Since then, the pace of the sea level rise slowed to ca
1 mm/yr and the estuary begun to accommodate in greater
proportion coarser sediments, partially introduced from the
continental shelf (Boski et al., 2002). In this period, the lagoonal
bodies in the vicinity of the estuary have been enclosed behind the
sand spits. The relative stabilization of the mean sea level led to the
development of vast salt-marshes in the intertidal zones covered by
halophytic plants such as Spartina densiora, Spartina martima,
Atriplex spp. and Salicornia patula.
The hydrologic regime of the Guadiana river is characterized by
a very irregular discharge, from almost zero during summer periods
up to a reported 11,000 m3/s for the winter peak of 1876 (Rocha &
Correia, 1994), i.e. half a century before the installation of the
river dams. For the low, (1 10 m3 s
1) summer discharges, the
mesotidal Guadiana Estuary is well mixed, but it is vertically
stratied in winter when the ow value are in the order of
1 103 m3 s
1). The maximum width of the water body is of 550 m
and depths are varying between 5 m and 17 m. The mixing zone is
within the rst 10 km from the mouth but brackish conditions may
extend 40 km inland. Since 2002 (closure of the Portuguese
Alqueva dam) this ux was reduced drastically.
Since the beginning of mining activities in the mid XVII century
in So Domingos Mine (Fig. 1), the high discharge winter periods
were used for the opening of mine reservoirs containing acid, metal
rich muds. During the operation period of the mine, mining wastes
and slurries were discharged from the mine, ca 100 km upstream,
directly to the Guadiana River, which transported the particulate
sulphides and waterborne metals to the estuarine zone, and then to
the Atlantic Ocean. The Estuary was thus exposed to severe heavy
metal pollution from So Domingo during one century e 1857 to
1966 e (Matos et al., 2002). Nowadays mine pollution is still
important (although with less intensity) due to the continuous
 J. Delgado et al. / Estuarine, Coastal and Shelf Science 88 (2010) 71e83
leaching of the mine residues that are still spreaded out near the
mine complex at So Domingos (Alvarez-Valero et al., 2008; Prez-
Lpez et al., 2008).
3. Materials and methods
For this work there have been collected a total of 100 sediment
samples of the channel margin (Fig. 2) distributed both along the
main channel of the Guadiana river estuary and the marshland
areas located in the municipal districts of Castro Marim and Vila
Real de Sto. Antonio (Portugal), and in the municipal district of
Ayamonte (Spain). Among all the sub-environments that can be
distinguished in an estuarine system, the channel margin, also
called low marshland, is located in the area closest to the tidal
channels. For this reason, it undergoes the tidal action (ooded
during high tide) and therefore represents an initial development
state of the marshes (Cceres, 1999).
The samples of sediment were collected with a manual drill on
the channel margins at the selected locations samples were prop-
erly kept in air-tight plastic bags and their positions (obtained with
GPS, Garmin Etrex Legend) were recorded for their subsequent
implementation in a geographic information system (GIS).
The wet sediments were placed in porcelain containers and
completely dried in a SELECTA DIGITHEAT 2001245 (150 l) model
oven at a temperature not higher than 40  C to remove humidity
without causing mineralogical changes in the samples. The samples
were sieved with a 2 mm mesh and divided in two sub-samples,
one to conduct the grain size study and the other for the chemical
analysis. The samples for the chemical analysis were grinded by
hand in an agate mortar and the 63 microm fraction was retained.
The elements concentrations were analyzed by Acme Analytical
Laboratories Ltd (Vancouver, Canada), accredited under ISO 9002,
through its Italian afliate (ERS srl, Napoli). Major oxides and
a number of trace elements evidencing possible environmental
impact, among which As, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb y Zn are
outstanding, were determined by optical (ICP-AES) and mass (ICP-
MS) spectrometry. Aqua regia extractable metal and metalloids (Ag,
As, Au, Ba, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Rb, Sc, Sr, Zn and Zr) were
also determined by digestion of 0.5 g of sample with aqua regia
extracts (3:1 HCleHNO3) at 95  C for 1 h, follow by ICP-AES anal-
ysis. This extraction is commonly used to determine the pseudo-
total metal content in environmental samples, which is considered
as a measure of the maximum potential hazard that could occur in
