Marine Pollution Bulletin 124 (2017) 421434

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Marine Pollution Bulletin

journal homepage: www.elsevier.com/locate/marpolbul

A method to assess the evolution and recovery of heavy metal pollution in MARK
estuarine sediments: Past history, present situation and future perspectives
Javier F. Brcena, Inigo Claramunt, Javier Garca-Alba, Mara Luisa Prez, Andrs Garca
Environmental Hydraulics Institute, Universidad de Cantabria, Avda. Isabel Torres, 15, Parque Cientco y Tecnolgico de Cantabria, 39011 Santander, Spain

A R T I C L E I N F O A B S T R A C T

Keywords: A methodology to assess the historical evolution and recovery of heavy metal pollution in estuarine sediments
Sediment cores was developed and is presented here. This approach quanties the distribution of heavy metals in sediment
Heavy metal pollution cores, and investigates the inuence of anthropogenic activities and/or core locations on the heavy metal pol-
Anthropogenic and natural sources lution, by proposing and using sediment quality indices and polynomial regressions.
Subtidal and intertidal areas
The method has been applied to the Suances Estuary conrming its suitability as a comprehensive and
Recovery assessment
Suances Estuary (SE)
practical management tool. In this estuary, the evolution of heavy metal pollution (since 19971998 to 2015)
pointed out the deeper the sediments, the more polluted, indicating a recovery at the upper layers due to the
closure and ending of washing discharges from mining, and the reduction of metal loads from industrial was-
tewaters. In terms of global pollution, the intertidal and subtidal sediments will require 43.1 2.8 and
8.6 0.6 years to be unpolluted, respectively.

1. Introduction 1998). However, under certain physicochemical conditions, heavy

Heavy metals are important pollutants due to their toxicity, long
persistence and bioaccumulation (Kumar et al., 2008; Chon et al., 2010;
Liu et al., 2016). In extreme situations, they may represent a serious risk
for living organisms and even for human health (Farias et al., 2007).
High levels of heavy metals in estuaries can be attributed to both nat-
ural and anthropogenic sources. Most heavy metals are natural products
of biogeochemical cycles (e.g. rock weathering) and volcanic activities
(Zhang et al., 2013). However, the rapid industrial and urban devel-
opments over the past century have intensively discharged heavy me-
tals into estuaries from a variety of anthropogenic sources such as in-
dustrial euents and domestic sewage (Smano et al., 2016; Wang and
Wang, 2016), urban storm-water runo (Bhattacharya et al., 2014),
mining exploitation (Irabien et al., 2008), and/or boating activities
(Sarkar et al., 2004). Thereby, heavy metal pollution has become a
serious problem in estuarine ecosystems (Cundy et al., 2003; Chapman
and Anderson, 2005; Pekey, 2006).
The fate of heavy metals in water systems is determined primarily
by partitioning and by transport (Smano et al., 2014). In general,
anaerobic and reduced nature of estuarine sediments favours the re-
tention of heavy metals (Lacerda and Abrao, 1984). Thus, estuarine
sediments have a large capacity to retain heavy metals from various
sources, and might act as sinks for them (Gibbs, 1977; Menon et al.,
metals previously trapped in the sediments may be remobilized to the
water phase and, consequently, act as a secondary source of con-
tamination to the estuary (Ridgway and Shimmield, 2002; Atkinson
et al., 2007). When metals are released to the dissolved phase from
sediments, the bioavailability is increased and, thus, the likelihood of
risk for aquatic life (Ankley et al., 1996).
According to this trapping capacity, the evolution of heavy metals in
estuarine sediments reects the geochemical history of a region in-
cluding any anthropogenic impact (Szefer and Skwarzec, 1988; Viguri
et al., 2007; Ye et al., 2012; Birch et al., 2013). The study of dated
sediment proles (cores) from industrialized estuaries is indeed a va-
luable tool to assess the sediment quality and to reconstruct the history
of heavy metal pollution, as the sediments in these areas are the major
reservoirs of heavy metals (Goldberg et al., 1978; Roy and Crawford,
1984; Karuppiah and Gupta, 1998; Cearreta et al., 2002; di Gregorio
et al., 2007; Larrose et al., 2010; Lim et al., 2013; Chakraborty et al.,
2014; Birch, 2017).
Therefore, the identication, control and removal of heavy metal
pollution from anthropogenic sources become essential in order to
protect and ensure the ecosystem services and the water body uses in
estuaries (Apitz, 2012; Legorburu et al., 2013). Accordingly, the main
objective of this work was to investigate whether the beginning and
ending of anthropogenic activities have inuenced the heavy metal

Corresponding author.
E-mail addresses: barcenajf@unican.es (J.F. Brcena), iigo.claramunt@alumnos.unican.es (I. Claramunt), garciajav@unican.es (J. Garca-Alba), luisa.perez@unican.es (M.L. Prez),
garciagan@unican.es (A. Garca).

