See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/320847125

Nickel, vanadium, and lead as indicators of sediment contamination of

marina, refinery, and shipyard areas

Article  in  Environmental Science and Pollution Research · November 2017

DOI: 10.1007/s11356-017-0503-3

CITATIONS READS

3 93

5 authors, including:

Thayane Lucia Pereira Monica Wallner-Kersanach

4 PUBLICATIONS   4 CITATIONS   
Universidade Federal do Rio Grande (FURG)
12 PUBLICATIONS   286 CITATIONS   
SEE PROFILE
SEE PROFILE

Luiza Dy Fonseca Costa Paulo Baisch

Universidade Federal do Rio Grande (FURG) Universidade Federal do Rio Grande (FURG)
19 PUBLICATIONS   55 CITATIONS    50 PUBLICATIONS   405 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

OCORRÊNCIA E CARACTERIZAÇÃO DAS FLORAÇÕES DE Trichodesmium spp. AO LARGO DA PLATAFORMA SUDESTE-SUL DO BRASIL View project

Lagoon in SC, Peri View project

All content following this page was uploaded by Paulo Baisch on 28 November 2017.

The user has requested enhancement of the downloaded file.

Environ Sci Pollut Res
https://doi.org/10.1007/s11356-017-0503-3
RESEARCH ARTICLE
Nickel, vanadium, and lead as indicators of sediment
contamination of marina, refinery, and shipyard areas
Thayane Lúcia Pereira 1 & Mônica Wallner-Kersanach 1 & Luiza Dy Fonseca Costa 1 &
Daniel Pereira Costa 1 & Paulo Roberto Martins Baisch 1
Received: 26 September 2016 / Accepted: 17 October 2017
# Springer-Verlag GmbH Germany 2017
Abstract Metallic elements found in the aquatic environment
may originate in areas where petroleum is refined and vessels
are maintained and repaired. This study aims to assess con-
tamination caused by nickel (Ni), lead (Pb), and vanadium (V)
in sediment of the Lagoa dos Patos estuary (RS, Brazil) and to
evaluate them as indicators of areas under the influence of
petroleum products and antifouling paints. Surface sediments
were collected in summer and in winter in areas of marinas,
shipyards, refinery, and a control station. High Pb and V con-
centrations in shipyards and at the Yacht Club showed that
some organisms may be affected by toxicity. High Pb results
of the index of geoaccumulation (Igeo) were found at the
Yacht Club and shipyards. Al, Ni, and V had similar distribu-
tion in the sediment in both seasons. Ni and V had high rela-
tion in winter at the Yacht Club and at the Santos Shipyard,
thus suggesting that these elements come mainly from petro-
leum products. The same happened to the relations between
Pb and V, as well as Pb and Ni at the Santos Shipyard. These
Responsible editor: Philippe Garrigues
* Thayane Lúcia Pereira
thayanelucia@hotmail.com
Mônica Wallner-Kersanach
monicawallner@furg.br
Luiza Dy Fonseca Costa
luiza_dy@hotmail.com
Daniel Pereira Costa
danielcosta@furg.br
Paulo Roberto Martins Baisch
baisch@mikrus.com.br
1
Instituto de Oceanografia, Universidade Federal do Rio Grande,
Campus Carreiros, Rio Grande, RS 96203-900, Brazil
elements are employed as useful tools as indicators to identify
places with moderate to high localized anthropogenic inputs
of petroleum derivatives and antifouling paints.
Keywords Nickel . Lead . Vanadium . Aluminum .
Sediment . Shipyards . Petroleum products . Antifouling
paints
Introduction
Metal contaminants in coastal and estuarine regions have be-
come a problem on a global scale due to its toxicity and accu-
mulation in the environment. These elements come from nat-
ural inputs and anthropogenic activities, mainly industrial and
port areas in estuaries, and sediment is an important compart-
ment which accumulates these contaminants. Therefore, sed-
iment has been considered an environmental indicator, since it
provides useful spatial and temporal information (Birch
2017).
The presence of shipyards worldwide in many coastal areas
may cause contamination of sediment with petroleum deriva-
tives, antifouling paints, solvents, PAHs, and metals related to
repair and maintenance of vessels (Chiu et al. 2006; Neşer
et al. 2012). Copper and zinc contamination results from
new generation antifouling paints, which contain concentra-
tions in percent of both elements (Costa et al. 2013, 2016), and
vanadium, nickel, and lead are found in petroleum products
due to lubricants and marine diesel oil (Nemr et al. 2006).
Nickel and lead, at lower concentrations (ppm), are also found
in the composition of antifouling paints but the concentration
depends on the paint brand (Costa et al. 2016).
High nickel and vanadium concentrations found in the
composition of petroleum are used for determining its quality
and maturation (Barwise 1990), because of the high