long term or in extreme environmental regimes (McGrath and
Cunliffe, 1985).
Other parameters such as total carbon and sulphur were
determined by Loss on Ignition (LECO).
Accuracy was calculated on Acmes in-house reference mate-
rials, DS7 and SO-18. Reference materials DS7 and SO-18 were
calibrated to an aqua regia digestion/ICP-MS determination against
published values for a concentrated HCl and HNO3 digestion of the
Canadian Certied Reference Materials Project (CCRMP) TILL-4 and
LKSD-2.
In addition, to check the quality of the analysis, a total of 9
replicates were analyzed. From them the Relative Percentage
Difference (% RPD) has been calculated as shown in Eq. (1). The
results for % RPD (Table 1) are reasonably good and the expected
value close to zero. Most values are below 1.5%, except for elements
such as Na 3.43%, Ag 2.2%, Rb 4.7%, Sc 2.0%, Sn 2.6% and Y 3.8%.
However these values are never higher than 5% RPD.
% RPD S
D=S D=2  100 (1)
Where: S determinate value of the samples, D value of the
duplicates.
73
The evaluation of analytical performance of the total concen-
tration was also made by analysing the Certied Reference
Materials (CRMs) STSD-1 and STSD-2 (Standard from stream sedi-
ments). As it can be seen in Table 1 the measured concentrations of
all the twenty-nine analytes overlap or are much closer to the
relative certied values for this standard. Exceptional values (Ag,
Au) correspond to elements which have very low concentrations, so
the analytical error is usually higher.
Generally, the ranges of recoveries (Eq. (2)) of the elements
under study (Fe, Al, As, Cd, Co, Cr, Cu, Ni, Pb and Zn) have been from
78.5 to 105%, except Cd, that does not present certied reference
value. As can be seen in Table 1, a good agreement is found between
our result of analysis and reference values.
% Recovery Obtained value=Certified values  100 (2)
The grain size study of the sediment samples was performed
using a particle size analyser Malvern Mastersizer 2000, with
approximately 20 g of sediment.
Multivariate analysis techniques have been widely used to
distinguish the natural and anthropic contribution of elements in
the estuarine system, based on the variables level of association. In
this way, principal components analysis (PCA) was carried out by
means of a Pearsons correlation matrix (0.05 signicance level) to
the variables and samples in order to establish possible relations
and input sources among polluting elements.
Enrichment factors (EF), which compare the concentration of
a given element in the environment with the one expected when
excluding anthropogenic contributions, that is, with the regional
level (background) have been calculated. For the calculation of EF,
the background values, established from the study of the sediments
in two deep cores located at the estuary ood plains (Delgado et al.,
2008) have been used.
EF distribution maps in order to survey sites of environmental
vulnerability in the Guadiana river estuary were generated by
means of data interpolation using the ordinary kriging technique
(Webster and Oliver, 2001). For this purpose, ArcGIS ESRI soft-
ware was used, at a 50 m resolution grids (raster images) where
each cell values (pixel) express the EF of the considered element in
sediments at a specic location. Weights of predicted values are
based not only in the distance between samples and the prediction
position, but also in the whole spatial distribution among the
measured propositions and their values. A maximum searching
radius of 300 m is established for nearby samples (based on
samples location and at least one interpolation point) in order to
obtain a high weight in the spatial distribution for surrounding
points among each other. Moreover, an interpolation barrier was
used (water surfaces) to avoid no-existing interpolations. Of course,
there exists some uncertainty like in any interpolation method, so
the interpolation points should be considered as possible expected
values, but no necessarily the true values, which could never be
obtained (Zhang, 2006).
4. Results and discussion
4.1. Grain size distribution
For a proper determination of the environmental quality of
sediments, characterization of the grain size is important, as the
metals responsible for pollution tend to accumulate in the
smallest grain-sized fractions, i.e., mainly in limes and clays. This
phenomenon is attributed to the high specic surface presented
by the nest fractions which, as a result, favour adsorption
processes (Forstner, 1983; Usero Garcia et al., 1997; Thuy et al.,
2000).
74 J. Delgado et al. / Estuarine, Coastal and Shelf Science 88 (2010) 71e83