http://dx.doi.org/10.1016/j.marpolbul.2017.07.070
Received 10 February 2017; Received in revised form 19 July 2017; Accepted 30 July 2017
Available online 12 August 2017
0025-326X/ 2017 Elsevier Ltd. All rights reserved.
J.F. Brcena et al.
Fig. 1. Map of the Saja-Besaya River Basin and the Suances Estuary, indicating the locations of subtidal (white colour) and intertidal (grey colour) areas; the three industrial areas and
discharges (IA1IA3); the two mining activities (Reocn mine and Cucha quarry); and the seven subtidal (CS1CS7; black triangles) and ve intertidal (CI1CI5; black circles) survey
stations.
pollution in estuarine sediments. Specically, our objectives are: a) to
quantify the horizontal and vertical distribution of heavy metals in the
sediment cores of Suances Estuary; b) to develop a methodology in
order to assess the historical evolution of heavy metal pollution and to
predict the recovery time in estuarine sediments, after the end or re-
duction of impacts from anthropogenic sources, by proposing and using
sediment quality indices and polynomial regressions, and c) to apply
the developed methodology to the Suances Estuary (N Spain).
2. Materials and methods
2.1. Study area and data collection
The Suances Estuary, henceforth SE, ( 4.0237/43.4007 lat/lon
ED50) is a mesotidal estuary located in the northern Spanish coast
(Fig. 1). It is approximately 5.5 km long with a 150 m mean width, and
a surcial area of 389 ha where intertidal ats occupy 76% of the es-
tuarine area (Brcena et al., 2012b).
During the last century, major industrial and mining activities
modied the estuary extracting heavy metals prior the estuary (mining
runo) and discharging heavy metals (industrial wastewaters) into the
estuary (Brcena et al., 2012a). A few kilometres upstream from the
estuarine mouth drains the Reocn deposit (see mine in Fig. 1), one of
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Marine Pollution Bulletin 124 (2017) 421434
the largest carbonate hosted ZnPb ores in Europe (Fernndez et al.,
2009). The archaeological evidences have proved that mining activities
have taken place in this area, at least, since Roman age (Iglesias, 1995).
Since 1856 until 2003 mineral deposits were continuously exploited.
Mining operations have extracted > 60 Mt grading 8.7% Zn and 1% Pb,
with relatively high concentrations of Cd in sphalerites (600 mg/kg)
(Velasco et al., 2003). Consequently, two manufacturing factories (IA1
and IA3) were installed next to the estuary (Fig. 1). Moreover, in 1935
the local chloralkali industry (see IA2 in Fig. 1) implemented the
electrolysis of brine using a Hg cell and, in late 1960s, the introduction
of a new technology that substantially reduced the Hg inputs to the
estuary (Toca, 1997). These industries are currently permitted to dis-
charge wastewaters that may contain low levels of Cd, Pb, Cu, Zn, and/
or Hg through integrated environmental permits granted by the Gov-
ernment of Cantabria (Smano et al., 2016).
Regarding the sediment sampling, 12 sediment PVC cores (50 cm
long and 4.5 cm diameter) were collected from 7 subtidal (CS1 to CS7)
and 5 intertidal (CI1 to CI5) estuarine areas in April 2015 (Fig. 1). First,
all PVC cores were pre-washed using 5% nitric acid and Milli-Q deio-
nized water and dried using hot air. At each sampling site, PVC cores
were taken using a KC Kajak Sediment Core sampler Model 13.030. A
professional scuba diver conducted the sampling of subtidal cores. The
geographical locations of the sampling stations were marked using a
J.F. Brcena et al.
Leica GS10 hand-held GPS. Compaction during sampling was con-
sidered to be negligible. Immediately after collection, sediment cores
were sealed by using rubber bungs at each end of the tube and covered
using plastic bags. Next, the intact sediment cores were transferred to
an icebox and carried to the laboratory. Upon arrival at the laboratory,
the cores were frozen at 20 C in order to avoid sample degradation.
2.2. Laboratory analytical methods
Samples from the cores were extracted at xed depths, namely: 1, 2,
3, 5, 7.5, 10, 15, 20, and 30 cm from the core surface. These samples
were obtained cutting a slice of 1 cm height in every one of the pre-
viously mentioned depths with a ceramic knife while the core sediment
was still frozen. Subsequently, the samples were oven dried at 50 C and
loosed with an agate mortar. Due to sediment aects all the spatial
distribution of metals in estuaries, we have performed a size normal-
ization by wet sieving (< 63 m), using MilliQ water and a nylon mesh
(Forstner and Wittmann, 1979; Klamer et al., 1990). As pointed out by
Birch et al. (2015), this procedure is rapid and inexpensive and reduces
the diluent associated with the coarse fraction (< 63 m) of the sedi-
ment. Thus, size normalization avoids the necessity of choosing valid
normalizing elements (e. g. Al, Fe, Co) and provides a metric (con-
centration), which is easily translated into enrichment.
The samples were used to determine the percentage of ne material,
the organic matter content, and the following metal concentrations
(units in mg/kg): Chromium (Cr), Nickel (Ni), Copper (Cu), Zinc (Zn),
Cadmium (Cd), Mercury (Hg) and Lead (Pb). Metal samples were di-
gested with aqua regia for 2 h at 95 C and analysed using the method
EPA 6020 A (EPA, 1998). The assurance procedures of the standard
quality of analysis included the analysis of blanks within each batch,
tests with certied reference material standards, and triplicate samples
of each batch to ensure the reproducibility of the results. Quality cri-
teria were 10 in reproducibility and 90110% in accuracy.
2.3. Methodology to assess the evolution and recovery of heavy metal
pollution in estuarine sediments