correlation between both elements (Nielsen et al. 2008). Thus,
they were used as environmental contamination markers for
bivalve mollusks (Chiffoleau et al. 2004) and lagoon sedi-
ments (Magallanes-Ordonez et al. 2015). Unlike nickel, even
though vanadium is found in petroleum products, it is not
easily found in other anthropogenic sources. Lead is mainly
found in marine diesel oil (Nemr et al. 2006). Since diesel oil
is an intermediate product in the petroleum refining process, it
may affect the aquatic environment when there is accidental
spill during vessel supply. It may have up to 5.0 ppm lead,
0.5 ppm vanadium, and 1.0 ppm copper (Reyes 2003).
Metals in shipyards have been scarcely reported in the lit-
erature (Chiu et al. 2006; Mokhart et al. 2002; Reddy et al.
2004), but no study has considered vanadium and nickel con-
tamination in these locations. Lead is also important because it
originates from the burning of petroleum derivatives in petro-
chemical industries. Their emissions also have both nickel and
vanadium, a fact that results in positive correlation between
them in the soil around refineries and suggests that these ele-
ments come from the same source (Soldi et al. 1996; Garcia
et al. 2010). Studies of petroleum refineries showed high con-
centrations of residual ash of lead, vanadium, and chrome,
besides residual ash of vanadium and nickel in fuel oil
(Alonso-Hernandez et al. 2011).
Although in the past there were few studies of Ni and V as
contamination markers for bivalve mollusk, lagoon sedi-
ments, and refinery soil, no investigations have focused on
sediment found in shipyards, marine areas, or even in refinery
areas located on the coast. In order to investigate the contam-
ination of Ni, V, and Pb in areas under the influence of petro-
leum derivatives and antifouling paints residues, an estuarine
area was selected as a case study. The development of ship-
yards, refinery, and marina facilities in Rio Grande, a city
located in the southern area of the Patos Lagoon estuary, in
the south of Brazil, and the temporal evolution of metal con-
tamination in the estuary (Wallner-Kersanach et al. 2016)
make it an important location to be investigated. Therefore,
this investigation aims at determining the degree of contami-
nation caused by Ni, Pb, and V concentrations in the sediment
in shipyards, refinery, and marina areas, with inputs of petro-
leum products and antifouling paints. This study should con-
tribute to the possibility of using the relation between these
elements worldwide, since metal contaminants are much more
persistent in sediment than organic compounds.
Material and methods
Study area
The Patos Lagoon, located in the south of Brazil, has an area
of 10,360 km2 and is one of the largest coastal lagoons in the
world. It has been classified as a coastal Bstrangled^ lagoon
Environ Sci Pollut Res
where the wind is the main driving force by comparison with
the tidal regime (Kjerfve 1986). The Lagoa dos Patos estuary
is about 250 km long and 40 km wide on average. It has low
tidal range (mean of 0.47 m), an average depth of 6 m, and a
complex hydrodynamics due to winds and river discharge
(Möller et al. 1996).
The seasonal pattern is characterized by the strong activity
of northeast (NE) winds from September to April and south-
west (SW) winds from May to September. Determining fac-
tors of these wind systems are circulation, salinity, and water
level variations (Möller et al. 1996). The system of NE winds
favors the high input of fresh water and the entrance of sea
water into the estuary (Costa et al. 1988). Strong El Niño
events usually cause an intense fresh water discharge into
the estuary, whereas La Niña events mean a drought period
and high entrance and permanence of seawater in the estuary
(Pasquini et al. 2012).
The hydrographic basin of the Lagoa dos Patos estuary has
been known by intense agricultural, port, and industrial activ-
ities which contribute to the entrance of all kinds of contam-
inants (Niencheski et al. 2002).
Therefore, sediment samples were collected at six locations
in the southern part of the estuary where heavy port and nav-
igation activities are carried out in Rio Grande. In each loca-
tion, three sampling sites were selected in areas with no input
of urban and industrial effluents (Fig. 1).
The Yacht Club, which has been open since 1934, is a
recreational place with a marina area where small vessels are
anchored. Samples were collected inside the inlet, near the
vessel repair area (YC 1) and between the mooring docks
(YC 2 and YC 3). YC 3 site is located close to the exit of
the inlet (Fig. 1a). The most common kind of vessel hull
repaired in this area is made of fiberglass.
The Gustavo Fernandes Filho Shipyard, which has operat-
ed for more than 100 years, is an important place where ves-
sels are also supply with marine diesel oil. Even though this
shipyard has carried out few activities related to vessel main-
tenance, wood, iron and fiberglass hulls have been repaired
there nowadays.
Samples were collected on the slipway where vessels are
moved from the water in order to be repaired (GFS 1), on the
right of the inlet exit (GFS 2) and on the left of the inlet exit at
the pier of the Marine Gas Station (GFS 3) (Fig. 1b).
The Riograndense Refinery has been refining petroleum
since 1937. Samples were collected on the margin of the inlet
(RR 1, RR 2, and RR 3) (Fig. 1c).
The Rio Grande Shipyard is the most recent industrial unit
for activities related to construction of oil platforms in Rio
Grande. Samples were collected in the exit of the estuary in
front of (RGS 1) and behind the shipyard (RGS 2 and RGS 3)
(Fig. 1d). The Santos Shipyard has had heavy activities related
to small and medium vessel repair for more than 20 years; it
has repaired wood, iron, and fiberglass hulls. It is located near
Environ Sci Pollut Res
Fig. 1 Sediment sampling sites in the Lagoa dos Patos estuary: a Yacht Club (YC), b Gustavo Fernandes Shipyard (GFS), c Riograndense Refinery
(RR), d Rio Grande Shipyard (RGS), e Santos Shipyard (SS); control station (CS)
the Pilot Station in Rio Grande and samples were collected at
SS 1, SS 2, and SS 3 sites (Fig. 1e).
A sampling site was selected as the control station, i.e., the
Torotama Island (Fig. 1), because it is far from the city and has
no port activities but small artisanal fishing boats.
Sampling
Samples of surface sediments up to 5 cm deep were collected
in the different sampling sites of the estuary in February
(summer) and in July and in August (winter) 2014.
Sediment samples were collected in triplicate by a stainless
steel Van Veen grab sampler at the three sampling sites of the
six locations in the estuary (Fig. 1), totaling nine samples per
location. Analyses of metals and total organic carbon (TOC)
were carried out in triplicate whereas a sub-sample was ob-
tained at each site for granulometry.
Samples for metals and granulometry were removed with
the help of a plastic spatula in order to collect the material that
was not in direct contact with the grab sampler. These samples
were kept in plastic bags and refrigerated until they were taken
to the laboratory.
Another aliquot of sediment material was collected for
TOC with the help of a stainless steel spatula, kept in glass
flasks previously washed with 20% HCl. Samples were
stored, as described before, and frozen for further analysis.
Physicochemical parameters, such as temperature and sa-
linity (WTW, Model 315i), were analyzed in water, as well as
pH (Mettler, MP 120) and Eh (ORP) (Oakton, Model 79255)
in the sediment.
Although the grain size fraction above 1000 μm was not
considered for the analysis of metals and total organic carbon,
it was taken into account for the determination of the grain size
because of the presence of this fraction in some sampling
stations.
Analytical procedures
Granulometry
The granulometric analysis was carried out in agreement with
the traditional method described by Suguio (1973). Firstly,
samples were oven-dried at 80 °C. Then, 30 g was weighed
and sieved in a set of sieves with defined mesh sizes. The
amount of sediment stored in each sieve was weighed and
the resulting values were used for calculating the percentage
of each grain size.