Fig. 2. Sampling points map showing the different sub-systems present in the Guadiana Estuary.
 J. Delgado et al. / Estuarine, Coastal and Shelf Science 88 (2010) 71e83 75

Table 1
Evaluation of the analysis performance by calculating the % RPD and comparison with certied values.

% RPD CAN STSD-1 CAN STSD-2

Obtained value Certied value % Recovered Obtained value Certied value % Recovered
Al2O3 1.49 8.67 9.00 96.3 16.0 16.1 99.4
Fe2O3 0.34 6.28 6.50 96.6 7.35 7.50 98.0
MgO 0.12 2.16 2.20 98.2 3.15 3.10 102
CaO 0.66 3.66 3.60 102 4.18 4.00 105
Na2O 3.43 1.73 1.80 96.1 1.70 1.70 100
K2O 1.31 1.24 1.20 103 2.13 2.10 101
TiO2 0.45 0.64 0.80 80.0 0.73 0.80 91.3
MnO 0.06 0.47 0.50 94.0 0.13 0.10 130
TOT/C 0.03 13.2 12.3 108 1.69 1.60 106
Ag 2.22 0.30 <0,5 e 0.40 0.50 80.0
As 0.60 19.8 23.0 86.1 33.3 42.0 79.3
Au* 0.20 0.01 0.01 67.5 0.0015 0.003 50.00
Ba 0.60 585 630 92.9 515 540 95
Be 1.40 1.00 1.60 62.5 4.00 5.20 76.9
Cd 0.10 0.90 Not data e 0.80 Not data e
Co 0.40 16.3 17.0 95.9 20.0 19.0 105
Cs 1.30 1.50 1.80 83.3 10.8 12.0 90.0
Cu 0.90 34.6 36.0 96.1 41.2 47.0 87.7
Mo 1.10 0.90 <5 e 10.3 13.0 79.2
Ni 0.50 19.3 24.0 80.4 49.2 53.0 92.8
Pb 0.50 37.4 35.0 107 68.5 66.0 104
Rb 4.70 e 3.00 e 95.7 104 92
Sc 2.00 12.0 14.0 85.7 14.0 16.0 87.5
Sn 2.60 3.00 4.00 75.0 5.00 5.00 100
Sr 0.90 193 170 114 455 400 114
V 1.20 89.0 98.0 90.8 100 101.00 99.0
Y 3.80 36.2 42.0 86.2 35.6 37.0 96.2
Zn 0.90 150 178 84.3 193 246 78.5
Zr 0.00 221 218 101 183 185 99.1

Mayor in %, trace in ppm (* ppb). % RPD (relative percentage difference).

The sediments have been classied according to the subdivision been analyzed for the 100 samples of surface sediments (Table 2).
established by Wentworth (1922) for the nest fractions (sand, Due to their siliciclastic nature, the sediments are mainly composed
mud and clay) and the percentages of the respective grain sizes of SiO2, Al2O3, with amount of 74%, presenting mean concentrations
have been projected on the triangular diagram suggested by Folk of 60.4% and 14.9% respectively. These are also followed by Fe2O3
(1954). The grain size data have allowed determining that 97.5% (5.71%), Na2O (2.45%) and K2O (2.37%). The rest of the analyzed
of the surface samples collected in the estuary are classied as elements are mean concentrations lower than 2%, reaching values
limes or sandy limes, whereas the rest (RG-1, RG-2, S-00-14, ES-7, of 0.07% in the case of MnO (Table 2). In general, the distribution of
S-5 and S-6), of sand or slightly lime sand-sized grain, correspond major oxides is very homogeneous for the whole estuary. The
to a sandy bar located in the main channel near Vila Real (Fig. 3). values that are clearly deviated from the mean belong to the
No big differences in the grain size distribution have been
observed for the different sub-environments studied. Usually, the
samples from the estuary inner areas (tidal channels and ood
plains) show higher contents in clays and limes, while the sandy
fraction is more abundant as we approach the source area (main
estuarine channel).
In general, the sediments corresponding to the main estuary
channel show slightly larger grain sizes when compared with the
sediments sampled in the secondary tidal channels (Fig. 3). The
percentage of average grain sizes for clay, lime and sand fractions is
15.03, 61.62 and 23.35%, respectively, for the samples of the main
channel, as opposed to 15.91, 72.46 and 11.63% for the samples of
the secondary tidal channels, which indicates that lime sediments
are more abundant in tidal channels, and that the sand percentage
is lower with respect to the main channel. As would be expected for
this kind of environments, there is a gradual decrease in the sand
rate in the inner areas of the tidal channels at the same time that
preferably lime and clay rates increase.

4.2. Geochemical characterization

4.2.1. Major oxides

Total concentrations of 9 major oxides (SiO2, Al2O3, Fe2O3, MgO, Fig. 3. Representation of the surface sediment samples in ternary classication
CaO, Na2O, K2O, TiO2, P2O5, MnO), along with other parameters diagram suggested by Folk (1954), from the fractions lower than 2 mm obtained by
such as LOI, TOT/C (total carbon) and TOT/S (total sulphur) have Malvern Mastersizer. (S: sand, Z: silt, sZ: sandy silt, zS: silty sand).
76 J. Delgado et al. / Estuarine, Coastal and Shelf Science 88 (2010) 71e83