In this work, we present a method to assess the evolution and re-
covery of heavy metal pollution in estuarine sediments in three steps: 1)
Hierarchical cluster analyses (Section 2.3.1); 2) Past history and present
situation of heavy metal pollution (Section 2.3.2); and 3) Future per-
spectives of heavy metal pollution (Section 2.3.3). Fig. 2 shows an
outline of the proposed methodology.
2.3.1. Hierarchical cluster analyses
Firstly, the analytical results data (units in mg/kg) were subjected to
hierarchical cluster analyses to identify groups of substances with si-
milar chemical behaviour and/or locations presenting a similar evolu-
tion of heavy metal pollution. The identication of location clusters was
conducted using Non-metric Multi-Dimensional Scaling (MDS), and the
identication of substance clusters using Spearman correlation rank (rs)
and Hierarchical Agglomerative Clustering (HCA) with the squared
Euclidean distance metric and complete linkage as the amalgamation
rule.
2.3.2. Past history and present situation of heavy metal pollution
The right interpretation of geochemical data, such as heavy metals
concentrations in sediments, usually requires the knowledge of re-
ference values or background concentrations to determine the number
of times current sediment concentrations are elevated above pristine
levels because expected values for one location may be extremely rare
in another place. However, core data should be interpreted with caution
because subsurface sediments may be aected by bioturbation (Luoma
and Phillips, 1988; Geyh and Schleicher, 1990) and post-depositional
mobilization (Ridgway and Price, 1987; Benoit and Hemond, 1991).
Therefore, core sites should be a low-energy region of deposition with
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Marine Pollution Bulletin 124 (2017) 421434
no observable bioturbation and chemical remobilization to obtain valid
background concentrations (Birch, 2017).
Background concentrations are established by examining down-core
metals data. Concentrations are background where metals data stabi-
lized at depth. Similar methods have been used successfully to assess
pre-anthropogenic levels in estuaries from many regions of the world
(Zwolsman et al., 1993; Deely and Fergusson, 1994; Taylor et al., 2004;
Gillis and Birch, 2006; Olmos and Birch, 2008; Diaz-Asencio et al.,
2009; Birch et al., 2012; Birch et al., 2015).
For this reason, several indices and factors have been proposed and
used in previous works to contextualize the heavy metal information (Li
et al., 2000; Birch et al., 2001; Viguri et al., 2007; Alyazichi et al.,
2016). In this method, we suggested using the geoaccumulation index
(Igeo) proposed by Mller (1969) and calculated with Eq. (1). The Igeo is
a widely used pollution index, which takes into account the possible
variations of the background data due to lithological variations. Thus,
Igeo determines and denes the metal contamination in sediments by
comparing current concentrations with pre-industrial levels.
CHM
Igeo = log2
1.5 Cbackground (1)
where CHM is the heavy metal concentration; Cbackground is the geo-
chemical background concentration of the metal. The constant 1.5 al-
lows for natural uctuations in the content of a given substance in the
environment and very small anthropogenic inuences (Kumar and
Edward, 2009).
The Igeo is an example of a single element assessment, while mul-
tiple-substance and/or location techniques have the advantage of
identifying and assessing a complex suite of sources (Birch et al., 2015).
Due to the non-dimensionality of the Igeo, in the present methodology,
we suggest averaging its values by substance and then by location to
obtain a global index (multiple-substance/location).
Therefore, the Igeo was computed for every depth core and all sub-
stances and, subsequently, we obtained two new indices: a multiple-
substance index called the averaged geoaccumulation index ( Igeoi ) of
each i-heavy metal; and a multiple-substance/location called the global
geoaccumulation index ( Igeo ) by clustered location using the Eq. (2).
The proposed indices Igeoi and Igeo represents the increasing or de-
creasing of heavy metal pollution for one and all substances in the
clustered locations, respectively.
n
Igeoi i = 1 n m Igeoi j
m
Igeo = =
n n
j=1 j=1 (2)
j
where Igeoi is the geoaccumulation index for the i-heavy metal at the j-
station, m is the number of considered heavy metals (substances), and n
is the number of survey stations. The pollution levels for the inter-
pretation of the Igeo are given in Table 1 (Mller, 1981).
2.3.3. Future perspectives of heavy metal pollution
In this subsection, the recovery forecast of heavy metal pollution in
estuarine sediments was performed using the averaged geoaccumula-
tion index of the i-heavy metal ( Igeoi ), the estuarine accumulation rates,
and polynomial regressions by clustered locations. For this type of
chronological investigation, it is important to demonstrate that no
erosion has taken place at the site of sampling otherwise accumulation
rates for metals will be erroneous. To perform this task, we used two
parameters that control this process: (1) the critical shear stress for
erosion (e, kg/ms2), and (2) the bed shear stress (, kg/ms2). If e >
then no erosion has taken place at the core site, and if e < then
erosion has taken place at the core site.
Once it is demonstrated that no erosion has taken place at the site
where the accumulation rate was calculated, rstly, polynomial ts of
the Igeoi were conducted as a function of depth. Secondly, we trans-
formed the depth-tted polynomials into a time-tted polynomials by
d Igeoi
multiplying the variation of Igeoi respect to the depth ( ), i.e. the
ddepth
J.F. Brcena et al. Marine Pollution Bulletin 124 (2017) 421434

