Marine Pollution Bulletin 184 (2022) 114100

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Marine Pollution Bulletin

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

Baseline

Historical mercury contamination in a major Latin American industrial and

port complex: The case of the Santos estuary, Southeastern Brazil
José Lourenço Friedmann Angeli *, Juliê Rosemberg Sartoretto , Bianca Sung Mi Kim ,
Paulo Alves de Lima Ferreira , Beatriz Benedetti , Michel Michaelovitch de Mahiques ,
Rubens Cesar Lopes Figueira
Instituto Oceanográfico – Universidade de São Paulo (IOUSP), Pça. do Oceanográfico. 191, Butantã, São Paulo 05508-120, Brazil

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

Keywords: The present study determined total mercury (Hg) in four 210Pb dated sediment cores to assess the historical
Mercury contamination anthropogenic Hg accumulation in the Santos estuary, Southeastern Brazil. Background levels were identified
Historical evolution using the deepest sections of the cores, corresponding to pre-industrial ages. Mercury distribution in the sediment
Sediment cores
cores (0.02–2.64 mg kg− 1) presented a large spatial and temporal variation. Contamination is highest in the
Santos estuary
upper estuary and indicates that the industrial hub, especially a chlor-alkali plant is the primary source of Hg. A
contaminant trap effect is observed in this area associated with high fine sediment accumulation and Hg fluxes.
The contamination pattern indicates that the regions not affected by direct inputs are influenced by reworking,
resuspension, and transport of contaminated sediments by tidal flows. The Hg enrichment in the upper layers of
the sediment cores demonstrates that the environmental actions fulfilled in the 1980s were insufficient to control
Hg pollution in the Santos estuary.

Sediments are considered a global sink for Hg and play an important
role in its geochemical cycle (Zhang et al., 2015). Mercury (Hg) and
methylmercury (MeHg) accumulation in coastal and estuarine sedi­
ments represent a significant threat to the local environment and human
population (Haris et al., 2017). More than 2800 tons of mercury is
predicted to be carried by rivers yearly, although only around 380 tons
are transported offshore. The remainder is trapped in coastal deposi­
tional environments, such as estuaries (UNEP, 2013). These are semi-
enclosed coastal bodies of water that form a transition zone between
marine and terrestrial environmental systems and, receive a large
amount of fine sediments from both marine and freshwater sources
(Gaulier et al., 2021; Azhikodan and Yokoyama, 2021). They are char­
acterized by strong physicochemical gradients such as, temperature,
salinity, flow velocity as well as, the often-associated sedimentary
changes (Elliott and McLusky, 2002). Given their location, connections
and resources, estuaries have been historically subjected to intense
human occupation, driven by urban and industrial needs (Lonsdale
et al., 2022).
The Santos estuary, located on the Southeastern Brazilian coast, is a
subtropical estuary bordered by mangroves (CETESB (Companhia de
tecnologia de saneamento ambiental), 2001) and surrounded by a
densely populated area that includes the most important petrochemical
and steel complex in Brazil (Cubatão Industrial Complex) and the largest
commercial harbour in Latin America (Martins et al., 2011), the Port of
Santos. The estuarine system is regarded as slightly stratified with a
salinity variation controlled both by semidiurnal tidal cycle (Harari and
Camargo, 2003) and the discharge of tens of small rivers originated in
the Serra do Mar coastal mountain chain (Mahiques et al., 2016), with
Precambrian metamorphic rocks of granitic composition being the
source of sediments to the system (Perrota et al., 2005). Historically, the
Cubatão Industrial Complex and the port of Santos activities have
released a large number of pollutants. Additionally, domestic sewage,
garbage dumps and landfills from a population of over 1.200.000 settled
in the cities of Santos and São Vicente are potential sources of pollutants
(Souza et al., 2018). Several authors have shown considerable levels of
organic (Martins et al., 2010; Martins et al., 2011; Cesar et al., 2014) and
inorganic (Luiz-Silva et al., 2008; Buruaem et al., 2013; Kim et al., 2016;
Kim et al., 2019; Angeli et al., 2021) contaminants in the Santos estuary.
However, studies addressing Hg contamination are still scarce (CETESB
(Companhia de tecnologia de saneamento ambiental), 2001; Hortellani
et al., 2005; Siqueira et al., 2005; Buruaem et al., 2013; Perina et al.,
2018), especially those concerning the history of Hg inputs during the

