Environ Earth Sci (2017) 76:548
DOI 10.1007/s12665-017-6886-0
ORIGINAL ARTICLE
Persistence and mobility of metals in an estuarine environment
25 years after closure of a lead smelter, Bahia State, Brazil
Gerlange Soares da Silva1 • Thomas Vincent Gloaguen1 • Carolina Fonseca Couto1
Paula Núbia Soares Dalto Motta1
Received: 27 February 2017 / Accepted: 5 August 2017 / Published online: 14 August 2017
Ó Springer-Verlag GmbH Germany 2017
Abstract A part of the Subaé River watershed in Bahia,
Brazil, is highly contaminated with toxic metals, due to a
former 33-year lead (Pb)-smelting activity that produced
approximately 500,000 tons of slag, primarily rich in Pb,
Zn, and Cd. This study aimed at determining the remaining
concentrations of trace metals, 25 years after the end of the
metallurgic activities, in the continental sediments of the
Subaé River upstream and downstream of the Pb smelter
and in the estuarine mangrove sediments, which are 4 km
away from the smelter. The river sediments were collected
at five sites in the fluvial continental channel and at four
sites in its estuary (channel and flood plain). Physico-
chemical analyses were performed, and pseudo-total Pb,
Zn, Cd, and Cu were extracted by aqua regia. The impact
of salinization of the fluvial environment by the rise in sea
level was studied by batch tests in fresh and saline waters.
Concentrations of Pb, Zn, and Cd were above the minimum
alert threshold (35, 123, and 0.60 mg kg-1, respectively) at
minimum two of the three sites downstream of the smelter
(continental area). In the estuary, Cd exceeded the alert
thresholds at five of the eight sites (0.68 mg kg-1),
whereas few contamination of others metals was detected.
The geoaccumulation index provided comparable conclu-
sions. Conversely, the enrichment factors were found to be
more applicable in such a variable environment: another
source of pollution in the estuary was detected, with similar
enrichment of Cu, Pb, and Zn, possibly the industrial
facilities in the region. We calculated the enrichment of
metals in the flood plain, compared it to the main channel
& Thomas Vincent Gloaguen
tgloaguen@gmail.com
1
Federal University of Reconcavo of Bahia, Rua Rui Barbosa,
710 - Centro, Cruz das Almas, BA 44380-000, Brazil
•
of the estuary and concluded that Cd accumulates in floo-
ded mangroves, while Pb remains in channel sediments.
The batch tests proved that salinization of the river can
release an average of 6, 20, and 60% of Pb, Zn, and Cd,
respectively.
Keywords Lead pollution  Enrichment factor  Estuarine
sediments  Desorption
Introduction
The environmental impacts of lead (Pb) and zinc (Zn) mine
tailings have intensified because of their accumulation
during the past few decades with majors concerns regard-
ing the degradation of aquatic environments (Jacob and
Otte 2004; Søndergaard et al. 2011; Cidu et al. 2012; Miler
and Gosar 2012; Omanović et al. 2015). Santo Amaro da
Purification, Bahia, is an example of high metal contami-
nation caused by the activities of smelting industry, where
pollutant emissions, generated by the Pb-smelting activity
of the Companhia Brasileira de Chumbo (COBRAC) from
1960 to 1993, left an environmental liability of approxi-
mately 500,000 tons of slag with a high content of metals,
primarily cadmium (Cd), Zn, and Pb. These metals were
stored for decades in the courtyard of the metallurgical
plant (Carvalho et al. 1984b; Anjos 2003; Paoliello and De
Capitani 2007; de Andrade Lima and Bernardez 2011). In
addition to the dispersion of metallic pollutants through
chimney emissions, the high rainfall in the area caused
dispersion of contaminants into the Subaé River by runoff
(Paredes et al. 1995; Anjos 2003; Hatje and Barros 2012)
and overflowing tailing pond waters (Anjos 2003). In these
last 25 years, this generated a major negative impact on
continental and coastal ecosystem, contaminating the soil,
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water, and organisms, thus, in turn, contaminating the
population that lives on agricultural products and consumes
marine fauna (Carvalho et al. 1984a, b, 1985, 1986, 1989;
Silvany-Neto et al. 1989; Zentner and Rondó 2004; Pao-
liello and De Capitani 2007; Arruda-Neto et al. 2009; de
Souza Guerra et al. 2010, 2014, 2015; Niemeyer et al.
2012a, b; Bomfim et al. 2015; Magna et al. 2016). Most of
the above-mentioned studies investigated the health of the
population and frequently found that the metal concentra-
tions in the blood, hair, saliva, and teeth were above the
threshold limit values. It is important to investigate the
environmental impacts of soil and sediment contamination
in relation to diseases and diffuse the contamination. Even
decades after the end of smelting activities, a current dif-
fuse pollution is still expected because high weathering
(tropical rainforest climate) enhances the erosion of Ver-
tisols, which is still highly polluted by metals due to the
extremely low displacement of metals, especially Pb,
within such clay soils. When the soil is eroded, trace metals
reach water bodies and rivers transport the pollutants to the
oceans (Oelkers et al. 2012). Several technical reports and
master’s thesis have been published on the metal concen-
trations in coastal sediments of the Santo Amaro region,
but they have been published in Portuguese language
(Hatje and Barros 2012) and have focused on areas pol-
luted by the petroleum industry or the areas that are too far
from the Subaé estuary (Onofre et al. 2007; Celino et al.
2008; Boaventura et al. 2011). A few studies (Santos et al.
2010; Hatje and Barros 2012; Bomfim et al. 2015) have
been conducted close to the estuary. Hatje and Barros
(2012) and Santos et al. (2010) found significant pollution
within the main channel of the river, whereas Hatje and