Total organic carbon
Determination of total organic carbon (TOC) followed the
method described by Zimmermann et al. (1997). Samples
were dried by a lyophilizer (Liotop-model L101) for 72 h.
Afterwards, they were macerated and 1-g dry sediment
from each place was weighed so that decarbonation could
be carried out with concentrated HCl vapor by a desicca-
tor for 24 h in order to remove inorganic carbon that
could be in the sample. Then, samples were kept in an
oven at 60 °C to constant weight. Analyses were carried
out by Perkin Elmer’s 2400 series CHNS/O Elemental
Analyzer.
In order to determine the accuracy of the TOC method, the
analysis of certificated reference materials, both acetanilide
and MESS-1(National Research Council—Canada), was
evaluated. Mean percentage recoveries of acetanilide and
MESS-1(n = 3) were 99.82 and 106.24%, respectively.
Metals
Surface sediments were used in their total granulometric
fractions (< 1000 μm). In order to carry out the analyses
of nickel (Ni), vanadium (V), lead (Pb), and aluminum
(Al), samples were oven-dried at 60 °C between 24 and
30 h. Afterwards, samples were macerated and 0.5-g dry
sediment was weighed for the digestion process which
was performed by a semi-strong extraction with 8 mL
Suprapur @ nitric acid (HNO 3 ) (Merck) and 2 mL
Suprapur@ hydrogen peroxide (H2O2) (Merck) in Teflon
tubes (González-Macías et al. 2006).
Tubes were placed in a water bath at 60 °C for 15 min in
order to release acid vapor before digestion which was carried
out by microwave (Mars Xpress—version 5) at 180 °C for
45 min. Samples were individually filtered through
Whatman quantitative filter paper (grade 44)and filled up to
50 mL with H2O Milli-Q. Determination of metals Ni, V, Pb,
and Al was conducted by inductively coupled plasma optical
emission spectrometry (ICP-OES) (Perkin Elmer, model 2100
DV).
The analytical accuracy of the method was ± 10% for the
metals, in agreement with Harris (2007). Determination of the
limit of detection (3σ) was based on the analysis of a sample
(n = 7) for the different metals. Values were 0.23 mg/kg for Ni,
1.24 mg/kg for V, 0.34 mg/kg for Pb, and 0.81 mg/kg for Al.
The reference material MESS-3, marine sediment, had a re-
covery percentage of 87% for Ni and V, 85% for Pb, and
110% for Al.
Index of geoaccumulation
The index of geoaccumulation (Igeo), proposed by Muller
(1969), was applied to evaluate metal contamination in
Environ Sci Pollut Res
sediment of each study area and was calculated as follows:
Igeo ¼ log2 ðCsed =1:5  Cback Þ
where Csed represents the mean metal concentration of a mea-
sured site, Cback is the baseline value or reference site, and
factor 1.5 is the possible variation from the baseline because
of lithological processes. Mean metal concentration of the
control station was used as reference site. The quantitative
scale of pollution intensity is defined in Table 1.
Data treatment
Normal data distribution was evaluated in agreement with
Shapiro’s test with significance level of 0.05. Data on the
pffiffiffi
metals in the sediment were transformed into x, log (x + 1)
and log (x) for Ni, Pb, and V in summer, respectively, and log
(x) for Ni, Pb, and V in winter so that they could have normal
distribution.
The program used for data treatment was R Core Team
2016). Differences among the sampling sites in each place
and among areas under analysis were investigated by the anal-
ysis of variance (ANOVA). Then, Tukey’s test was carried
out, taking into account a 99% (p < 0.01) confidence interval.
Spearman’s correlation coefficients (r; p < 0.05) were de-
termined to measure the association strength of the variables,
considering metals, pH, TOC, and granulometry of all sam-
pling sites together (n = 54). Regression (r2; p < 0.05) was also
conducted in order to study the relation among the metals
under analysis at each sampling site separately, totaling nine
samples per analyzed metal.
Results and discussion
Sediment parameters
Even though temperature and salinity have just been analyzed
in water, these parameters showed the status of the estuary
along the sampling period (Table 2). Water mean temperatures
were higher in summer than in winter, while salinity values
oscillated between 0.1 and 28.96 in summer and between 0
and 3.58 in winter. Low salinity found in summer may be
attributed to high rainfall, a fact that contributes to the increase
in fresh water in the estuary. The exception was the RGS site,
whose mean salinity value was 28.96 in summer, related to the
influence of the sea on this area since sampling was carried out
on a different day, by comparison with the other sampling sites
(Table 2).
In addition, pH values in the sediment were slightly alka-
line, a typical characteristic of estuarine sediments (Table 2).
In summer, Eh values varied in the sediment and were mostly
Environ Sci Pollut Res