Table 2 Similarly, the results obtained for Cu are also outstanding,

Descriptive statistics of the major and trace elements of the Guadiana estuary ranging from 1.2 to 73.0 ppm, with a mean value of 50.0 ppm. Other
sediments. Major in %, trace in ppm except for Au (ppb). SD represents standard
deviation of the mean and Bk the background levels established by Delgado et al.
elements follow this decreasing order: Pb, Ni, As, Cr and Co with
(2008). mean values of 32.9, 27.8, 25.5, 19.2 and 17.1 ppm, respectively.
Concentrations registered for Cd are also signicant, ranging from
Element n Min Max Mean Median SD Bk
0.5 to 1.4 ppm, showing a mean value of 0.2 ppm, which must be
SiO2 100 42.4 96.6 60.4 58.6 0.92
taken into account due to the high toxicity of this element.
Al2O3 100 1.06 18.4 14.9 15.8 0.33 17.4
Fe2O3 100 0.27 7.50 5.71 6.09 0.14 6.40 Taking into account the variability of total concentrations
MgO 100 0.05 2.04 1.61 1.70 0.04 (Table 2) of the trace elements, two large groups with different
CaO 100 0.15 2.69 0.97 0.89 0.04 behaviours can be roughly distinguished: (1) elements such as Ba,
Na2O 100 0.25 3.71 2.45 2.48 0.05 Co, Cr, Ni, Rb, Sr and Zr, which tend to be homogeneously distrib-
K2O 100 0.56 2.96 2.37 2.43 0.04
TiO2 100 0.07 1.12 0.91 0.96 0.02 0.89
uted; and (2) a group composed mainly of As, Cd, Pb and Zn which
P2O5 100 0.02 0.24 0.15 0.15 0.00 show a very heterogeneous variability.
MnO 100 0.01 0.19 0.07 0.05 0.00 0.06
LOI 100 0.90 25.2 10.4 10.7 0.39 4.3. Relationship between variables: PCA
TOT/C 100 0.12 7.23 1.82 1.69 0.09
TOT/S 100 0.01 1.69 0.21 0.17 0.02
To complete a proper geochemical characterization of the
Ag 100 0.05 0.30 0.10 0.12 0.01 sediments, a Principal Component Analysis (PCA) has been con-
As 100 1.30 81.8 25.5 26.4 1.21 15.8
Au* 100 0.02 128 4.00 5.55 1.27
ducted using Pearsons correlation coefcients. The coefcients
Ba 100 58.9 488 380 364 6.73 obtained have been represented in Table 3.
Cd 100 0.05 1.40 0.20 0.23 0.02 0.09 The data used for the analysis were Si, Al, Fe and Mn among the
Co 100 0.60 24.8 17.1 16.1 0.45 16.4 major oxides, and As, Cd, Co, Cr, Cu, Ni, Pb and Zn among the metals
Cr 100 1.60 24.0 19.2 17.6 0.46 21.7
and metalloids analyzed, since they have been described in
Cu 100 1.20 73.0 50.0 47.6 1.76 28.2
Hg 100 0.01 4.43 0.34 0.56 0.08 numerous works as constituent elements of acid mine drainage
Mo 100 0.10 3.80 1.00 1.28 0.09 associated with the polymetallic sulphurs of the Iberian Pyrite Belt
Ni 100 0.70 41.6 27.8 26.1 0.75 32.4 (e.g. Fernndez-Caliani et al., 2009). Also, the clay content of the
Pb 100 1.30 62.5 32.9 32.0 1.17 18.6 samples has been included, as it plays a key role in the accumula-
Rb 100 19.4 144 110 105 2.41 134
Sc 100 0.10 15.0 3.90 4.45 0.27
tion of contaminant metals in the sediments (Fernndez-Caliani
Sr 100 15.4 168 131 129 1.97 123 et al., 1997).
Zn 100 4.00 483 168 162 7.10 75.4 The results show high correlation coefcients between Al, Fe,
Zr 100 23.7 416 231 224 5.87 224 Co, Cr and Ni, along with very high values between As, Zn, Cd and
Major in %, trace in ppm (* ppb). n (number of samples). SD (standard deviation), Bk CuePb. Similarly, the existence of high inverse correlations SieAl
(background levels by Delgado et al., 2008). and SieFe has been checked.
The variables analyzed, which represent 81% of the total of
sample variability, have been represented in Fig. 4. In this gure, the
samples from the river sandy bar located in the main channel. In projection factors for axes X (F1) and Y (F2) represent 68% and 13%
the secondary tidal channels, the pattern is typical of these envi- of the variance, respectively. Factor F1 explains very clearly the
ronments, with a decrease in the rate of SiO2 and an increase in differences in the composition of the sediments based on Si
Al2O3 and Fe2O3 as we move away from the main channel. This concentration, as stated by Morales (1993), which can be distin-
evolution of major oxides is in agreement with the grain size guished because they are part of the detritic fraction of sediments
distribution described above. (range between gravels and medium-sized limes). This fact is
The ratio SiO2/Al2O3 evidences the textural maturity of the supported by the high inverse correlation coefcients (Table 3)
sediments. This is due to the relative enrichment of Al-rich phil- with respect to Fe (
0.95) and Al (
0.94), which are represented
osilicates dependent of Si-rich phases that are produced in ne- symmetrically opposed to Si in the diagram. The clay fraction tends
grained sediments (Weltje and Eynatten, 2004). to group with Fe and Al, including also Mn and other metals such as
In this way, a decrease in the rate SiO2/Al2O3 is related to Co, Cr and Ni (all of them show high correlations between each
a decrease in grain size and, as a result, with a decrease in textural other), and which therefore tend to accumulate in the nest frac-
maturity. The sediments of the Guadiana estuary show a low tions of the sediments (Table 3). This association (Group-I) may be
textural maturity (SiO2/Al2O3 < 5), except for the samples located in considered in principle as of natural origin, since Co, Cr and Ni are
the levee (river bank) located of the main channel, where rates of commonly part of the phylosilicates (Borrego et al., 2004), that by
44 and 98 for samples RG-1 and RG-2, respectively, are found. These surface alteration processes are formed in the basin, mobilized and
high values evidence a high textural maturity and imply that these transported to the estuary, where they tend to accumulate in the
sediments have undergone a very long sedimentary cycle (Lpez- clay fraction of sediments. This one, with a different behaviour from
Gonzlez et al., 2006). the rest of the metals studied, has been similarly described by other
authors such as Morillo et al. (2004) in a study of the sediments of
4.2.2. Trace elements the platform in the littoral of Huelva. In addition, in the materials
Trace element concentrations such as Ag, As, Au, Ba, Cd, Co, Cr, that form the low basin of the Guadiana River, numerous forma-
Cu, Hg, Mo, Ni, Pb, Rb, Sc, Sr, Zn and Zr have been analyzed (Table 2). tions of basic rocks (constituents of the unit Complex volcanic
The highest concentrations are presented by elements such as sedimentary, CVS) are found. These are a potential source of
Ba, Zr, Zn, Sr, Rb, whose mean values exceed 100 ppm. These high elements such as Co, Cr and Ni, among which, for example, the so
values are associated to shell fragments for the case of Sr and Rb, or called Paymogo Volcanic Axis can be mentioned (Donaire et al.,
to heavy minerals such as zircon for the case of Zr, very abundant in 1998).
the nearby coastal sediments (Fernndez-Caliani et al., 1997). The behaviour of elements such as As, Cd, Cu, Pb and Zn is
Zn shows very uctuating values between 4.00 and 483 ppm, represented by factor F2. These elements tend to form a new group,
with a mean of 168 ppm. so that they may show a different origin from that already
 J. Delgado et al. / Estuarine, Coastal and Shelf Science 88 (2010) 71e83 77