Barros (2012) and Bomfim et al. (2015) found that metals,
except Cd, were less concentrated in sediments of man-
groves soils. The concentration of the metals has been
determined in previous studies, but the natural concentra-
tions of the metals have to be established to calculate the
geoaccumulation index (IGEO) and define the real accu-
mulation of metals in the sediment (Loska et al. 1997; Ji
et al. 2008; Hasan et al. 2013; Zahra et al. 2014). However,
in transitional environments, such as an estuary, only these
concentrations are not sufficient to assess pollution; it also
depends on the accumulation of highly variable fine par-
ticles (clays and oxides) present in the estuary and man-
groves that naturally accumulate metals. The enrichment
factor (EF) normalizes with aluminum, differentiating
quartz from the clay mineral aluminosilicates, minimizes
these differences; it distinguishes natural processes, such as
weathering of rocks rich in these elements, from anthro-
pogenic processes, such as the disposal of substances from
industrial or municipal activities (Loska et al. 1997;
Kaushik et al. 2009; Zhang et al. 2009; Hasan et al. 2013;
Antunes et al. 2016).
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Environ Earth Sci (2017) 76:548
In the estuaries system, metals behave according to a
strong physicochemical gradient. The rising sea level due
to global warming can cause salt water intrusion in the
estuarine and fluvial environment of coastal cities, mov-
ing the salinity intrusion points further upstream by sev-
eral kilometers (Li et al. 2015; Yang et al. 2015; Chen
et al. 2016; Ketabchi et al. 2016; NOAA 2017). Consid-
ering that there are already mangroves in the southern
part of the city of Santo Amaro, a significant salinization
of the river sediments around the smelting plant is
expected by 2050.
This study aimed at evaluating the distribution of Pb,
Zn, Cd, and Cu in sediments of the Subaé River, 25 years
after a major contamination by Pb smelter to identify the
effective current level of contamination, to determine the
enrichment in the different fluvial environments, and to
investigate how the increase in salinity due to the rise in
sea levels can mobilize the metals.
Sampling area and methodology
Sampling area
This study was conducted in the Subaé River watershed
from the municipality of Feira de Santana (source) to the
estuary plain in the municipality of Santo Amaro, upstream
and downstream of a primary lead smelter, and in its
estuary in the municipality of the São Francisco do Conde
region (Fig. 1).
The main water source of the Subaé River is the Subaé
lagoon in Feira de Santana, which drains in an area of
655 km2, under a rainy tropical climate with an annual
temperature of 25 °C and a rainfall of 1800 mm/year. The
river covers about 55 km from the source to its estuary in
São Francisco do Conde in the Todos os Santos Bay. The
estuarine system of the river spans to the last 10 km of the
river course with an average flow of 2.71 m3 s-1.
Sampling and analysis
In the continental area, the sediment samples at the stream
bed were collected at a depth of 0–15 cm (three subsam-
ples) with a stainless suction auger. In the estuary area, the
sediment samples were collected at a depth of 0–15 cm
(three subsamples) with a plastic shovel. The samples were
then dried at a temperature of B50 °C, disaggregated,
homogenized, and sieved through a 2-mm mesh.
The granulometry analysis was performed following the
method of Empresa Brasileira de Pesquisa Agropecuária
(2011), according to which the clay was determined by the
pipette method and the sand by sieving. The organic matter
(OM) was determined by the gravimetric method (Empresa
Environ Earth Sci (2017) 76:548
Fig. 1 Location of the sampling sites of river sediments in the Subaé River, Bahia
Brasileira de Pesquisa Agropecuária 2013). In this method,
10 g of the sample, previously dried at 100–105 °C in an
oven for 6 h, is burned and then placed in a muffle furnace
at 550 °C for 3 h. The extraction of the metals was per-
formed by digestion, which was carried out at 140 °C for
2 h in a digester block by a reflux system using 0.75 g of
the sediment directly into the digestion tubes with a mix-
ture of concentrated HCl:HNO3 (3:1).
In order to evaluate the effect of metal mobilization dur-
ing the rise in the sea level, the desorption batch test of the
fresh and saline water was carried out using the continental
river sediments close to the estuary and the proper estuary
sediments. Artificial seawater, made with deionized water
([18 MX cm) and Tropic MarinÒ Sea Salt, diluted 100
times, 10 times, and not diluted (pH = 8,11; [Na?] =
10,598 mg kg-1; [Cl-] = 18,434 mg kg-1; [K?] =
-1 2- -1
371.36 mg kg ; [SO4 ] = 2593.62 mg kg ), was used
as the desorbing solution. An amount of 5 g of sediments was
placed in 50 mL of the solution in a polyethylene tube, in
triplicate, agitated in a rotative agitator for 2 h at 21 °C and
centrifuged at 2000 rpm for 5 min. Then, the solution was
filtrated using pre-washed No. 540 filters and stored at 4 °C.
All analyses were performed in triplicate and each set
consisted of 20 samples. Three blanks and a reference sample
(2709 San Joaquin) were considered to ensure the quality
Page 3 of 12 548
control. The concentrations of Al, Ca, Mg, Fe, Mn, Cd, Pb,
and Cu were determined by using the ICP-OES (pseudo-total
extraction) and flame AAS (batch tests) methods.
The metal concentrations were compared with the ref-
erence values for fresh water and marine sediments
(Buchman 2008). The geoaccumulation index (IGEO; Eq. 1)
and the enrichment factor (EF; Eq. 2) were calculated
using aluminum as a normalizing element for EF (Loska
et al. 1997) and the unaffected sediments as a reference
sediment:
 