Table 1 Classification of sediment contamination based on the index of contamination by Ni did not vary among all places.
geoaccumulation (Igeo)
However, in winter, mean concentrations at the control station
Igeo value Class Pollution classification were just significantly (р < 0.01) lower than the ones found at
YC and GFS sites. The highest Ni concentrations were found
<0 0 Background levels at YC2 (15 mg/kg) and at YC3 (13 mg/kg) sites, close to the
0–1 1 Unpolluted mooring docks with recreational vessels due to the highest
1–2 2 Unpolluted to moderately polluted mean TOC concentration by comparison with the other places
2–3 3 Moderately polluted (Table 2). Mean Ni concentrations were also high at GFS1 site
3–4 4 Moderately to strongly polluted (19 mg/kg) on the slipway of the shipyard in winter, by com-
4–5 5 Strongly polluted parison with summer. At this site, the percentage of silt and
>5 6 Very strongly polluted clay was higher (20%) than the one at the other sites located in
this place, as well as the TOC content (1.71%).
Source: Muller (1969)
Mean Ni concentrations in winter at YC and GFS sites
were significantly (р < 0.01) higher than the ones found at
RR, RGS, and SS. It happens because the YC is a marina area
reducers, showing the anoxic tendencies of the sediment at the
with small recreational vessels. Even though the GFS
different sampling sites. Eh was not quantified in winter.
Shipyard has not operated, environmental liability has been
TOC mean values in summer (1.71%) and in winter
involved due to more than 100 years of operation. Nowadays,
(1.58%) were higher at the YC site (Table 2), where there is
vessels have been supplied in this area, a fact that contributes
vessel maintenance and low water renovation. The lowest
to the increase in Ni contents in this place.
values were found at the control station in both seasons. The
However, the highest Ni concentrations at YC and SS sites
granulometry analysis resulted mostly in fine sand (0.125–
are a little lower than the contents found in the Lagoa dos
0.250 μm), at all sampling sites under analysis.
Patos estuary by Santos et al. (2004) and much lower than
the ones found in other estuaries in Brazil and in the world,
Metal contamination as shown in Table 3. Likewise, in general, Ni concentrations
are below the limit that may lead to negative effects on the
Nickel (Ni) biota (Buchman 1999; EPA 2015) (Table 3).

Mean Ni concentrations in summer at YC, GFS, RR, and

SS sites were 8-fold, 7-fold, 18-fold, and 21-fold, respec-
tively, higher than the contents found in the control sta-
tion; thus, they were significantly (р < 0.01) higher than
the ones at the CS (Fig. 2). The control station is located
in a more sheltered area with small artisanal non-
motorized vessels.
High variability in concentrations in summer at the sam-
pling sites in each place shows that, in general, the
Lead (Pb)
Similarly to Ni, Pb concentrations did not vary significantly
(p < 0.01) in summer at the sampling sites located in each
place under investigation (Fig. 2). Mean Pb contents in the
sediment in all places in summer did not have significant
difference from the ones found at the control station
(р < 0.01). The YC1 (53 mg/kg) and GFS1 (209 mg/kg) sites

Table 2 Mean values of physicochemical parameters: water temperature and salinity; pH, Eh (redox potential), total organic carbon (COT) and
dominant fine sand fraction (0.125–0.250 μm %) of the sediment collected at three sites in each study area in the estuary

Study areas Temperature (°C) Salinity pH Eh (mV) TOC (%) Granulometry fine sanda
(%)

Summer Winter Summer Winter Summer Winter Summer Summer Winter Summer Winter

Yacht Club 25.71 13.13 2.83 1.67 7.35 7.54 − 298.67 1.71 1.58 42.49 31.89
Gustavo Fernandes Filho Shipyard 24.83 14 0.1 0.5 7.11 7.36 − 266.11 1.37 1.26 54.0 67.95
Riograndense Refinery 32.9 18 2.3 3.58 7.35 7.16 − 179.56 0.54 0.34 69.91 71.84
Rio Grande Shipyard 25.7 14.2 28.96 0.7 7.27 7.30 − 178.00 0.52 < 0.27 77.42 63.26
Santos Shipyard 25.27 14.7 3.03 0.0 7.23 7.73 − 320.67 1.12 1.21 60.61 52.53
Control station 31.7 17.6 1.3 0.0 7.43 7.60 − 217.11 < 0.27 < 0.27 76.72 71.38
a
Dominant composition
 Environ Sci Pollut Res