Fig. 2. Schematic view of the proposed methodology to estimate the spatial and temporal recovery of heavy metal pollution in estuarine sediments.

Table 1 3. Results
Geoaccumulation index (Igeo) and pollution level (Mller, 1981).
3.1. Analytical data: metals in sediment cores of the Suances Estuary
Class Value Pollution level

0 Igeo < 0 Unpolluted The results of the analytical determinations in the estuarine sedi-
1 0 Igeo < 1 Unpolluted to moderately polluted ments (cores) are presented in Figs. 3 and 4 for the subtidal (CS1CS7)
2 1 Igeo < 2 Moderately polluted
and intertidal (CI1CI5) locations, respectively. The total number of
3 2 Igeo < 3 Moderately to heavily polluted
4 3 Igeo < 4 Heavily polluted measurements was the metal concentration in 12 cores (x-axes in Figs. 3
5 4 Igeo < 5 Heavily to extremely polluted and 4) with 9 core-slice depths (1, 2, 3, 5, 7.5, 10, 15, 20, 30 cm; y-axes
6 Igeo 5 Extremely polluted in Figs. 3 and 4) for 7 metals (Cr, Ni, Cu, Zn, Cd, Hg, Pb; Panels a) to g)
of Figs. 3 and 4), i.e., 756 analytical data (units in mg/kg).
For the raw results of the analytical determinations, readers are
depth-recovery rate by the accumulation rates in order to obtain the referred to Table A.1 (supplementary information). This table shows the
dI geoi
variation of Igeoi respect to the time ( ). From this variation, the core name, the core-slice depth, the percentage of solids > 63 m, the
dt
future value of Igeoi can be calculated as a function of the surcial value percentage of organic matter, and the heavy metal concentrations
of Igeoi using the Eq. (3): (units in mg/kg).
From a rst analysis, Cr displayed concentrations lower than
dIgeo i 20 mg/kg in the upper layers (< 10 cm) of the subtidal cores (Fig. 3a),
Igeo future i = Igeo surface i + t i
dt (3) concentrations between 20 and 50 mg/kg in the lower layers
(> 10 cm) of the subtidal cores (Fig. 3a), and concentrations from 10 to
where Igeo future i is the averaged geoaccumulation index of the i-heavy higher than 50 mg/kg (e.g. 95 mg/kg in CI4) in all the intertidal cores
metal for the future, Igeo surface i is the averaged geoaccumulation index (Fig. 4a). Likewise, Ni concentrations (Figs. 3b and 4b) of the upper
i dIgeo layers were mainly lower than 20 mg/kg and, for the deepest layers,
of the i-heavy metal for the surface, is the variation of Igeo i respect
dt
to the time (time-recovery rate), and ti is the required time of the i- concentrations were between 20 and 50 mg/kg. Cu concentrations
heavy metal to reach a future value of Igeo. (Figs. 3c and 4c) were, in general, lower than 30 mg/kg, although a
Now, we could prognosticate the required time to reach any en- dierence between the subtidal and intertidal cores was detected. The
vironmental threshold for each i-heavy metal, if heavy metal pollutant subtidal cores (Fig. 3c) showed concentrations at the surface lower than
loads will not vary and the recovery will progress under unforced and 20 mg/kg and from 20 to higher than 50 mg/kg at the deeper layers
natural conditions. Therefore, we transformed the Eq. (3) to solve the (e.g. 104 mg/kg in CS4), whereas the intertidal cores (Fig. 4c) pre-
required time ( ti) as indicated in the Eq. (4): sented a more constant prole of concentrations between 20 and
50 mg/kg. It was noticeable the Zn (Figs. 3d and 4d), at all the stations
THRESHOLD
( Igeoi Igeoi
SURFACE
) and depths except for CI2, presented concentrations between 3000 and
t i = 7500 mg/kg, being extremely high at the lowest levels (e.g. 68,000 mg/
d Igeo
dt i (4) kg at 30 cm in CS2 or 34,000 mg/kg at 30 cm in CS7). Similarly, Cd
(Figs. 3e and 4e) displayed concentrations between 6 and 15 mg/kg in
where Igeoi THRESHOLDand Igeoi SURFACE
are the values of Igeoi for any general, and concentrations at 30 cm depth higher than 15 mg/kg like
pollutant threshold (e.g. Igeo = 0) and for the surface, respectively. 62 mg/kg in CS7. In the case of Pb (Figs. 3g and 4g), concentrations
were from 170 to higher than 850 mg/kg for all the cores, with the
exception of CS1 and CS6, being especially high at depths below 10 cm

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Fig. 3. Distribution of the metals in the estuarine cores (mg/kg) at the subtidal locations (CS1 to CS7): a) Cr; b) Ni; c) Cu; d) Zn; e) Cd; f) Hg; g) Pb.

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Fig. 4. Distribution of the metals in the estuarine cores (mg/kg) at the intertidal locations (CI1 to CI5): a) Cr; b) Ni; c) Cu; d) Zn; e) Cd; f) Hg; g) Pb.

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Fig. 5. (a) Graphical representation of the non-metric Multi-Dimensional Scaling analysis for the core sediments (n = 108, 7 variables). (b) Graphical representation of the non-metric
Multi-Dimensional Scaling analysis for the 4 upper layers (depth 5 cm) of the core sediments (n = 48, 7 variables). Note that intertidal samples are represented by grey triangles and
subtidal samples by black triangles. (c) Dendrogram of the hierarchical cluster analysis for heavy metals (n = 108, 7 variables).

in subtidal stations (e.g. 11,924 mg/kg at 30 cm in CS2 or 5424 mg/kg
at 30 cm in CS7). A similar behaviour was found for Hg (Figs. 3f and
4f), although the magnitude of its concentrations were much lower,
ranging between 0 and 5 mg/kg, and lower than 2 mg/kg at the upper
levels.
Finally, it was noteworthy the results of the intertidal station CI5
(Fig. 4) showed the highest concentrations of any metal. Cr, Ni, and Cu
presented 95, 98, and 71 mg/kg at the surface, respectively. Zn con-
centrations were in the same range than other stations, although this
core displayed a more constant prole of concentrations higher than
6000 mg/kg. Cd concentrations were for the entire core higher than
15 mg/kg. Lastly, Hg and Pb presented similar concentrations to other
stations, but CI5 displayed much higher values when comparing to
other cores at all layers.
3.2. Application to the Suances Estuary of the proposed methodology
might be a better indicator of the present situation in order to detect
dierent spatial patterns of heavy metal pollution. Consequently, a
second MDS, with only the samples of the layers above 5 cm (n = 48, 7
variables), was performed (Fig. 5b). This analysis clearly dierentiated
two clusters: the supercial subtidal and intertidal samples.
The second step was conducting a rs (Table 2) and a HCA (Fig. 5c) in
order to detect groups of substances. The rs and HCA used all the
measured samples and variables (n = 108, 7 variables).
The Spearman correlation matrix (Table 2) evidenced that Zn is
highly related (rs > 0.9) to Pb and Cd. A close relation between Zn and
Pb with Cu also exists (rs > 0.8). Ni is highly related (rs > 0.9) to Cr.
Hg only shows a moderate correlation (rs > 0.6) with Cu. These re-
lationships can be easily noticed in the dendrogram of the HCA
(Fig. 5c). According to these results, the behaviour of heavy metals was
segregate in three groups of substances: (1) Cr and Ni; (2) Hg; and (3)