½MS
IGEO ¼ log2 ð1Þ
1:5½MR
EF ¼
½MS =½AlS
ð2Þ
½MR =½AlR
where [M] and [Al] are the metal and aluminum concen-
trations, respectively, in the sediment analyzed (S) and in
the reference sediment (R) (in mg kg-1).
Results
The continental river sediments (Table 1) showed high
concentrations of OM at sites 1 (92.5%) and 2 (94.6%).
The high OM content at site 1 is contributed by the remains
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Table 1 Physical and chemical values (major and minor metals) of the Subaé river sediments
pH OM Sand Silt Clay Ca Mg Fe Al Mn Cu Cd Pb Zn
(% g kg-1) (mg kg-1)

Continental river channel

P1 6.40 92.5 20.2 21.3 58.5 196 1173 17,985 2106 48 13.0 0.33 6.4 46.1
P2 5.58 94.6 67.1 22.4 10.5 248 1317 17,592 16,029 288 13.4 0.17 11.0 52.0
P3 3.08 1.1 70.4 20.2 9.5 309 1928 11,028 8727 106 10.7 1.79 429.3 1356.4
P4 3.12 0.8 78.0 17.6 4.5 519 2074 14,347 10,008 144 11.6 0.90 470.2 1597.0
P5 2.85 0.3 89.2 7.9 3.0 170 2538 13,292 10,988 381 9.1 0.38 68.9 306.0
Mean value 4.21 37.8 65.0 17.9 17.2 288 1806 14,849 9572 193 11.5 0.71 197.2 671.5
Estuarine river flood plain
P6fp 5.23 86.6 3.0 81.1 15.9 338 8622 29,656 41,034 139 39.8 0.91 31.3 164.7
P7fp 6.50 86.1 0.5 28.8 70.7 508 10,987 36,810 54,512 292 40.2 0.53 37.2 207.1
P8fp 5.10 95.4 51.5 23.1 25.4 116 2346 8337 385 54 8.4 0.29 5.8 37.3
P9fp 4.96 85.3 7.6 26.1 66.4 562 11,695 34,237 2057 267 40.1 0.87 28.7 173.3
Mean value 5.45 88.3 15.7 39.8 44.6 381 8412 27,260 24,497 188 32.1 0.65 25.8 145.6
Estuarine river channel
P6c 4.55 95.8 5.8 88.3 5.9 187 3214 11,383 13,467 65 12.3 0.40 8.8 58.2
P7c 5.93 85.2 34.6 7.8 57.6 499 11,351 37,029 53,022 246 39.8 0.89 30.9 196.9
P8c 4.09 90.1 48.9 21.2 30.0 253 5216 17,358 876 106 19.9 0.93 11.9 82.4
P9c 6.75 88.7 36.5 26.2 37.4 1922 10,289 24,607 1277 209 28.2 0.61 13.9 105.4
Mean value 5.33 89.9 31.5 35.9 32.7 715 7518 22,594 17,161 156 25.0 0.71 16.4 111.8
BTS sediments: mean minimal* – – – – – – – – – 36 4.2 0.0 3.8 8.8
BTS sediments: mean maximal* – – – – – – – – – 861 51.6 1.7 62.3 113.7
* Geometric mean of minimal and maximal values from 36 studied reported by Hatje and Barros (2012)