Fig. 2 Mean concentrations of

metals (mg/kg, dry weight) in
different sampling sites: control
station (CS 1 , CS 2 , CS 3
), Yacht Club (YC 1 , YC
2 , YC 3 ), Gustavo
Fernandes Shipyard (GFS1 ,
GFS2 , GFS3 ),
Riograndense Refinery (RR 1
, RR 2 , RR 3 ), Rio
Grande Shipyard (RGS1 ,
RGS2 , RGS3 ) and
Santos Shipyard (SS1 , SS2
, SS3 ) in the Lagoa dos
Patos estuary in summer (left) and
winter (right); mean values ± SD
(n = 3), in each sampling site

had Pb values significantly (p < 0.01) higher than the ones
found at RGS and RR.
All Pb contents at the YC1 site, in the marina, and at ship-
yards GFS and SS were the highest ones, even if Pb at the
shipyard SS did not show significant differences from YC and
GFS sites. Higher Pb concentrations in summer at YC1,
GFS1, and SS1 sites, near the slipway of the marina and the
shipyards reflect the input of contaminants from marine diesel
oil and release of Pb from residues of antifouling paints, com-
monly found on the slipway at these sites (Costa et al. 2013,
2016). Since contamination by residues of antifouling paints
has been observed in marinas (Turner 2010), ports, and slip-
ways for recreational vessels, Pb is a concern due to its toxic-
ity (Huntingford and Turner 2011).
In winter, mean Pb contents were significantly (p < 0.01)
higher at YC and GFS than the ones found at RGS (Fig. 2),
probably because TOC values at YC and GFS were higher of
those found in other places (Table 2).
Pb contents were very high at GFS site; in fact, they were
higher than values found in other estuaries (Table 3) and
higher than the background value found for the Lagoa dos
Patos estuary (13.4 mg/kg) (Niencheski et al. 2002).
However, these concentrations were lower than the ones
found at the Hong Kong Shipyard (Chiu et al. 2006), but
agreed with the contents found at the Alang-Sosiya Shipyard
(Reddy et al. 2004). Taking into account reference values
based on sediment toxicity tests with bivalves, maximum Pb
concentrations found in the sediment at the GFS shipyard are
Table 3 Heavy metal concentration ranges (mg/kg) and mean values (± SD) in the total fraction of sediment of the sites in the study area and their comparison with different locations

Locations Seasons Ni Pb V Al References

Yacht Club (YC 1, YC 2, and YC 3) Summer Mean ± SD 3.73–15.50 3.89–53.21 15.24–62.34 6961–56,879 This study
Winter Mean ± SD 10.99 ± 1.31 31.31 ± 28.63 44.18 ± 6.83 37,195 ± 8709.51
9.43–22.58 4.65–46.21 22.41–77.35 1482–2545
Environ Sci Pollut Res

17.14 ± 0.29 19.40 ± 15.67 56.64 ± 6.63 2098.22 ± 226.69

Gustavo Fernandes Filho Shipyard (GFS 1, GFS 2, and GFS 3) Summer Mean ± SD 8.27–12.86 2.22–209.39 32.84–41.20 23,903–33,439
Winter Mean ± SD 10.88 ± 1.13 89.94 ± 80.54 35.76 ± 4.47 28,333 ± 5815.71
17.51–19.81 1.04–130.39 48.52–61.98 21,684–73,487
18.66 ± 1.20 65.68 ± 19.98 55.25 ± 1.06 51,979 ± 2787.91
Riograndense Refinery (RR 1, RR 2, and RR 3) Summer Mean ± SD 6.94–12.37 1.80–3.09 9.45–23.72 3161–5280
Winter Mean ± SD 8.86 ± 4.51 2.66 ± 0.81 18.06 ± 12.04 4454 ± 1234.73
2.83–4.65 1.06–1.92 6.81–8.01 42,647–65,487
3.45 ± 1.15 1.55 ± 0.11 7.32 ± 0.21 54,065.19 ± 3467.36
Rio Grande Shipyard (RGS 1, RGS 2, and RGS 3) Summer Mean ± SD 1.55–8.60 0.42–3.52 5.19–33.36 2383–3293
Winter Mean ± SD 4.78 ± 0.85 1.69 ± 2.68 17.49 ± 10.40 2838 ± 1327
1.49–2.57 0.60–0.87 8.52–11.02 4216–5833
1.87 ± 0.25 0.73 ± 0.06 9.36 ± 0.84 4815 ± 155.07
Santos Shipyard (SS 1, SS 2, and SS 3) Summer Mean ± SD 5.27–14.45 2.23–58.16 5.34–20.14 16,463–41,246
Winter Mean ± SD 8.74 ± 2.19 21.30 ± 27.04 29.84 ± 7.43 27,569 ± 6901.72
4.16–14.24 1.08–7.03 16.49–51.45 5235–6392
10.33 ± 0.24 3.14 ± 1.44 37.62 ± 3.15 5774.89 ± 628.02
Control station (CS 1, CS 2, and CS 3) Summer Mean ± SD 0.49–0.66 2.47–3.76 0.12–0.43 1508–1616
Winter Mean ± SD 0.56 ± 0.01 3.11 ± 0.57 2.88 ± 0.17 1476 ± 88.56
1.50–2.74 2.85–4.79 3.87–4.33 10,622–44,473
2.31 ± 0.79 4.08 ± 2.21 4.10 ± 0.23 30,827.33 ± 33,360.38
Lagoa dos Patos estuary, RS, Brazil 2.6–34.6 2–41.2 – Santos et al. (2004)
Baía de Salina Cruz-Mexico 5–1101 5–123.7 14.76–544.7 González-Macías et al. (2006)
Baía de Salina Cruz-Mexico 5–1101 5–123.7 14.76–544.7 González-Macías et al. (2006)
Santos and São Vicente estuarine complexes, SP, Brazil 2.96–4.85 14.6–66.2 0.1–104.8 Cesar et al. (2007)
Ribeira Bay. Angra dos Reis, RJ, Brazil 20.9–51.6 2–36 4–66 Freret-Meurer et al. (2010)
Pearl River estuary, China 39.2–76.6 1.9–88.5 90–136 Liu et al. (2011)
Hong Kong Shipyard, China 93 1958 – Chiu et al. (2006)
Alang-Sosiya Shipyard, India 172 169 – Reddy et al. (2004)
PELa 42.8 112.18 – Buchman (1999)
ERMb 51.6 218 –
AETc 110 400 57
Environmental ProtectionAgency (EPA)d 20.9 – 57 EPA (2015)