Table 2
3.2.1. Hierarchical cluster analyses Spearman correlation matrix for the concentrations of heavy metals (n = 108, 7 vari-
Firstly, a MDS for all the cores and depths was carried out (see ables).
Fig. 5a) to nd locations presenting a similar evolution of heavy metal
pollution (n = 108, 7 variables). This analysis showed three separate Cr Ni Cu Zn Cd Hg Pb
groups: a cluster of subtidal samples (grey triangles); another cluster of Cr 1.00
intertidal samples (black triangles); and a third one with both type of Ni 0.93 1.00
samples (grey and black triangles). A detailed analysis of the latter Cu 0.44 0.60 1.00
group revealed that the samples corresponding to those of the deepest Zn 0.26 0.43 0.82 1.00
Cd 0.36 0.57 0.79 0.91 1.00
layers, presenting the highest metals concentrations for all the stations
Hg 0.30 0.38 0.61 0.50 0.49 1.00
and indicating the largest heavy metal loads of the system were coming Pb 0.21 0.39 0.80 0.96 0.85 0.42 1.00
from the past activities (industrial and mining). Thus, supercial layers

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J.F. Brcena et al. Marine Pollution Bulletin 124 (2017) 421434

Fig. 6. Geoaccumulation index (Igeo) for the studied heavy metals in the subtidal sediment cores (CS1 to CS7). a) Cr; b) Ni; c) Cu; d) Zn; e) Cd; f) Hg; g) Pb.

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Fig. 7. Geoaccumulation index (Igeo) for the studied heavy metals in the intertidal sediment cores (CI1 to CI5). a) Cr; b) Ni; c) Cu; d) Zn; e) Cd; f) Hg; g) Pb.

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J.F. Brcena et al.
Cu, Zn, Cd and Pb.
3.2.2. Past history and present situation of heavy metal pollution
In the present investigation, we used to establish background con-
centrations the normalized data of the sedimentary core sampled down
at CI5 to a depth of 8 m by Irabien et al. (2008) in the SE. This site is a
low-energy region of deposition with no observable (~ 20 cm) bio-
turbation and chemical remobilization. Background metal concentra-
tions (units in mg/kg) were determined by calculating the concentra-
tion of metals displaying consistently low values towards the base of the
core, being: 6.7 for Cr, 9.7 for Ni, 4.9 for Cu, 80.6 for Zn, 2.0 for Cd, 0.1
for Hg, and 15.6 for Pb.
Taking into account the results of the step 1, the step 2 was sepa-
rately carried out for the subtidal (CS1 to CS7) and intertidal (CI1 to
CI5) locations. Firstly, we computed the geoaccumulation index for
every core at each depth and all substances using Eq. (1) and inter-
preted its values with the classes provided by Table 1. Figs. 6 and 7
show the Igeo for the studied heavy metals in the subtidal and intertidal
sediment cores, respectively.
As displayed in Fig. 6, the pollution of subtidal sediments can be
segregated in the three groups of substances (see Section 3.2): (1) Cr
and Ni; (2) Hg; and (3) Cu, Zn, Cd and Pb. Moreover, this pollution can
be also separated as a function of the depth cores (see Section 3.2) in
two groups: (I) upper layers (< 10 cm); and (II) lower layers
( 10 cm).
Following this clustering, (1) the pollution level of Cr and Ni (Fig. 5a
and b) was mainly unpolluted (Igeo < 0) in the upper layers (I), and
moderately polluted (1 Igeo < 2) in the lower layers (II). (2) The
pollution level of Hg (Fig. 5f) was mainly unpolluted (Igeo < 0) in the
upper layers (I), and moderately polluted (1 Igeo < 2) in the lower
layers (II). (3) Cu, Zn, Cd and Pb displayed the highest degree of heavy
metal pollution in the subtidal sediments, ranging the pollution levels
of Cu and Cd (Fig. 5c and e) between unpolluted to heavily polluted
(0 Igeo < 4) in the upper layers (I), and between moderately to ex-
tremely polluted (1 Igeo < 5) in the lower layers (II). For Zn and Pb
(Fig. 5d and g), the pattern of pollution level was very like Cu and Cd,
although the values of Igeo were even higher, ranging the pollution le-
vels of Zn and Pb between heavily to extremely polluted (3 Igeo < 5)
in the upper layers (I), and being extremely polluted (Igeo 5) in the
lower layers (II).
In the case of the intertidal sediments (Fig. 7), the pollution of in-
tertidal sediments can be segregated in the three groups of substances
(see Section 3.2): (1) Cr and Ni; (2) Hg; and (3) Cu, Zn, Cd and Pb.
Following this clustering, (1) the pollution level of Cr and Ni (Fig. 6a
and b) presented a gradient from unpolluted to moderately polluted at
CI1 (0 Igeo < 1) to heavily polluted at CI5 (3 Igeo < 4). (2) Hg
(Fig. 6f) showed a broad range of pollution level from unpolluted
(Igeo < 0) to extremely polluted (Igeo 5). (3) The proles of Cu, Zn,
Cd and Pb displayed a pattern very similar to the previous groups,
varying the pollution levels of Cu and Cd (Fig. 6c and e) between un-
polluted to heavily polluted (0 Igeo < 5). For Zn and Pb (Fig. 6d and
g), the values of Igeo were higher than the values of Cu and Cd, ranging
their pollution levels between moderately to extremely polluted
(2 Igeo 5). Moreover, the results of CI5 showed the highest pollu-
tion levels of any metal except for Hg at CI4.
Finally, we calculated the Igeoi and Igeo using the Eq. (2) and in-
terpreted its values with Table 1. As an example, Fig. 8 displays the
obtained values of Igeo (global values for metal combined), indicating a
global picture of the past history and present situation of the heavy
metal pollution in the sediments of the SE.
On the one hand, the subtidal sediments (black dots in Fig. 8a)
showed a decrease of the heavy metal pollution from the bottom/past
(heavily polluted) to the surface/present (moderate polluted). On the
other hand, the intertidal sediments (grey dots in Fig. 8b) displayed an
increase of the heavy metal pollution from the bottom/past (moderate
polluted) until the core depth of 10 cm (moderate to heavily polluted)
430
Marine Pollution Bulletin 124 (2017) 421434
Fig. 8. Global geoaccumulation index (dots) and polynomial ts (solid lines) as a function
of the core depths: a) Subtidal locations (black colour); b) Intertidal locations (grey and
blue colour). Note that displayed data are the global values for metal combined. (For
interpretation of the references to colour in this gure legend, the reader is referred to the
web version of this article.)
and, from this layer to the surface/present, a slight decrease of the
heavy metal pollution without changes in the pollution level (see blue-
edged grey dots). Therefore, this depth-evolution presented a maximum
at 12 cm approximately (dashed blue line in Fig. 8b) related to the nal
washing processes of the Reocn mine (see Fig. 1).
3.2.3. Future perspectives of heavy metal pollution
Analogously to the step 2, the step 3 of the methodology was also
carried out for the subtidal (CS1 to CS7) and intertidal (CI1 to CI5)
locations. Firstly, polynomial ts of the Igeoi were conducted as a
function of depth. Secondly, we transformed the depth-tted poly-
nomials into time-tted polynomials using the accumulation rate cal-
culated by Irabien et al. (2008) from the sedimentary core sampled
down at CI5 in the SE, being its magnitude of 1.7 0.11 cm/year for
the 00.5 m depth interval.
To demonstrate that no erosion has taken place at CI5 in the SE, we
used the estuarine average value of the critical shear stress for erosion
(e) obtained from eld data by Smano et al. (2014), being 0.097 kg/
ms2, and the 3D hydrodynamic model calibrated by Brcena et al.
(2016) to compute the magnitude of the bed shear stress () during one-
year simulation. Fig. 9 shows the timeseries of (a) river ow and (b)
astronomical tide used as boundary conditions; and (c) the evolution of
during the one-year simulation at CI5. Note that the selected period
adequately represents the seasonal wet-dry periods of the river ow and
the alternating neap-spring cycles of the tide (Brcena et al., 2016).
Therefore, any hydrodynamic variable computed from this model, such
as bed shear stress, can be considered as representative at any specic
site. Summarizing, CI5 is optimum to obtain the accumulation rate
because it is a low-energy region of deposition with no erosion taking
place (e > ). Accordingly, the length of the cores (30 cm) comprised
a period of about 17.6 1.02 years, since 19971998 to 2015.
For instance, we linearized the evolution of the Igeo for the subtidal
2
d Igeo
cores (solid black line in Fig. 8a), obtaining a R = 0.9172, with
ddepth
0.0886 cm 1, and 0.1506 0.0097 year 1. Regarding the in-
geo d I
dt
tertidal sediment cores (Fig. 8b), the best polynomial t was a second
order curve, obtaining a R2 = 0.9681 (solid grey line in Fig. 8b).
Considering the mentioned accumulation rate, the maximum occurred
approximately in 2008. From this maximum, we linearized the
J.F. Brcena et al. Marine Pollution Bulletin 124 (2017) 421434