Table 3
Pearson correlation matrix for the parameters analyzed in the surface sediment samples of the Guadiana estuary. Alpha signicance level 0.05.

Clay SiO2 Al2O3 Fe2O3 MnO As Cd Co Cr Cu Ni Pb Zn

Clay 1
SiO2 L0.70 1
Al2O3 0.78 L0.95 1
Fe2O3 0.77 L0.94 0.96 1
MnO 0.27
0.39 0.41 0.46 1
As 0.44 L0.54 0.54 0.64 0.12 1
Cd 0.37
0.20 0.28 0.31
0.02 0.55 1
Co 0.77 L0.81 0.89 0.90 0.55 0.52 0.44 1
Cr 0.78 L0.89 0.88 0.88 0.40 0.48 0.22 0.82 1
Cu 0.64 L0.82 0.82 0.83 0.19 0.72 0.44 0.74 0.77 1
Ni 0.80 L0.91 0.94 0.94 0.51 0.55 0.28 0.90 0.92 0.78 1
Pb 0.63 L0.79 0.78 0.77 0.02 0.63 0.28 0.65 0.73 0.89 0.72 1
Zn 0.49 L0.55 0.59 0.62 0.04 0.80 0.74 0.61 0.49 0.80 0.56 0.71 1

In bold, signicant values (except diagonal) at the level of signicance alpha 0.05 (two-tailed test).