* Corresponding author.
E-mail address: louangeli@usp.br (J.L.F. Angeli).

https://doi.org/10.1016/j.marpolbul.2022.114100
Received 17 May 2022; Received in revised form 29 August 2022; Accepted 30 August 2022
Available online 22 September 2022
0025-326X/© 2022 Elsevier Ltd. All rights reserved.
J.L.F. Angeli et al.
past century.
This study aims to establish background levels, identify temporal
trends, and assess Hg contamination in sediment cores under the hy­
pothesis that the acceleration of urbanization and industrialization
during the mid-twentieth century was the primary reason of Hg
contamination in the region. Finally, addressing these issues, and aiming
the conservation of marine resources, are essential aspects of the United
Nations Sustainable Development Goals (SDGs).
Sediment cores were sampled, in April 2012, from four locations in
the studied region (Fig. 1), specifically: in the Santos estuary, near the
Port of Santos (S1); downstream the Cubatão Industrial Complex (S2); in
the São Vicente estuary, nearby a solid waste dump (S3); also in the São
Vicente estuary, next to mangrove areas (S4). Sediment cores were
collected with a gravity core sampler. The sediment cores were frac­
tionated into 2-cm-thick slices and freeze-dried. A previous study of the
historical evolution of trace element contamination was published
(Angeli et al., 2021).
Grain size analysis was conducted through wet sieving in a 0.063 mm
mesh sieve, in order to quantify the fine fraction (clay + silt; <0.063
mm). This technique was chosen since metal concentrations increase
with decreasing grain size of the material, due to surface area and host
minerals changes (Loring and Rantala, 1992). The results were previ­
ously described in Angeli et al. (2021) Total organic carbon (TOC) was
determined in decarbonated subsamples in Costech C–N an Elemental
Analyzer.
Metal extraction (Al, Fe, Sc, and V) was performed in bulk samples
following SW 846 US EPA 3050B (USEPA, 1996), in which the silicate
structure is not dissolved. An adapted version of method SW 846 US EPA
7471 A (USEPA, 1998) was used for Hg analysis. The selected metals
were determined using inductively coupled plasma optical emission
spectroscopy (ICP-OES, Varian, model 710ES), with a coupled vapor
generated accessory (VGA) for Hg analysis. Quality control was assessed
by subjecting a reference material ERM – Estuarine Sediment CC5 80 n◦
0369 (European Reference Materials) (n = 7) to the same analytical
method. The method presented a relative standard deviation of 7 % and
a recovery of 97 %. In addition, all of the samples presented values
Fig. 1. Sampling core locations (S1, S2, S3, S4) along the Santos estuary.
2
Marine Pollution Bulletin 184 (2022) 114100
above the detection limit of the method (DL = 0.006 mg kg− 1, m = 0.6 g;
v = 45 mL).
Mass accumulation rates (MAR) were calculated based on the excess
210
Pb (210Pbxs) activity profiles obtained for the studied cores by Angeli
et al. (2021). The mass accumulation rates is obtained from the formula:
[ ]
1 I (A)tot − I (A)z
φ(z) =
λ (A)z
where, φ is the mass accumulation rate at depth z; λ is the constant decay
for 210Pb (0.0311 yr− 1); I (A)tot is the total inventory; I (A)z is the in­
ventory from the top until depth z and; (A)z is the 210Pbxs activity at
depth z.
Mercury fluxes were calculated by multiplying the Hg concentrations
by the mass accumulation rate (derived from the 210Pb dating method)
according to Cochran et al. (1998) with the formula:
Fi = Si[Hg]
where Fi = mercury flux at i interval (μg g− 2 cm − 2 yr− 1), Si = the
accumulation rate derived from 210Pb method (g cm− 2 yr− 1) for the i
interval and Hg = Hg concentration (μg g− 1).
The degree and trends of contamination were evaluated through the
calculation of the Enrichment factor (EF) (Zoller et al., 1974). The EF is
calculated according to the following formula:
( M)
X sample
EF = ( M)
X background
where M is the concentration of Hg and X is the concentration of the
normalizing element. By convention, if 0.5 ≤ EF ≤ 1.5, the trace element
is provided as a weathering product from crustal rocks; meanwhile, an
EF > 1.5 indicates an anthropogenic contribution (Zhang and Liu,
2002).
Pre-anthropogenic contaminant levels (also known as background)
must be assessed to measure human induced changes. The data must be
normalized (either size or elemental normalization) to remove the
J.L.F. Angeli et al. Marine Pollution Bulletin 184 (2022) 114100