Fig. 9. Timeseries of (a) river ow and (b) astronomical tide used as boundary conditions; and (c) the evolution of the bed shear stress (grey line) during the one-year simulation at CI5
and the estuarine average value of the critical shear stress for erosion (black line) obtained from eld data by Smano et al. (2014).

evolution of the
Igeo (solid blue line in Fig. 8b), obtaining a As shown in Table 4, the intertidal sediments required more time

d Igeo than the subtidal sediments to reach any pollution level for all metals
0.0339 cm 1,
2 d Igeo
R = 0.9292, with and
ddepth dt
because the recovery rates were smaller and the starting pollution
0.0576 0.0037 year 1.
d
Igeoi surface for each i- levels were higher. In terms of global pollution, the intertidal and
Table 3 shows the obtained values of and Igeoi
ddepth subtidal sediments of the SE will require 43.13 2.80 and
heavy metal and for the average of all substances (global), namely the 8.59 0.56 years to be unpolluted (Igeo < 0), respectively. In terms

d Igeo
and Igeo surface . Note that the depth-recovery rates (slopes) were of single-metal pollution, the subtidal sediments were already un-
ddepth
considered negatives since the Igeo was decreasing with time, indicating polluted for Cr and Ni. The other metals displayed a decreasing trend of
the sediment depuration. On the one hand, the depth-recovery rate in the required time to be unpolluted in the following order Zn >
the intertidal sediments presented a decreasing trend in the following Pb > Hg > Cu > Cd. Moreover, the required time to be unpolluted
order Hg > Cu > Cr > Pb > Ni > Zn > Cd; and, in the subtidal in the intertidal sediments showed a decreasing trend as follows
sediments, as follows Pb > Hg > Cd > Zn > Cu > Ni > Cr. On Zn > Cd > Pb > Hg > Cu > Cr > Ni (Table 4).
the other hand, the metal pollution at the surface in the intertidal se-
diments presented a decreasing trend in the following order Zn > 4. Discussion
Pb > Hg > Cd > Cu > Cr > Ni; and, in the subtidal sediments, as
follows Zn > Pb > Hg > Cu > Cd > Cr > Ni. 4.1. Analytical data: metals in sediment cores of the Suances Estuary
Lastly, Table 4 summarizes the prognosticated time ( t in years) to
reach every class of Igeo (see in Table 1) for the seven metals and the The metal concentrations observed in the sediment cores were in
global pollution at both locations by means of the Eq. (4). line with previous works performed in the SE, being extremely high for
Zn, Pb, and Cd and very high for Hg and Cu. For instance, Smano et al.