mentioned for group-I. It is well known that elements such as As,
Cd, Cu, Pb and Zn are associated to acid mine drainage processes of
the IPB polymetallic sulphurs (Fernndez-Caliani et al., 1997; Olas
et al., 2006). As a result, it could be expected that the main
contributions of these elements to the environment were produced
by this process, which has been contrasted in the inner zones of the
Guadiana river low basin (Grande et al., 2005; Delgado et al., 2009).
Thus, the negative values of F2 seem to gather the group of
elements with a natural origin derived from erosion, transport and
sedimentation processes typical of the drainage basin, while the
values grouped according to the positive variation of F2 would
represent those elements mainly related to historical mining
activity (Group-II).
4.4. Enrichment factors
4.4.1. Normalization of the geochemical data
The variability of trace metals in sediments can be natural or
inuenced to some degree by anthropogenic sources. Since the
metals coming from these sources usually accumulate in the ne
fraction of the sediment, the study of enrichment factors requires
previous compensation or normalization of grain size on the metal
variability in different textural samples (Aloupi and Angelidis,
2001). Numerous conservative and normalising elements have
been suggested in the bibliography such as Al, Cs and Fe: Al (Hirst,
1962a, 1962b; Bruland et al., 1974; Bertine and Goldberg, 1977;
Sharman et al., 1984; Carral et al., 1995), Li (Loring, 1991), Cs
(Ackermann, 1980; Grousset et al., 1995) and Fe (Piper, 1971;
Blomqvist et al., 1992; Herut et al., 1993).
Due to the existence of local geochemical background values
established for the Guadiana estuary by Delgado et al. (2008),
where the best approaches to sediment textural variability are
proved to be obtained by normalising with Al, in the present study
Al has been chosen as the normalising element, so that the data can
be comparable. The relationships found between Al and the metals
responsible for contamination, as well as between Al, Si and the
clay fraction, have been represented in Fig. 5. As show in Fig. 5,
linear correlation coefcients higher than R2 0.44 (Al2O3 vs Clay)
have been obtained in all cases, reaching values up to R2 0.81 for
the case of Al2O3 vs Ni.
4.4.2. Calculation of enrichment factors
Another factor to be taken into account in the establishment of
enrichment factors for studies on contaminant elements in estuarine
and/or marine sediments is the geochemical background. This value
will be fundamental to distinguish whether an element present in
the environment appears naturally or, on the contrary, it is inu-
enced by anthropogenic activities (Daskalakis and OConnor, 1995;
Liu et al., 2003). As a result, the local geochemical background
values established by Delgado et al. (2008) were chosen when con-
ducting this study, so that the work could drive to proper interpre-
tations on the environmental quality of the estuary sediments.
Quantication of the environmental quality of an estuary can be
established by calculating the enrichment factor using the
following expression (Eq. (3)).

FE M=Nsample =M=Nbackground (3)

Where: [M]sample metal concentration for the studied sample,

Fig. 4. Representation of the principal component analysis (PCA) for the total of
samples analyzed in the Guadiana river estuary. Alpha signicance level 0.05.
[M]background regional Background, [N]sample concentration of
the normalising element for each sample, [N]background value of
the normalising element in the background.
Analysing the meaning of the enrichment factor, an EF value of 1
indicates a predominantly natural origin for that element in the
sediment, whereas higher values indicate enrichment due to either
natural causes (biotic input) or anthropic inuence. EF values lower
than 1 can reect remobilisation and loss of that element in relation
to the normalising element, or overestimation of the contents of the
reference metals (Mil-Homens et al., 2006).
Based on the observation of the enrichment mean values (Fig. 6)
obtained for Fe, Mn, As, Cd, Co, Cr, Cu, Ni, Pb and Zn (main evidence
78 J. Delgado et al. / Estuarine, Coastal and Shelf Science 88 (2010) 71e83

Fig. 5. Examples of linear relationship between Aluminium, Silica, clay and some metals in surface samples of sediments in the Guadiana river estuary.

of pollution in estuarine environments), the elements have been
divided into 3 groups:
(1) Impoverished or poorly enriched element (FE z 1): Fe, Mn, Co,
Cr and Ni.
(2) Enriched element (1 < FE < 2): As, Cd, Cu and Pb.
(3) Strongly enriched element (FE  2): Zn.
In the rst group, corresponding to impoverished or poorly
enriched elements, the elements that present a natural origin in the
Guadiana estuary have been associated. This origin has been
deduced from the relationships found between those elements and
Al and the percentage of clay in the samples. The elements Fe, Mn,
Co, Cr and Ni in most of the samples present values very close to 1,
which supports that these elements do not seem to be inuenced
by anthropic activities in the study area. This association was
3 mostly urban wastes (discharging without purify) and minority
2 Guadiana river estuary. They can be useful to identify input of
EF
1 other anthropic activities in the study area, mostly urban wastes
1.94
1.77 1.86
1.02 1.08
1.00 0.96 0.92
highlighted in this coastal area by authors like Morillo et al. (2004)
related preferably with the residual fraction and therefore associ-
ated with the bedrock of the study area.
In the last two groups of elements heavy metals (As, Cd, Cu, Pb
and Zn) associated to sulphide deposits are grouped in accordance
with numerous works on contamination by heavy metals in the IPB.
These metals are characterized by a fairly homogeneous distribu-
tion of concentration and have been associated in some studies to
processes related to leachate and surface alteration of polymetallic
sulphides in the IPB (Ruiz, 2001) and inner zones of the Guadiana
river low basin (Delgado et al., 2009), and to mine-related
processes which have been developed in the IPB for approximately
4500 years (Leblanc et al., 2000; Nocete et al., 2005).
This would result in a fairly homogeneous distribution that
could be called diffuse, but with high enrichment values with
respect to background. Nevertheless, some anomalies with
maximum EF values for As, Cd Cu and Zn have been detected,
probably as a result of other anthropic activities in the study area
port activities and industrial efuents.
Median EF which allow to classied elements in three groups,
are representative of the current state of contamination in the
contaminant elements of anthropic origin into the system, either as
2.47 a result of an historical mining activity in the IPB, or as a result of
(discharging without purify) and minority port activities and
1.84
industrial efuents.