confounding effect of variable grain size (Birch et al., 2020). Early
studies assessed background levels using materials such as world
average shale (Turekian and Wedepohl, 1961). However these values do
not take into account regional catchment variations, or mineral and
chemical composition moreover, they do not represent local background
levels (Birch, 2017). In our case, background levels (BLs) were obtained
by using the average Hg levels of the three deepest samples from the
bottom of each core (Tables S1, S2, S3 and S4). Considering the chro­
nology (Angeli et al., 2021), these samples represent pre-anthropogenic
conditions. Moreover, the normalization was achieved using Sc as a
normalizing element. This element was selected due to its lithogenic
nature and conservative behavior with a strong association with the
fine-grained sediment fraction (UNEP, 1995).
The Hg concentrations along with Al, Fe, Sc, V and TOC are listed in
Table 1. Average mud content was highest in core S1 and S2, while the
lowest average was found in core S4. The spatial variation of grain size
distribution reflects the hydrodynamics of the environment. The domi­
nance of the mud fraction in cores S1 and S2 indicates low energy set­
tings, whereas lower mud levels in S3 and S4 reflects higher energy
environments. Mean Hg concentrations were higher in core S1 followed
by core S2, S3 and S4.
Pearson correlation matrix (Table S5) shows significant positive
correlation between the mud fraction and the particle-size proxy ele­
ments Al, Fe, V and Sc meanwhile, Hg showed, in general, no significant
correlation, indicating different depositional patterns for Hg and these
metals. Total organic carbon (TOC) can influence Hg distribution and
speciation in the sediment providing biding sites in sediment surface
(Chakraborty et al., 2015). Significant positive correlation between total
Hg and TOC is widely reported due to their strong affinity (Machado
et al., 2016; Xiao et al., 2017; Liu et al., 2017; Yu et al., 2021). However
other studies have observed no correlation, especially in polluted coastal
areas (Kehrig et al., 2003; Wu et al., 2013; Yu et al., 2021). The signif­
icant positive correlations between Hg and TOC in sediment cores S3
and S4 indicates a geochemical affinity between these two variables in
relatively preserved environments, meanwhile, the negative correlation
between Hg and TOC in cores S1 and S2 suggests possible local Hg
sources in these regions of the estuarine system.
The Hg concentration profiles for each sediment core are shown in
Fig. 2. Sediment core S1 showed an average concentration of 0.10 mg
kg− 1, showing a clear peak in the late 1980s, followed by a sharp
decrease in the uppermost layers of the core. The concentrations of Hg in
S2 ranged from 0.05 to 0.12 mg kg− 1 from the base of the core until the
early 1990s. Then they showed an abrupt increase, reaching up to 2.64
mg kg− 1 around the early 2000s, followed by a decrease until recent
times. Numerical models show a residual circulation from the Santos
channel into the estuarine system, resulting in a net landward transport
of particles by tidal currents in the upper estuary (Damasio et al., 2020).
Therefore, tidal currents promote an advective transport of the con­
taminants adsorbed onto these particles to the upper estuary, where
lower dynamics favor their deposition (Angeli et al., 2021).
Mercury is a particle reactive element, thus in the absence of local
sources, areas with lower sedimentation rates usually have lower Hg
levels in the sediment. This behavior is the case for cores S3 and S4, at
São Vicente, which showed the lowest concentrations for the region,
ranging from 0.02 to 0.18 mg kg− 1 and from 0.02 to 0.08 mg kg− 1,
respectively. The concentration of Hg in core S3 showed a steady
behavior until the early 2000s, when a sharp increase was observed in
the uppermost layers, whereas no clear trend was observed for core S4.
The Hg fluxes were calculated using MAR and Hg concentration to
understand the influence of sediment deposition on the Hg contamina­
tion over the years (Fig. 3). Fluxes of Hg varied from 0.001 to 0.26 mg
cm− 2 yr− 1 in S1. A gradual increase is observed from the beginning of
the 1900s until the early 1970s. A decrease follows a peak in 1980s until
the early 2000s. The S1 flux profile resembles its concentration profile,
however, instead of decreasing until the uppermost layers, it shows a
final increase until recent times. This increase is probably related to the
higher sediment deposition in recent times (Angeli et al., 2021) rather
than direct mercury inputs to the area. The Hg fluxes in S2 varied from
0.01 to 5.16 mg cm− 2 yr− 1. The temporal pattern of Hg flux followed the
concentration profile, with a clear peak in the early 2000s.
In the São Vicente estuary, mercury fluxes varied between 0.01 and
0.08 mg cm− 2 yr− 1 in the core S3. The Hg flux shows a slight increase
around the 1970s and a sharp increase, reaching its maximum in the
early 2000s. The Hg fluxes ranged from 0.02 and 0.05 mg cm− 2 yr− 1 for