of the undecomposed plants in the lagoon and the
wastewater from the city of Feira de Santana (Cruz et al.
2013). On the other hand, the high OM content at site 2 is
contributed by the vegetation on the river bank. The
presence of branches and trunks into the river used to form
small dams causing water to flow slowly also led to organic
matter deposition (de Aguiar et al. 2012). In the estuary
area, the OM contents were also high at all sites (Table 1),
as previously reported by Bomfim et al. (2015) and Borges
et al. (2007); this could be attributed to mangrove
ecosystems (high production of organic matter with low
export due to the river-tidal movements).
There is a predominance of the sand fraction over the
fine fractions (silt and clay) in the continental area
(Table 1), with a percentage above 67% at almost all sites
except for site 1 that showed about 20% of the coarser
material because of the presence of lentic water. The
increasing trend of the sand content of the river course
(from site 1 to site 5) can be attributed to the presence of
desert-derived sandstones of the Brotas Group (Late Cre-
taceous) from mid to low watershed.
At the estuary, a predominance of the fine particles
(silt ? clay) at each site was also observed by Bomfim
et al. (2015). In mangrove areas, the presence of fine sed-
iment is common due to the low river hydraulic force in the
coastal plains and the opposite force of oceanic tides, but a
clear difference can be observed between the river bed and
the river merge, where the former is generally more sandy
(de Aguiar et al. 2012).
Major metals followed the same order of magnitude
(Fe [ Al [ Mg [ Ca [ Mn, and for the mean values see
Table 1) in both the continental and estuarine areas. Mg
and Al concentrations were higher in the estuary area with
the average values being four (Mg) and two (Al) times
higher than those in the continental area. The higher con-
tent of the clay-sized particles in this environment concords
with the higher concentration of Fe and Al, as clays and
especially oxides, are naturally rich in these elements. The
calc-alkaline metals, Ca and Mg, probably originate from
carbonate lenses in shales (Santo Amaro group, Barremian
age) and certainly from the marine influence. The metal
oxides enriched in this environment are the primary carri-
ers of geochemical trace metals (Johnson 1986; Wen et al.
2008), making the environment more vulnerable to metal
contaminants transported by rivers, primarily associated
with the particulate matter (Oelkers et al. 2012).

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The concentration of the trace metal Cd is the lowest at
all sites, ranging from 0.17 to 1.79 mg kg-1 (Table 1),
which is still above the minimum warning limit (TEL;
Table 2) at sites 3 and 4 (continental area and fresh water).
Lead shows the highest concentrations among the ‘‘trace’’
metals, ranging from 5.81 to 470.23 mg kg-1, which are
above Threshold Effects Levels values (TEL—NOAA) in
the sediments from the sites 3, 4, and 5, and above Severe
Effect Level values (SEL—NOAA) in the sediments from
the sites 3 and 4, indicating severe effects, especially, on
the biota. These high values largely exceed the mean
maximal value in the sediments of the Todos os Santos Bay
(in which the Subaé River flows) calculated from the 31
maximal values reported by Hatje and Barros (2012);
however, the values are consistent with those found by in
the Subaé River channel (Hatje and Barros 2012). Zinc also
showed the same behavior, with the concentrations going
above 1300 mg kg-1 (sites 3 and 4). These values were
two fold higher than those reported by Hatje and Barros
(2012) and ten times higher than the mean maximal value.
For copper, all the concentrations in the continental river
sediments are lower than TEL (35.7 mg kg-1).
In estuary sediments, the concentrations of Cu, Pb, and
Zn follow the trend reported for the worldwide mangroves
(MacFarlane et al. 2007). The Cd concentration ranges
from 0.29 to 0.93 mg kg-1, exceeding the minimum
warning value (TEL) at all the four sites (considering
channel and flood plain). Similar results were obtained by
Garcia et al. (2007) in São Francisco do Conde and Madre
de Deus-BA and by Bomfim et al. (2015) who studied the
mangrove soils from proximal areas. This situation clas-
sifies the environment as potentially toxic, because Cd,
being a highly toxic element, poses a serious threat to the
marine organisms by its persistence and accumulative
nature even at low concentrations (Fonseca et al. 2013).
The average concentrations of Pb in estuary sediments
range from 5.81 to 37.24 mg kg-1, which are similar to the
data obtained for mangroves in this area (Onofre et al.
2007; Bomfim et al. 2015). The concentration is below or
slightly higher than TEL, thus the risk of toxicity by Pb in
Table 2 Sediment quality
Fresh water
guide values for trace metals in
fresh and marine water sediment TEL PEL
adopted by NOAA (mg kg-1,
dry basis) Cu 35.7 197
Cd 0.60 3.53
Pb 35 91.3
Zn 123 315
TEL value below which adverse effects are rarely expected; PEL-level of likely effects; SEL-level of
severe effects
a
Average values of seven river sediments samples from 0 to 30 cm depth, within unused forest
Page 5 of 12 548
the estuary can be considered extremely low. Zn shows a
similar behavior, but its concentration is close to PEL at
site 7, indicating that the risk of Zn toxicity is a bit higher
than that by Pb. In addition, the sediments also carry a
potential toxicity conferred by Cu, which also exceeds the
TEL value at the estuary. According to (Hatje et al. 2009),
Cu is enriched in most part of the Todos os Santos Bay due
to the release of wastewater from the oil refinery and others
industries near the city of Salvador. The sediments with a
lower concentration in metals were found at site 8, which
could be explained by its sandy texture, as it contains low
concentrations of Fe, Al, and Mn, which could be ascribed
to less metal containing particles such as oxides and clays
(co-precipitation, adsorption).
Discussion
Contaminants transported by particulates
In the continental area, significant correlations were found
among the concentrations of Fe, Ca, Mg, and the minor
elements such as Cu, Pb, and Cd. The overall correlation
between Pb and Cd (1.0) indicated that they might have the
same anthropogenic source. The inverse correlation
between organic matter and Pb and Cd indicates that the
presence of OM induces the formation of organometallic
complexes with the particulate and dissolved organic
matters (POM and DOM) that are transported by the river.
In estuary sediments (Table 3), the trace metals showed
a different behavior than in the continental sediments with
strong correlations with Al, Fe, and Mn, as previously
reported in the same (Boaventura et al. 2011; Bomfim et al.
2015) or similar environments (Du Laing et al. 2009; Hatje
and Barros 2012; Marchand et al. 2012). These observa-
tions reflect a possibility of co-precipitation of both Fe/Mn
sulfides and oxides during the redox processes in the
mangrove soils and sediments (Tables 4 and 5). A positive
correlation of metals with clay also enhances the impor-
tance of clay-sizes particles (such as clay minerals).
Sea water Reference sediment (site 2)a
SEL TEL PEL
110 18.70 108 14.1
10.00 0.68 4.21 0.14
250 30.24 112 8.68
820 124 271 45.6
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Table 3 Pearson correlation matrix (r) in Subaé river sediments of the continental area
OM Sand Silt Clay Cd Pb Cu Fe Mn Ca Mg Al