0
4.5. Sites of environmental vulnerability in the Estuary
Fe Mn As Cd Co Cr Cu Ni Pb Zn
Fig. 6. Mean EF for the studied elements in the Guadiana estuary (values on a loga- For a better understanding of the problems entailed by heavy
rithmic scale). metal contamination in coastal ecosystems, EF maps of potentially
 J. Delgado et al. / Estuarine, Coastal and Shelf Science 88 (2010) 71e83 79

Fig. 7. Mapping by Krigings method of the EF of As, Cd, Co, Cr, Cu, Ni, Pb and Zn.
80 J. Delgado et al. / Estuarine, Coastal and Shelf Science 88 (2010) 71e83

Fig. 7. (continued).
 J. Delgado et al. / Estuarine, Coastal and Shelf Science 88 (2010) 71e83
contaminant elements in the estuary have been drawn using GIS.
Also, it allows the development of a tool to make monitoring of the
coastal system easier (Mattakalli et al., 1996; Lathrop et al., 2001;
Chica-Olmo et al., 2004), locating zones of greater environmental
vulnerability.
Arsenic shows EF values generally raging from 1 to 2 with
a mean value close to 2, which suggests that, this element is
enriched along the whole study sector (Fig. 7a). This homogeneous
distribution, that could be attributed to a constant input of this
element from acid mine drainage, contrasts with a positive
anomaly detected in the proximities of the harbour and yatch club
of Ayamonte (EF > 6), which evidences the presence of a punctual
input of anthropic origin, possibly related to port activity or urban
wastes (Fig. 7a).
Cadmium is the element with the highest enrichment in the
whole estuary, with mean values as high as 1.94. In general, most
of the data present an EF variation rate between 1 and 4, which
leads to assume a similar behaviour to that described for As.
Likewise, eventual sources of element accumulation in the estua-
rine sector have been detected. They are located between the
towns of Vila Real de Sto. Antonio and Ayamonte and at the
internal zone of the Castro Marim tidal channel (EF > 7), as shown
in Fig. 7b.
Cobalt and Cr (Fig. 7c, d) are elements that evidence a homoge-
neous natural origin, with EF mean values of 1.08 and 0.96
respectively. Both elements present EF values very close to 1 in the
whole estuary, with small uctuations mostly related to occula-
tion/precipitation processes in water mixing zones. Although Cr EF
are slightly lower, its relationship with the residual fraction of the
sediments was demonstrated (Morillo et al., 2004).
Cooper EF map (Fig. 7e) shows values ranging between 1 and 2.
Thus, these values, along with such a homogeneous distribution,
highlight a diffuse historical contamination of mining origin in
most of the estuary, as happens for other elements such as As and
Cd.
Analysing Ni distribution (Fig. 7f), it could be presumed that the
presence of this element in the estuary is due to geogenic contri-
butions. It is true for most of the estuary, but when studying
punctual values in detail, it can be observed that, in spite of that
practically the whole estuary presents EF very close to 1, there exist
extremely high EF values located in the junction of the tidal channel
of Castro Marim and Carraqueira with the main estuarine channel.
This locally strong Ni EF values appear to be related to the urban
wastes and aquiculture farms.
Lead and Zn present EF ranging from 1 to 3 for almost all study
area (Fig. 7g, h), with a mean value of 1.8 for Pb and 2.5 for Zn.
Higher EF (2 < EF < 4) for Pb were determined in zones near the
International Bridge (border between Spain and Portugal) and
downstreams. This phenomenon may be related to the Pb pollution
(leaded gasoline) associated to the trafc on the bridge. Upstreams,
the EF maintain values in the same range, followed by a dilution
effect of seawater reaching values even lower than 1 at the river
mouth.
The general distribution of Pb is similarly consistent with that
described for As, Cd and Cu. In this sense, samples located upwaters
of the International Bridge present EF values higher than 1, for
example: S-00-19 (EFPb 1.47) 11 km upstream from the sample
RG-20 (EFPb 1.15), RG-17 (EFPb 1.58), RG-11 (EFPb 1.45), RG-10
(EFPb 1.79) and S-00-12 (EFPb 1.83). For detail information on EF
values, see Annex 1 in the supplementary information. Thus,
a general range of variation 1 < EF < 2 is established along the
estuary, which again reveals a diffuse historical contamination of