Table 1
Descriptive statistics of the geochemical parameters. Mud content (%), total organic carbon (TOC) (%) and concentrations of Al, Fe, V, Sc and Hg (mg kg− 1).
Mud (%) TOC Al Fe V Sc Hg

S1
Min 26,10 0,71 9037,72 11,460,00 13,11 1,73 0,02
Max 98,90 3,48 42,139,10 33,569,60 35,64 6,30 0,56
Mean 76,79 1,61 26,302,57 24,973,06 25,60 4,25 0,09
SD 28,45 0,71 9722,90 7276,74 6,97 1,48 0,13
Background 98,60 1,42 31,980,95 30,708,60 28,61 5,27 0,02

S2
Min 27,46 0,37 20,363,90 22,912,50 29,54 4,09 0,05
Max 94,20 3,30 44,209,70 38,769,10 57,98 7,65 2,64
Mean 73,05 2,08 35,023,03 34,193,80 46,46 6,18 0,34
SD 21,16 0,78 6798,22 5057,53 8,64 1,11 0,62
Background 78,01 1,89 40,974,65 36,920,10 51,30 6,85 0,09

S3
Min 29,20 0,57 16,374,10 15,918,50 20,65 2,37 0,02
Max 66,50 14,15 38,026,10 29,267,80 34,22 4,75 0,18
Mean 44,76 4,03 24,093,46 22,069,93 25,49 3,17 0,05
SD 9,98 4,17 5579,28 4048,27 3,86 0,62 0,05
Background 51,85 1,22 25,357,70 20,616,50 24,13 3,20 0,03

S4
Min 13,24 0,31 5222,53 5077,16 6,51 0,84 0,02
Max 44,28 1,90 15,892,20 14,860,30 16,25 2,18 0,08
Mean 23,44 0,89 9587,04 8982,09 10,08 1,30 0,04
SD 8,23 0,52 2693,39 2675,03 2,59 0,36 0,01
Background 34,38 1,04 11,473,69 12,230,65 12,89 1,69 0,05

3
J.L.F. Angeli et al.
Fig. 2. Vertical profiles of Hg concentration (mg kg− 1) along with TEL (red dotted line) and PEL (black dotted line). (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article.)
2
Fig. 3. Hg fluxes (mg cm−
core S4 with a gradual rise from the early 1960s towards the top,
reaching its maximum around 1998. Without local sources in the São
Vicente estuary, our findings suggest that the concentrations result from
sediment reworking and atmospheric emissions. Global emissions to the
atmosphere were thought to have peaked in the 1970s, then declined for
the next two decades before stabilizing between 1990 and 2005.
Nevertheless, between 2000 and 2005, there were some signs of slight
increases in emissions (UNEP, 2013).
The assessment of Hg concentrations in the Santos estuary sediment
cores showed that samples from the Santos channel (S1), the upper
Marine Pollution Bulletin 184 (2022) 114100
yr− 1) along the sediment cores.
estuary (S2), and the São Vicente channel (S3) exceeded the Hg
threshold effect limit (TEL) of 0.13 mg kg− 1(Buchman, 2008) (Fig. 2).
The concentrations of Hg around the 2000s in the core S2 exceeded the
probable effect level (PEL) of 0.70 mg kg− 1 (Buchman, 2008), above
which adverse effects frequently occur, posing a high ecological risk to
the environment. Hortellani et al. (2005) found that 60 % of the
investigated areas of the Santos estuary presented mercury levels above
0.13 mg kg− 1 and under 0.70 mg kg− 1. Although high levels beneath the
surface may seem harmless, if sediments are disturbed by natural or
anthropogenic processes, Hg may be released into the surrounding
4
J.L.F. Angeli et al. Marine Pollution Bulletin 184 (2022) 114100