OM 1.0
Sand -0.7** 1.0
Silt 0.6* -0.6* 1.0
Clay 0.7** -1.0** 0.4ns 1.0
ns
Cd -0.6* 0.3 0.04ns -0.3ns 1.0
Pb -0.6* 0.2ns 0.2ns -0.3ns 1.0** 1.0
Cu -0.1ns -0.1ns 0.4ns 0.01ns 0.6* 0.6** 1.0
Fe 0.3ns -0.3ns 0.5ns 0.3ns 0.1ns 0.2ns 0.7** 1.0
Mn -0.3ns 0.7** -0.6* -0.7** -0.2ns -0.2ns -0.2ns -0.3ns 1.0
ns ns ns ns
Ca -0.5* 0.3 0.3 -0.4 0.9** 0.9** 0.7** 0.3 -0.2ns 1.0
ns ns ns
Mg -0.9** 0.6** -0.5 -0.6* 0.6* 0.6** 0.5 0.2 0.3ns 0.6* 1.0
Al -0.2ns 0.7** -0.1ns -0.8** 0.0ns 0.1ns 0.1ns -0.01 0.7** 0.2ns 0.3ns 1.0
ns not significant
** Significance level between two variables (p \ 0.01); * significance level between two variables (p \ 0.05)

Table 4 Pearson correlation

OM Sand Silt Clay Cd Pb Cu Fe Mn Ca Mg Al
matrix (r) of metals in Subaé
river sediments of the estuary OM 1.0
area
Sand 0.7* 1.0
Silt 0.1ns -0.6ns 1.0
Clay -0.8** -0.3ns -0.6ns 1.0
ns ns
Cd -0.6* -0.4 0.1 0.3ns 1.0
ns
Pb -0.8** -0.6* -0.1 0.6* 0.7* 1.0
Cu -0.9** -0.6* -0.1ns 0.7* 0.8** 0.9** 1.0
Fe -0.9** -0.5ns -0.2ns 0.8** 0.8** 0.9** 1.0** 1.0
Mn -0.8** -0.4ns -0.4ns 0.9** 0.5ns 0.8** 0.9** 0.9** 1.0
ns ns ns ns ns
Ca -0.5 -0.4 -0.2 0.6* 0.4 0.4 0.6* 0.6* 0.7** 1.0
Mg -0.8** -0.5ns -0.3ns 0.8** 0.7* 0.8** 1.0** 1.0** 1.0** 0.8** 1.0
Al -0.6* -0.5ns 0.1ns 0.4ns 0.4ns 0.8** 0.7* 0.7* 0.4ns -0.2ns 0.4ns 1.0
ns not significant
** Significance level between two variables (p \ 0.01); * significance level between two variables
(p \ 0.05)