Table 3
d Igeoi

Depth-recovery rate of i-heavy metal ( ), and averaged geoaccumulation index of i-heavy metal ( Igeoi ) at the surface, for the intertidal and subtidal locations.
ddepth

Location Index Cr Ni Cu Zn Cd Hg Pb Global

Intertidal
d Igeoi 0.0377 0.0266 0.0403 0.0113 0.0075 0.0541 0.0283 0.0339
ddepth
Igeoi
surface 1.650 0.744 1.916 4.945 2.007 2.637 4.010 2.558

Subtidal
d Igeoi 0.0512 0.0548 0.0883 0.0987 0.1046 0.1055 0.1169 0.0886
ddepth

Igeoi
surface 0.147 0.746 0.637 4.089 0.473 1.498 3.248 1.293

431
J.F. Brcena et al. Marine Pollution Bulletin 124 (2017) 421434

Table 4
Prognosticated time to recover the heavy metal pollution of the Suances Estuary's sediments based on the pollution levels set for Igeo.

Location Metal t (years)

Igeo < 0 Igeo < 1 Igeo < 2 Igeo < 3 Igeo < 4

Intertidal Cr 25.75 1.67 10.14 0.66 Reached Reached Reached

Ni 16.46 1.07 Reached Reached Reached Reached
Cu 27.97 1.82 13.38 0.87 Reached Reached Reached
Zn 257.42 16.73 205.36 13.34 153.31 9.96 101.25 6.58 49.19 3.20
Cd 157.41 10.23 78.97 5.13 0.54 0.04 Reached Reached
Hg 28.68 1.86 17.80 1.16 6.93 0.45 Reached Reached
Pb 83.35 5.42 62.56 4.07 41.78 2.71 20.99 1.36 0.20 0.01
Global 43.13 2.80 25.78 1.67 8.43 0.55 Reached Reached
Subtidal Cr Reached Reached Reached Reached Reached
Ni Reached Reached Reached Reached Reached
Cu 4.25 0.28 Reached Reached Reached Reached
Zn 24.37 1.58 18.41 1.20 12.45 0.81 6.49 0.42 0.53 0.03
Cd 2.66 0.17 Reached Reached Reached Reached
Hg 8.35 0.54 2.78 0.18 Reached Reached Reached
Pb 16.34 1.06 11.31 0.74 6.28 0.41 1.25 0.08 Reached
Global 8.59 0.56 1.95 0.13 Reached Reached Reached

(2014) reported high concentrations of heavy metals in surface waters,
Coz et al. (2007) in surface sediments, and Irabien et al. (2008) in core
sediments. Therefore, the estuarine sediments might be a major deposit
of Zn, Pb, and Cd and, to a lesser extent, of Hg and Cu, because of the
intensive anthropogenic activity during the last century. This deposit
might supply a secondary pollution due to geophysical (i.e., oods,
dredging) and/or geochemical eects (diusive processes derived from
the concentration gradient between water and sediments).
Concentrations of these metals were also in line with those found in
other estuarine systems highly impacted by mining and/or industrial
activities, such as the Sydney Estuary (Birch, 2017), and the Derwent
Estuary (Jones et al., 2003) in Australia; the New Bedford Harbor
(Cantwell et al., 2008) in USA; the Gironde Estuary (Masson et al.,
2006) in France; the Makupa Creek (Muohi et al., 2003) in Africa; the
Victoria Harbor (Wang et al., 2013) in Hong Kong; the Jinzhou Bay (Li
et al., 2012) in China; the Cochin Estuary (Jose et al., 2011) in India or
the Tinto-Odiel Estuary (Vicente-Martorell et al., 2009), and the Bilbao
Estuary (Rodriguez-Iruretagoiena et al., 2016) in Spain. Thus, these
type of estuaries could be used as suitable locations to test the proposed
methodology.
4.2. Application to the Suances Estuary of the proposed methodology
4.2.1. Hierarchical cluster analyses
As shown in Fig. 5, two well-dened groups appeared in the sedi-
ments separated by location: the subtidal and intertidal samples. This
dierentiated behaviour might be explained from the hydrodynamic
and transport conditions of the stations (Brcena et al., 2012b, 2016,
2017), as those of the main channel (subtidal) were more homogeneous
than those of the tidal ats (intertidal), which depend on more factors
such as drying and wetting periods, river oods, presence of dikes, and/
or bioturbation.
Metals were segregate in three groups of substances: (1) Cr and Ni;
(2) Hg; and (3) Cu, Zn, Cd and Pb (see Fig. 5 and Table 2). The seg-
regation of Cr and Ni might suggest that their sources were coming from
outside the estuary as concentrations were signicantly lower than the
others metals (CI5 was an exception). Zn, Pb, and Cd were grouped
together since they shared a common source: the mineral deposits of the
Reocn mine. Although Cu was grouped with these three metals, the
distances were bigger because there was another source in the wa-
tershed: the industrial manufacturing (IA1 and IA3). Finally, Hg pre-
sented a completely dierent behaviour as its source was the chloralkali
plant (IA2).
4.2.2. Past history and present situation of heavy metal pollution
The geoaccumulation index (Igeo) and the proposed averaged ( Igeoi )
and global ( Igeo ) geoaccumulation indices (see in Fig. 2), used to il-
lustrate the evolution of heavy metal pollution (since 19971998 to
2015), pointed out the deeper the sediments are, the more polluted.
This is especially right for the subtidal stations due to the main metal
inputs to the estuary were coming from wastewater discharges (aquatic
matrix). Moreover, CI5 showed the highest pollution levels of any
metal. This pattern might be caused by the addition of a diusive source
in the area (see in Fig. 1): the Cucha quarry (Fernndez-Mendiola et al.,
2015).
The other pollution patterns might be explained by three changes in
the main sources feeding the SE: (1) the closure on 31 March 2003 of
the Reocn mine due to the exhaustion of the mineral reserves and,
subsequently, the end of washing discharges from this mine in 2008
(Fernndez et al., 2009); (2) the Spanish chloralkali producers signed a
voluntary contract to reduce drastically Hg emissions between 2005
and 2011 (Irabien et al., 2008); and (3) a signicant decrease in metal
inputs, reected in integrated environmental permits (Bello Bugallo
et al., 2013), due to the combined approach adopted by the European
Union legislation in the framework laid down by 2000/60/EC (WFD),
2008/1/EC (IPPCD), and 2013/39/EU (EQSD) Directives. In the SE
since 2006, the three industrial areas (see in Fig. 1) are holding an
integrated environmental permit to discharge wastewaters that may
contain low levels of Cd, Pb, Cu, Zn, and/or Hg (Smano et al., 2016).
4.2.3. Future perspectives of heavy metal pollution
The complete recovery of intertidal sediments (unpolluted) pre-
sented a decreasing trend in the following order
Zn > Cd > Pb > Hg > Cu > Cr > Ni; and, in the subtidal sedi-
ments, as follows Zn > Pb > Hg > Cu > Cd > Cr and Ni.
In this study, we assumed the accumulation rate at CI5 as uniform
for the whole estuary (1.7 0.11 cm/year). However, this rate might
be estimated using 210Pb dating techniques (Robbins and Edgington,
1975; Appleby and Oleld, 1978; Bruns and Hass, 1999; Appleby, 2001;
Boer et al., 2006) in each of the sample locations. Thus, accumulation
rates will be spatially dependent and the forecast will be more accurate.
As we mentioned, it is important to demonstrate that no erosion has
taken place at the site of sampling, otherwise accumulation rates and
prognosticated times to recovery will be erroneous. Thus, we calculated
the percentage of time surpassing the critical shear stress for erosion at
each core site during the one-year simulation (Table 5).
As shown in Table 5, erosion has not taken place at any intertidal
site (e > during all the year), conrming the validity of these lo-
cations to apply the proposed methodology. In the case of subtidal sites,