a
PEL probable effects level
b
ERM effects range median
c
AET apparent effects threshold
d
Reference value of chronic toxicity for the biota, based on the oil spill in the Gulf of Mexico in 2010

among effects range median (ERM) and apparent effects
threshold (AET) (Table 3).
Vanadium (V)
Vanadium concentrations in the sediment in summer had sim-
ilar distribution to the Ni ones. At the control station, V con-
tents were significantly (p < 0.01) lower than the ones found in
the other places under analysis (Fig. 2). It means that higher
vanadium concentrations can be mainly found in places where
there is input of petroleum derivatives. Regarding these
places, significant differences in the concentrations were
found at YC and GFS, by comparison with RGS, where V
contents were lower, since the sampling sites, located beside
the shipyard, do not get direct input of contaminants.
Just like what happened in summer, V distribution in the
sediment in winter was similar to the Ni one. V contents at YC
and GFS were significantly (p < 0.01) higher, i.e., 9-fold and
7-fold, respectively, than at the control station (Fig. 2). Both
places are sheltered areas with limited water circulation and
renovation, a fact that favors metal accumulation in the sedi-
ment. Such concentrations are similar to the ones found in port
sediments in Brazil (Cesar et al. 2007; Freret-Meurer et al.
2010), but vanadium data is scarce in the sediment of shipyard
areas worldwide; thus, data comparison is not feasible
(Table 3).
The comparison between the maximum V concentrations
found in the sediment at YC and GFS shows that they are
higher than the reference value (57 mg/kg) suggested by
Buchman (1999) and by the Environmental Protection
Agency (EPA 2015). This value shows adverse effects of V
on the marine polychaete genus Neanthes, according to stud-
ies of bioessays with sediments (Table 3).
Aluminum (Al)
The lowest values of Al at the control station (Fig. 3) in com-
parison with other sampling location in summer and winter
may be related to the normal lower Al concentration in the
upper estuarine region of the Lagoa dos Patos, which range
from 1.3 to 4.8% according to Niencheski et al. (2002). Fine
sand deposited on the lagoon margins (Calliari et al. 2009) and
lower values of organic carbon are characteristics for this es-
tuarine region, as found at the control station.
However, the lowest estuarine region may show Al con-
centrations up to 14% (Niencheski et al. 2002). Therefore, Al
concentrations found in the sampling sites are considered nor-
mal for the estuarine sediment. Al concentrations were higher
in winter than in summer and its distribution tendency was the
same as Ni and V (Fig. 3). In the estuarine sediments, the Al
contents depend on the texture of the sediments. Most proba-
bly, the highest levels of Al during the winter are the result of
the higher contribution of clayey detrital material from the
Environ Sci Pollut Res
Lagoa dos Patos basin, which increases the fine sedimentation
of the estuarine. These conditions are observed during the
winter season (Calliari et al. 2009).
Relation between sediment parameters and metals
Sediments have been considered important environmental in-
dicators and the concentration of metals in this compartment
has been related to physicochemical parameters,
granulometry, and organic matter (Förstner and Wittman
1979). Regarding this matter, considering the correlation be-
tween these parameters and mean concentrations found in all
sampling sites together, results indicated a negative but signif-
icant correlation between pH and metal concentrations in sed-
iment in summer, with highly significant correlation for Al
(Table 4a). Despite the fact that water salinity during sampling
at the Lagoa dos Patos is usually low, higher salinity and pH is
always present in summer in the Lagoa dos Patos estuarine
water. It may affect release of metals from the sediment, which
occurs naturally in estuarine areas because of the availability
of metals by anionic complexation or cation adsorption
(Atkinson et al. 2007; Turner et al. 2004). Availability of labile
metals from sediment (Costa and Wallner-Kersanach 2013)
and of suspended particulate matter (Costa and Wallner-
Kersanach 2013), which is known at the Lagoa dos Patos
estuary, depends mostly on salinity and pH changes. In gen-
eral, the dynamics of parameters, such as pH, salinity and
TOC, usually affects the mobility and toxicity of metals in
the sediment through particle-sediment interactions, such as
adsorption-desorption, precipitation and dissolution processes
(Hong et al. 2011), but interaction among these parameters
may depend on the estuary condition and behavior.
Correlation between NixPb and VxPb in the sediment was
moderate in summer (Table 4a) and strong in winter
(Table 4b), while highly significant correlations were ob-
served between Ni and V (r = 0.91; p < 0.05) in summer
(Table 4a) and in winter (r = 0.99; p < 0.05) (Table 4b).
Exception was observed for Al in summer; it indicates a
moderately significant correlation only with Pb (Table 4a).
TOC concentrations are also strong and positive correlated
with Ni, Pb, and V. Granulometry, represented mostly by fine
sand, indicated negative but significant correlation with all
elements, except Al.
Weak correlation between Al and fine sand in both sampling
periods (Table 4a, b) is due to the fact that this element in the
estuary is predominantly associated with clay minerals (Baisch
1994; Baisch and Wasserman 1998). High freshwater discharge
of the Lagoa dos Patos in winter reflects the low correlation
found between fine sand and TOC with Ni, Pb, and V. Highly
significant correlation between Al with Ni (r = 1.0; p < 0.05) and
V (r = 0.99; p < 0.05) was observed; it is stronger than the one
found in summer sampling. Significant correlation between Al
and Ni and Pb and V confirms that these elements are associated
Environ Sci Pollut Res