aquatic environment. Table 2

Empirical sediment quality guidelines are a useful screening tool to Mercury concentrations in estuarine and coastal sediments in Brazil and around
identify locations and evaluate contaminant's risks (Birch, 2018). the world.
However, from a management standpoint, it is critical to understand Location Hg (mg kg− 1) Reference
how far the system has deviated from its original state. We used the Guaratuba Bay, Southern Brazil 0.005–0.03 Conrad and Sanders,
Enrichment Factor (EF) to measure the human-induced contamination. 2017
An EF of 1.5 times is considered the threshold between the background Laranjeiras Bay, Southern Brazil 0.01–0.02 Conrad and Sanders,
condition and sediment affected by human activity meanwhile, EFs of 2017
Guanabara Bay, Southeastern Brazil 0.1–3.22 Covelli et al., 2012
1.5–3, 3–5, 5–10 and >10 are considered evidence of minimal, moder­
Sepetiba Bay, Southeastern Brazil <0.005–0.29 Gonçalves et al., 2018
ate, considerable and severe modification, respectively (Birch, 2017). Todos os Santos Bay, Northeastern 0.005–3.5 Hatje et al., 2019
All cores showed no enrichment until the early 1950s (Fig. 4). The up­ Brazil
permost layers of the sediment cores S1, S2 and S3 reveal the highest Tapajós River, Brazilian Amazon 0.02–0.15 Lino et al., 2019
EFs, indicating severe contamination. Despite preservation programs Daya Bay, China 0.01–0.09 Zhao et al., 2016
Bohai Sea, China 0.011–0.22 Liu et al., 2019
and remediation actions, carried out by the Environmental Control Terminos Lagoon, Southern Gulf of 0.006–0.138 Ruiz-Fernández et al.,
Agency of the São Paulo State (CETESB (Companhia de tecnologia de Mexico 2019
saneamento ambiental), 2001) improved the environmental quality in Ria de Aveiro, Portugal 0.008–0.258 Martins et al., 2013
the 1980s, the 2000s were characterized by overall deterioration and Augusta Harbour, Sicily, Italy 0.28–680 Romano et al., 2021
Tanglanchuan River, China 0.35–74.6 Song et al., 2018
moderate enrichment for anthropogenic trace metals (Jesus et al., 2020;
Santos estuary, Southeastern Brazil 0.04–1.19 Hortellani et al., 2005
Angeli et al., 2021). On the other hand, core S4 showed no sign of Santos estuary, Southeastern Brazil 0.02–2.64 This study
enrichment throughout the core. Therefore, this region could still be
considered pristine regarding metal contamination.
Core S2, located at the upper estuary, is the most contaminated by Hg variation of levels found in Guanabara Bay (Southeastern Brazil; Covelli
and indicates the industrial area as the main source of contamination. et al., 2012) and Todos os Santos Bay (Northeastern Brazil; Hatje et al.,
The main possible source of contamination is the chlor-alkali plant 2019), two of the largest and most affected coastal embayments of
located at the Cubatão river. Nonetheless, Hg may derive from this point Brazil. The Hg levels in this study were significantly lower than those in
source as well as other chemical and petrochemical industries and port sediments from Southwest China (Song et al., 2018) and from Augusta
terminals located downstream. Harbour, Italy (Romano et al., 2021), both sites historically affected by
A comparison of the Hg concentrations in the sediments with the former chlor-alkali plants.
results of estuarine and coastal sediments in Brazil and around the world A well-known source of Hg in the upper estuary is a Chlor-Alkali
(Table 2) revealed that they were significantly higher than those from Plant (CAP) that discharges its effluents into the Cubatão River, the
Guaratuba and Laranjeiras Bay, (Southern Brazil; Conrad and Sanders, most polluted river and the primary Hg dispersion agent in the studied
2017), from Sepetiba Bay (Southeastern Brazil; Gonçalves et al., 2018), area (Luiz-Silva et al., 2002). Over the years the company accumulated
Tapajós River (Northern Brazil; Lino et al., 2019), Daya Bay and Bohai 3000 tons of waste from these Hg cells. In 1975, the company consumed
Sea (China; Zhao et al., 2016; Liu et al., 2019), Terminos Lagoon 440 g of mercury per ton of chlorine produced. The Hg contaminated
(Mexico; Ruiz-Fernández et al., 2019) and the Ria de Aveiro (Portugal; effluents from this plant have been treated from 1977 onwards (before
Martins et al., 2013). Mercury concentrations were in the same range of they were discharged directly into the Cubatão river after being treated