Table 5 Contamination level as a function of enrichment factor with a reference environment (Loska et al. 1997; Ji et al.
Enrichment factor 2008; Hasan et al. 2013; Zahra et al. 2014). Site 2 was
considered as a reference, as site 1 is very close to the city
EF \ 2 Deficiently to minimal enrichment
of Feira de Santana. Site 2 is located in a distal unused
2 \ EF \ 5 Moderate enrichment
forest area, its background values are lower than those
5 \ EF \ 20 Significant enrichment
found by Argollo (2001) at the bottom of sediment core in
20 \ EF \ 40 Very high enrichment
the BTS (50 cm deep, dated about 100 years) and close to
EF [ 40 Extremely high enrichment
those reported by (Hatje and Barros 2012). No copper
pollution was detected in the continental area, while the
high IGEO reported for Cd, Pb, and Zn reflects the pollution
Sources of pollution caused by these metals, which might have originated from
the smelting plant. The pollution by Cd covered the entire
Geoaccumulation index (IGEO) is used to quantify the studied area with a large peak indicating its accumulation
accumulation of a metal in an environment by comparing (IGEO [ 3, values of IGEO greater than 2 indicate moderate

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Environ Earth Sci (2017) 76:548
to high contamination). The large distribution of Cd in the
water environment is the result of its high mobility in this
environment, especially in mangrove environment, where
Cd retained by organic matter and labile sulfide is easily
released (Xu et al. 2016). Du Laing et al. (2008, 2009) also
demonstrated the role of salinity in Cd mobilization in the
intertidal sediments. These processes lead to the dilution of
the metal in the estuary and the Todos os Santos Bay by the
oceanic transport. Therefore, the high values of IGEO in the
estuary indicate that there is a constant supply of Cd by the
weathering of Subaé watershed, even 30 years after the end
of metallurgical activities in the basin. This high input is
attributed to the erosion of the remaining polluted soil (this
information only available in master’s thesis in Asevedo
2012 and Peixoto 2013). With regard to lead and zinc, a
pollution peak was evidenced at the sites near the metal-
lurgical plant with high to extremely high accumulations
(IGEO [ 4); unlike cadmium, very low accumulation of Pb
and Zn was detected in the estuary area (IGEO \ 2 indicates
no contamination or moderate contamination), which
confirms the low mobility of these metals and their accu-
mulation near the source (metallurgy).
The values of IGEO are consistent, but there are differ-
ences in the mineralogy and texture between the conti-
nental and estuarine areas, and even between the different
environments of a river (point bar, cut bank, etc.), which
causes some bias in the interpretation. The enrichment
factor, another index that normalizes the aluminum con-
tent, reduces the effect of the variability of the clay content
because Al is present in the kaolinite and montmorillonite
but absent in the quartz that is the main constituent of the
sand fraction. The enrichment factor of these metals varied
from 1 to [100 in the continental area (Table 6) indicating
high contamination by Cd, Pb, and Zn, except for site 2 that
corresponds to our reference sediment. The high enrich-
ment near the metallurgical plant conforms to the IGEO
values. However, IGEO values point to unpolluted sedi-
ments (IGEO \ 0) near the spring, close to the city of Feira
de Santana ([600,000 haba). It can be asserted that the EF
values are more consistent, pointing to significant enrich-
ment (between 5 and 10) induced by industrial and urban
activities.
In the estuary area, the sediments at sites 6 and 7 are not
or minimally enriched. It is important to emphasize that
despite the high concentrations of metal in these two sites,
the low EF values point to the absence of any anthro-
pogenic contribution. This means that the fine sediments
(silt and clay contents are high in these locations) would be
the main contributors of metals. The increase in clay
content resulted in the enrichment of both Al and trace
metals, thus enrichment factors remained low.
While observing the concentrations of metals, lower EF
values were expected at sites 8 and 9 as compared to sites 6
Page 7 of 12 548
and 7, but these two sites had higher EF values, ranging
from 20 to 40, which indicated a very high degree of
anthropogenic contribution. However, the low concentra-
tions of Al because of a more sandy texture indicate that at
sites 8 and 9, these sediments have no minerals that natu-
rally contain or adsorb trace metals; thus, the enrichment
factor revealed that, despite its relatively low absolute
values, these sediments are contaminated by Cd, Pb, and
Cu. The high enrichment of Cu, which was only moderate
near the lead smelter, revealed a secondary source of pol-
lution from the Todos os Santos Bay. It could the oil
refinery of Madre de Deus (Landulfo Alves de Mataripe—
RLAM), 15 km away from the sampled area and/or the
multi-sectoral industrial center of Aratu (SUDIC 2017),
which is 30 km away from the sampled area, composed of
154 companies (chemical, food, metallurgy, furniture,
nonmetallic minerals, plastics, fertilizers, electronics,
beverages, textiles, etc.). In contrast to the continental
region, the estuarine EF values for Pb, Zn, and Cu were
similar, as shown by the ratios EFPb/EFCu and EFZn/EFCu
close to 1. This indicates that, in the estuary, Pb and Zn
pollution probably resulted from these refinery/industrial
facilities, and not from the smelting plant. Argollo (2001)
analyzed sediment core close to the Aratu harbor and
detected a rapid simultaneous increase of Cu, Pb, and Zn
from 1950 until now (some values triplicated). An inves-
tigation, using isotopic analysis to distinguish these sources
of pollution (Ritson et al. 1999; Han et al. 2015; Hu et al.
2015; Chen et al. 2017), needs to be carried out further.
This secondary source also releases cadmium in the clay/
oxide environment as demonstrated by its extremely high
EF value at this site (136, 56).
Mobility and availability of metals
We investigated the transfer of metals between the channel
of the river and the flood plain. The ratio between the metal
concentrations in the two environments (RFP/C) shows an
irregular behavior (Fig. 2a). For example, we see that the
concentration of copper in the flood plain can be 3.2 times
lower than its concentration in the channel (RFP/C = 0.34;
P6) to 2.4 times higher (RFP/C = 2.4; P8). The same
behavior was also seen for the other metals. We could
verify that the metals seem to be concentrated in the
channel at P6 and P9 sites, while they concentrate in the
plain at P8 site. Therefore, in order to eliminate the min-
eralogical variation in such a fluctuating environment, we
calculated the enrichment factor by weighting by the alu-
minum concentration (Eq. 2, but in this case, S is the flood
plain sediment and R is the channel sediment). The results
were much more consistent and homogeneous (Fig. 2b).
We observed a systematic enrichment of the Cd in the
plain, and on the contrary, a depletion of Pb at all the four
123
548 Page 8 of 12 Environ Earth Sci (2017) 76:548