Fig. 3 Mean concentration of Al (mg/kg, dry weight) in different (RR 1 , RR 2 , RR 3 ), Rio Grande Shipyard (RGS1 ,
sampling stations: control station (CS1 , CS 2 , CS 3 ), RGS2 , RGS3 ) and Santos Shipyard (SS1 ,SS2 ,SS3 )
Yacht Club (YC 1 , YC 2 , YC 3 ), Gustavo Fernandes in the Lagoa dos Patos estuary in summer (left) and winter (right); mean
Shipyard (GFS 1 , GFS2 , GFS3 ), Riograndense Refinery values ± SD (n = 3), in each sampling site

with aluminosilicate minerals in winter. In general, regardless of navigation, contribute to retain contaminants in the sediment.
the sampling season, correlation between Ni and V was highly However, in places where water circulation is more intense, such
significant. as the other study areas where there is contamination contribu-
tion, the relation between Ni and V was also observed, such as
the cases of RGS (r2 = 0.64) in summer and of SS (r2 = 0.98) in
Relation Ni x V xPb winter. However, in general, RR and RGS did not show any
relation between Ni and V, probably because there are neither
Direct relation between Ni and Vat each sampling site was found direct nor intense anthropic contributions to these places. Even
by this study. Regression values for elements Ni and V at YC though Garcia et al. (2010) got a strong relation (r2 = 0.88) be-
showed that they were related both for data collected in summer tween Ni and V in the soil around the RR, no relation was found
(r2 = 0.53) and for data collected in winter (r2 = 0.94). It means in the estuarine sediment close to this refinery. It happens because
that inlets with low water renovation, where there is recreational the effluents of this plant have been adequately treated; thus,
results found in the sediment close to the plant had low concen-
trations of both elements.
Table 4 Spearman’s correlation coefficient among mean Data collected in winter showed a relation (r2 = 0.74) between
concentrations of metals (mg/kg), pH, TOC (%), and fine sand (%) elements V and Pb, both at GFS and SS, as well as at YC
(a) pH TOC Ni Pb V Al (r2 = 0.57). Ni and Pb had a relation of r2 = 0.70 at SS and of
pH r2 = 0.55 at YC. It means that, although Pb can be found in the
TOC − 0.58 composition of petroleum derivatives, besides the expected rela-
Ni − 0.57 0.65 tion between Ni and V, these elements may also relate to Pb,
Pb − 0.78 0.75 0.62 which can be found in marine diesel oil.
V − 0.53 0.78 0.91 0.66 Despite high relations between Ni and V found at YC and ES
Al − 0.92 0.26 0.34 0.57 0.32
in winter, in general, relations among elements in winter were
Fine sand 0.32 − 0.69 − 0.81 − 0.66 − 0.93 − 0.11
more frequent than in summer at the sampling sites. The cause of
(b) pH TOC Ni Pb V Al
this difference may lie on issues related to the activities devel-
oped in each place and/or fewer seawater changes in the estuary.
pH
High relation between Ni and V corroborates previously findings
TOC − 0.08
in the literature (Chiffoleau et al. 2004, Garcia et al. 2010 and
Ni 0.24 0.55
Magallanes-Ordonez et al. 2015).
Pb − 0.11 0.42 0.79
V 0.32 0.57 0.99 0.71
Al 0.26 0.59 1.00 0.76 0.99
Index of geoaccumulation
Fine sand 0.71 − 0.60 − 0.09 − 0.19 − 0.10 − 0.13

Significant correlation coefficients values (p < 0.05) are shown in italics Igeo results of all elements in the sediment showed that most
for summer (a) and winter (b) sampling sites have some anthropogenic input in both summer
 Environ Sci Pollut Res