Fig. 4. Enrichment Factor (EF) of Hg along the sediment cores of the Santos estuary.

5
J.L.F. Angeli et al.
in sedimentation boxes) (Siqueira et al., 2005). Nevertheless, moni­
toring programs conducted by the CETESB indicate the presence of Hg in
its effluents between 1979 and 1999 (CETESB (Companhia de tecnologia
de saneamento ambiental), 2001). Considering the recent trends,
anthropogenic activities likely continue to influence the Hg cycle in the
Santos estuary.
Over the last years, several environmental studies recognized the
anthropogenic impact of polycyclic aromatic hydrocarbons (PAHs),
linear alkylbenzenes (LABs) and trace metals (mainly Cu, Pb, Zn and Hg)
in sediments of the Santos estuary. It has been possible to identify the
pollution sources based on the location and chronology of pollution. The
primary possible source of Hg is a Chlor-alkali plant located at the upper
estuary, as well as inputs from petrochemical plants located next to the
port area.
The main findings of this research are: (1) the presence of a highly
contaminated sector in the upper estuary next to the Cubatão Industrial
Complex; (2) a contaminant trap effect in this sector associated with
increased sediment accumulation and Hg fluxes; (3) patterns of
contamination in the regions not affected by direct inputs are caused by
reworking, resuspension, and transport of contaminated sediments by
tidal flows.
This study shows that the Santos estuary sediment cores record
valuable environmental information. It has been shown that despite the
efforts for contamination control set in the 1980s, the Hg levels
continued to rise in the following years, demonstrating that the policies
were, to some degree, ineffective due to intense economic activities in
the region (port of Santos and Cubatão Industrial Complex). A recom­
mendation arising from this research is an increase in monitoring pro­
grams and government environmental regulations.
Funding
This study was partially supported by the Coordenação de Aperfei­
çoamento de Pessoal de Nível Superior – Brasil (CAPES) – Finance Code
001 and from the São Paulo Science Foundation (FAPESP, grant 2009/
01211-0; 2011/50581-4 and 2017/08987-0), the Oceanographic Insti­
tute of the University of São Paulo (IOUSP), and the Laboratory of
Inorganic Marine Chemistry (LaQiMar).
Data availability
The authors declare that the data supporting the findings of this
study are available within the article or its supplementary information.
CRediT authorship contribution statement
José Lourenço Friedmann Angeli: Conceptualization, Investiga­
tion, Writing – review & editing. Juliê Rosemberg Sartoretto: Inves­
tigation. Bianca Sung Mi Kim: Formal analysis. Paulo Alves de Lima
Ferreira: Methodology, Software. Beatriz Benedetti: Methodology.
Michel Michaelovitch de Mahiques: Writing – review & editing.
Rubens Cesar Lopes Figueira: Resources, Supervision.
Declaration of competing interest
The authors declare that they have no conflict of interest.
Data availability
Data will be made available on request.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.marpolbul.2022.114100.
6
Marine Pollution Bulletin 184 (2022) 114100
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