Table 6 Geoaccumulation index and enrichment factor in the Subaé river sediments
IGEO Cu IGEO Cd IGEO Pb IGEO Zn EF Cu EF Cd EF Pb EF Zn EF Pb/EF Cu EF Pb/EF Zn

Continental river channel

P1 -0.60 0.85 -0.98 -0.49 7.92 20.29 6.33 8.66 0.80 0.73
P2 -0.56 -0.15 -0.19 -0.32 1.07 1.33 1.43 1.28 1.33 1.12
P3 -0.89 3.27 5.09 4.38 1.57 26.28 102.24 61.46 65.25 1.66
P4 -0.77 2.28 5.22 4.62 1.48 11.53 97.65 63.10 65.84 1.55
P5 -1.12 1.03 2.45 2.24 1.06 4.41 13.03 11.01 12.28 1.18
Mean value -0.93 2.20 4.25 3.75 1.35 11.01 50.68 34.95 37.50 1.45
Estuarine river flood plain
P6fp 1.01 2.30 1.31 1.34 1.25 2.85 1.58 1.59 1.27 1.00
P7fp 1.02 1.53 1.56 1.67 0.95 1.25 1.42 1.50 1.50 0.95
P8fp -1.23 0.64 -1.12 -0.80 28.00 96.33 31.41 38.40 1.12 0.82
P9fp 1.02 2.23 1.19 1.42 25.02 54.03 29.05 33.33 1.16 0.87
Mean value 0.27 1.47 0.54 0.76 8.72 18.69 10.90 12.43 1.25 0.88
Estuarine river channel
P6c -0.68 1.11 -0.52 -0.16 1.17 3.81 1.36 1.71 1.16 0.79
P7c 1.01 2.27 1.29 1.60 0.96 2.15 1.21 1.47 1.26 0.83
P8c 0.01 2.34 -0.08 0.34 29.10 136.56 28.31 37.21 0.97 0.76
P9c 0.51 1.73 0.14 0.70 28.33 61.35 22.68 32.65 0.80 0.69
Mean value 0.51 2.11 0.45 0.88 9.26 26.21 9.20 12.13 0.99 0.76

sites studied was noted. The mobility of cadmium in such

an aquatic redox environment (Zhao et al. 2013; Xu et al.
(a) 3.5
2016), which facilitates its availability in solution (Du
3.0 Laing et al. 2008), may explain the transfer of the channel
to the flood plain, where it accumulates. Bomfim et al.
metal]FP / [metal]C

2.5
P6 (2015) and Hatje and Barros (2012) also observed a higher
2.0 contamination of Cd in the mangrove soils and sediments.
P7
1.5 P8 On the other hand, the processes of complexation and/or
1.0 P9 sorption on carbonates of Pb (Acosta et al. 2011) may
result in very low concentrations in the seawater that
0.5
invades constantly the mangrove flood plain, thus
0.0 explaining its depletion in this ecosystem. Despite these
Cu Cd Pb Zn
behaviors, Pb accumulation was higher in the organisms,
(b) 2.0 especially mussels (Santos et al. 2013). Regarding Cu and
1.8 Zn, neither enrichment nor depletion in the flood plain was
1.6
Enrichment factor

noted at a significant level.