432
J.F. Brcena et al.
Table 5
Percentage of time surpassing the critical shear stress for erosion at each core site of the Suances Estuary during the one-year simulation.
CI1 CI2
Time (%) 99.98 100
CS1 CS2 CS3
Time (%) 69.03 83.87 72.61
the values of are between 30% (CS1) and 5% (CS7) of the time above
the e, presenting a behaviour highly linked to the forcing (see Fig. 9).
Accordingly, erosion has taken place at subtidal locations with dierent
behaviours: (1) CS1CS3 sites are being eroded by the tide, especially
during spring tides, and following the same neap-spring cyclic pattern;
(2) CS5CS7 sites are only being eroded by the river oods and fol-
lowing the dry and wet periods; (3) erosion is generated, at CS4 site, by
the tide and the river oods, presenting a mixed pattern. Due to these
erosion patterns, the prognosticated times to recovery the SE sediments
at the subtidal locations should be interpreted with caution, especially
at CS1CS4 sites.
Finally, the calculation was performed considering only the values
of Igeoi
surface
because the exchange processes occur at the surface (active
layer of sediments), derived from the concentration gradient between
the interstitial water between the solid particles of sediment and the
bottom of the water column (Smano et al., 2016).
5. Summary and conclusions
A methodology to assess the historical evolution of heavy metal
pollution in estuarine sediments and to predict the recovery time to
reach a determined pollutant threshold, after the cessation of impacts
from anthropogenic sources, by proposing and using sediment quality
indices and polynomial regressions (see in Fig. 2), was developed and
applied to the SE. Specically, we quantied the horizontal and vertical
distribution of heavy metals in the sediment cores, and investigated
whether the beginning and ending of anthropogenic activities, and/or
the sediment location have inuenced the heavy metal pollution in
estuarine sediments.
In the SE, mining and industrial activities as well as the cessation of
mining and the reduction of industrial loads have left their distinct
landmark on the geochemical records (sediment cores). This evolution
of heavy metal pollution (since 19971998 to 2015) pointed out the
deeper the sediments, the more polluted, indicating a recovery of heavy
metal pollution at the upper layers (depuration processes) due to the
closure in 2003 and ending of washing discharges in 2008 from the
Reocn mine, and, to a lesser extent, the reduction of metal con-
centrations discharged by the three industrial areas in 2006 due to the
integrated environmental permits granted by the Government of
Cantabria.
On the one hand, a detailed analysis by location revealed that the
subtidal sediments at the upper layers were less polluted than the in-
tertidal sediments and, consequently, the prognosticated time to re-
covery was smaller. On the other hand, a detailed analysis by substance
revealed that the most hazardous metal in the intertidal sediments was
Zn (Heavily to extremely polluted) > Pb (Heavily polluted) > Hg
(Moderately to heavily polluted) > Cu (Moderately polluted) > Cd
(Moderately polluted) > Cr (Moderately polluted) > Ni (Unpolluted
to moderately polluted). In terms of global pollution, the intertidal and
subtidal sediments of the SE will require 43.13 2.80 and
8.59 0.56 years to be unpolluted, respectively.
The proposed methodology might increase the awareness of citizens
and regulators in areas where heavy metal pollution is likely to be
hazardous inside an estuary and help researchers, technicians and/or
433
Marine Pollution Bulletin 124 (2017) 421434
CI3 CI4 CI5 Global
100 99.95 100 99.98
CS4 CS5 CS6 CS7 Global
81.44 98.48 91.95 95.67 84.72
regulators to manage them more eciently. Finally, results will ulti-
mately lead to focus sustainable management objectives and policy
decision-making in the water quality eld by recognizing the main
sources of pollution, the denition of priority areas for recovery, the
development of environmental permits, and/or the optimization of se-
diment monitoring designs.
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.marpolbul.2017.07.070.
Acknowledgements
Dedicated to the Memory of Juan Jos Poo Noriega. Mr. Inigo
Claramunt was supported by means of a FPI scholarship of the Spanish
Government (BES-2013-064619). The work described in this paper is
part of a research project nanced by the VI National Plan (20082012)
for Research in Science & Technological Innovation of the Spanish
Government (VERTIZE CTM2012-32538).
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