mining source. A recent study of suspended particulate matter
(SPMs) in the Guadiana estuary (Caetano et al., 2006) has shown
that during periods of moderate ow (i.e. winter rains) the SPMs
81
comprise iron-rich particles containing 3e12 wt.% Fe, 20e80 ppm
Pb and higher levels of Cu and Zn. Similarly, recent studies of Pb
isotopes as tracers of mining pollution in molluscs of the Guadiana
Estuary (Company et al., 2008), conrm that the isotopic signature
of Pb in the Estuary is strongly linked to anthropogenic Pb mine-
related pollution from Mina de So Domingos in Portugal and
Las Herreras in Spain, and that geogenic Pb derived from the
erosion of the Devonian or Carboniferous rocks, if present, is very
small (Company et al., 2008). Thus, given that the methodology
applied eliminates possible geochemical alterations produced by
the grain size, and EF values have been obtained from Background
normalized data, the results are consistent with the available lead
isotopic data.
Zn has a similar general distribution but EF values are higher
than Pb (S-00-19 (EFZn 4.11), RG-20 (EFZn 1.33), RG-17
(EFZn 2.17), RG-11 (EFZn 1.43), RG-10 (EFZn 2.71) and S-00-12
(EFZn 2.64)). This element presents EF much higher than the
mean value in the proximities of the harbour of Ayamonte
(4 < EF < 5), as well as in the middle zone of the Castro Marim tidal
channel, with values exceeding up to 6 times the local background
(Table X). These high EF values can probably be related to the
existence of an additional input source of anthropic origin in these
areas, the rst related to the harbour activities, and the second
probably related to the aquiculture or urban washes.
5. Conclusions
This study has allowed us to show the existence of diffuse
historical contamination in the sediments of the Guadiana estuary
related with AMD generated in the inner zones of the basin, and to
prove that EF calculation along with a GIS based spatial analysis by
ArcGIS is a great tool to assess the environmental quality of
estuarine systems.
PCA analysis allowed to distinguish two main association of
elements characterized by common behaviours and origin: 1) As,
Cd, Cu, Pb and Zn mostly of anthropic origin, mainly derived from
AMD processes generated in inner zones of the basin and from
sources of contamination located in the proximities of the towns; 2)
Fe, Mn, Co, Cr and Ni are associated with the clay fraction of sedi-
ments probably of natural origin (except for some punctual
anomalies of Ni).
Enrichment factor maps allowed to dene three groups of
elements characterized by different input sources: (1) Impov-
erished or poorly enriched element: Fe, Mn, Co, Cr and Ni, (2)
Enriched element: As, Cd, Cu and Pb, (3) strongly enriched
element: Zn.
From the EF distribution maps, zones of environmental
vulnerability have been established in the Guadiana estuary, where
relevant geochemical anomalies of trace elements have been found.
These zones are: 1) harbour and town of Ayamonte, As anomaly-
related zone; 2) Outskirts of the towns of Ayamonte and Vila Real,
with high Cd enrichment factors; 3) Castro Marim tidal channel
represents a Ni contamination source for the main estuarine
channel; and 4) Harbour of Ayamonte, Castro Marim tidal channel
and International Bridge, where important Zn and Pb concentra-
tions are registered.
GIS based spatial analysis and Kriging interpolation method,
have been proven to be a powerful tool to represent the distribution
of enrichment factor (EF) of elements in the study area. The EF maps
helped in the identication of both acidic mine waters and some
human activities as possible source of contaminants in the sedi-
ments of the Guadiana Estuary.
Finally these results show the pollution risk of the ecosystem
and underline the requirement of environmental attention to avoid
possible future incidences.
82 J. Delgado et al. / Estuarine, Coastal and Shelf Science 88 (2010) 71e83
Acknowledgements
This study has been developed in the framework of the project
INTERREG IIIA MEGASIG: Monitoring and environmental
management of the Guadiana estuary wetlands. JDR also
acknowledged a Ph.D. grant of the Huelva University.
Appendix. Supplementary data
Supplementary data associated with this article can be found in
the online version, at doi:10.1016/j.ecss.2010.03.011.
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