in flood plain

1.4
P6 The desorption tests of metals in fresh to saline water
1.2
1.0
enriched
P7 revealed a differential behavior among the metals origi-
depleted
0.8 P8 nating from the lead smelter (Fig. 3). As expected, Cd was
0.6 P9
the most available metal, and water salinity enhanced its
0.4 mobility. Chloro-complexation (Du Laing et al. 2008; Zhao
0.2 et al. 2013) and ion exchange (Du Laing et al. 2008) seem
0.0 to be the main mechanisms. Acosta et al. (2011) also
Cu Cd Pb Zn
observed the higher release of Cd, by applying different
Fig. 2 a Increase of concentrations of metals in flood plain sediments marine salts (NaCl, CaCl2, MgCl2, and Na2SO4) at differ-
compared to channel sediments and b enrichment factors in flood ent ionic strengths in polluted sediments. In our batch
plain with Al content as reference—EF = ([metal]FP/[Al]FP)/ testes, the release was higher, as more than half of the
([metal]C/[Al]C)

123
Environ Earth Sci (2017) 76:548 Page 9 of 12 548

samples released about [90% of the total cadmium in a 100

saline environment (seawater). Furthermore, the risk of Cd
biodisponibility was not restricted to this environment, as

[Metal]DESORBED (%)
even in the deionized water, the Cd release was up to 99%.
In the presence of some salts (low salinity), Du Laing et al. Pb
(2008) also detected the release of Cd but at a lower rate. 10 Cd
Thus, the high availability of Cd, observed in our study,
Zn
can be attributed to the osmotic effects of deionized water.
In some cases, the availability of Zn reached 50% and the
saline water was the most efficient extractor, except for P4.
In this highly contaminated sediment (P4), saline water 1
caused a decrease in the desorption of Zn and Cd. This may SW SW 1:10 SW 1:100 H2O
be due to the precipitation of metal salts such as carbonates
Fig. 4 Mean relative desorption values of Cd, Pb, and Zn from the
Subaé River sediments, according to the water salinity. SW sea water
% Cd desorption
100
90
(Acosta et al. 2011). Pb was much less desorbed than Cd
80
70 and Zn, generally less than 10% in fresh water and 20% in
60 saline water, except for P4, where 41% of Pb was desorbed.
50 In all the sediments, the average release of Pb was quite
40
low and exceeded 2% only in seawater, whereas the
30
20 average release of Cd and Zn reached 10 and 30% in all
10 situations (Fig. 4).
0
SW SW 1:10 SW 1:100 H2O

Conclusion
% Pb desorption
100
90 The contamination of Cd and Pb still occurs in the Subaé
80 River environment even 25 years after the closure of a lead
70 smelter in the city of Santo Amaro. The continental sedi-
60
50 ments closer to the smelter still have a high enrichment of
40 Cd, Zn, and Pb (10, 60, and 90 times higher, respectively,
30 than the reference). This can severely affect the biota
20 according to international thresholds. In the estuary area,
10
0 an accumulation of Cd was detected. In a transitional
SW SW 1:10 SW 1:100 H2O environment, such as an estuary, we demonstrated than the
contamination by metals can be determined more precisely
% Zn desorption with the enrichment factor (EF) than the geoaccumulation
100 index (IGEO) because IGEO does not reflect the chemical and
90
80
mineralogical changes in sediments within an environment.
70 In contrast to IGEO, the enrichment factors indicated the
60 contamination of Cu, associated with Pb and Zn, coming
50 from another pollution source, possibly the refinery or
40
30 industrial facilities around the Bay. The enrichment factors
20 also allowed to detect a transfer of Cd from the channel
10 river to the flood plain estuary (mangrove environment),
0 while Pb was found to be retained in the channel sedi-
SW SW 1:10 SW 1:100 H2O
ments. Due to the changes in salinity (e.g., when the sea
P3 P4 P5 level rises), the seawater intrusion could release on average
P6m P7m P8m 6, 20, and 60% of Pb, Zn, and Cd, respectively. Even at a
P9m P6c P7c
minor intrusion, with important influence of the river dis-
Fig. 3 Relative desorption of Cd, Pb, and Zn from the Subaé River charge (diluted seawater), the release could still exceed
sediments, according to the water salinity. SW sea water 10% for Cd and 30% for Zn.

123
548 Page 10 of 12
Acknowledgements This study was supported by the Conselho
Nacional de Desenvolvimento Cientı́fico e Tecnológico, CNPq/Brazil
(Research Funding 480647/2012-7), and a grant from the Coor-
denação de Aperfeiçoamento de Pessoal de Nı́vel Superior, CAPES/
Brazil. We would like to thank Professor Mark Hodson from the
University of York, England, for his support in the analysis of sedi-
ments and salinity tests.
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