Table 5 Ni, Pb, and V index of geoaccumulation (Igeo) of surface Conclusion

sediment in summer and winter at the sampling sites

Sampling sites Igeo value—summer Igeo value—winter The sediment in shipyard, marina, and refinery areas showed
that there were differences in the contamination by Ni, Pb, and
Ni Pb V Ni Pb V V, thus inferring that these elements are related to anthropo-
YC 1 2.15 3.51 1.82 3.86 6.97 6.33
genic activities, whose intensity varies in every place under
investigation. Similarities among the concentrations of the
YC 2 4.21 − 0.26 3.85 5.12 4.32 7.72
elements were found in the marina area at YC and at the
YC 3 4.03 2.98 3.67 4.90 3.66 7.43
shipyards GFS and SS.
GFS 1 3.94 5.49 2.94 4.93 8.47 7.05
Ni concentrations, in general, do not cause effects to organ-
GFS 2 3.77 3.64 3.25 4.85 7.48 7.24
isms. Maximum V concentrations in the sediment at the Yacht
GFS 3 3.30 − 1.07 2.93 4.75 1.50 7.40
Club and the oldest shipyard (GFS) suggest probable chronic
RR1 3.12 − 1.37 2.46 2.84 2.17 4.45
effects on the organism, such as polychaetes. However, toxic-
RR 2 3.88 − 0.60 1.13 2.14 1.53 4.22
ity has been conditioned on the chemical speciation and bio-
RR 3 3.05 − 0.60 2.28 2.12 2.39 4.29
availability of the elements occurring in the sediment, which
RGS 1 2.32 − 0.41 1.69 1.98 1.24 4.91
should be investigated. Maximum Pb contents at GFS in both
RGS 2 0.88 − 3.48 0.27 1.19 0.72 4.55
seasons may cause effects range median to microorganisms in
RGS 3 3.36 − 2.03 2.95 1.27 0.95 4.54
the sediment. The index of geoaccumulation (Igeo) in the
SS 1 4.10 3.64 2.37 2.68 4.26 5.49
sediment of each sampling site indicated that Pb is the main
SS 2 2.65 − 0.42 3.47 4.45 1.83 7.14
concern at the Yacht Club and shipyards, followed by V. They
SS 3 2.95 − 1.06 2.14 4.28 1.55 6.94 were more significant in winter than in summer.
Relationship among elements was confirmed when all
sampling sites were tested together and separately. A highly
significant correlation between Ni and V in sediment was
and winter sampling periods (Table 5). In general, Ni and V observed in both sampling periods, when all sampling sites
indicated moderate pollution in the summer, but there was were considered together, despite the high correlation among
strong pollution by Ni at YC2 and SS1 sites and from moder- TOC and elements Ni, Pb, and V only in summer. Correlation
ate to strong pollution by V at YC2, YC3, GFS2, and SS2. between Pb and the metals Ni and V was also moderate in
Since this area at YC is sheltered and has low water renova- summer and strong in winter.
tion, particles of residues of paints or of petroleum derivatives Considering the sampling sites separately, it could be ver-
deposit on the sediment and are submitted to weak dispersion. ified that relations among elements Ni, Pb, and V were also
Most Pb results in the summer were unpolluted but YC1, higher in winter by comparison with summer, with the highest
GFS1, and SS1 were moderately polluted, while GFS1 indi- significant relations between Ni and V at YC and GFS.
cated very strong pollution, an evidence of the fact that this Because of the significant relations between Ni x V, besides
site receives significant anthropogenic contributions. All these Pb x V and Pb x Ni in each sampling site, this study showed
sites are near the vessel maintenance, and GFS1 is close to the that the relation between elements may be a useful tool to
site (GFS2) where the supply of diesel of vessels occurs next identify elements of the same anthropogenic sources, in this
to the shipyard. case, petroleum derivatives and antifouling paints. Although
Igeo results in winter indicated from moderate to further investigations are needed in other estuaries, it may be
strong Ni pollution at all YC, GFS, and SS sites, and from inferred that such relations are more significant mainly in lo-
strong (RR and RGS) to very strong pollution (YC, GFS, cations where environmental liability ranges from moderate to
and SS) by V. High Igeo values in sediment were also high, when there are few local activities and the sediment is
observed for Pb, which was classified as moderately to not easily remobilized. High Pb concentrations found in the
strongly (YC3) polluted, strongly (SS1 and YC2), and marina area at the Yacht Club and in the shipyards have
very strongly (YC1, GFS1, and GFS2) polluted. Increase caused concern because it is a non-essential element with high
in Igeo results in the winter may be due to the intensifi- toxicity. Pb concentrations in the sediment in locations which
cation of fine sediment transportation from the lagoon to were more affected by contamination must be monitored and
the sea, since freshwater discharge increases in this period measured, and appropriate discharge of residues in marinas
of the year. It may also have influenced increase in the and shipyards, must be taken to improve the quality of the
mean concentration of metals at the control station in environment. The use of the relation between these elements
winter (Table 3). as indicators of contamination should be investigated in other
In general, Igeo values showed that the contamination had estuaries. This may be useful in the future to carry out an
the following behavior: Pb > V > Ni. environmental diagnosis of impacted areas worldwide and as
Environ Sci Pollut Res
a basis for environmental monitoring and/or remediation
programs.
Acknowledgments The authors would like to thank the National
Council for Scientific and Technological Development (CNPq) for the
research grant given to Thayane Lúcia Pereira.
References
Alonso-Hernandez CM, Bernaz-Castillo J, Bolanos-Alvares Y, Gomes-
Batista M, Diaz-Asencio M (2011) Heavy metal content of bottom
ashes from a fuel oil power plant and oil refinery in Cuba. Fuel 90:
2820–2823. https://doi.org/10.1016/j.fuel.2011.03.014
Atkinson CA, Jolly DF, Simpson SL (2007) Effect of overlying water pH,
dissolved oxygen, salinity and sediment disturbances on metal re-
lease and sequestration from metal contaminated marine sediments.
Chemosphere 69:1428–1437. https://doi.org/10.1016/j.
chemosphere.2007.04.068
Baisch PRM (1994) Les oligo-éléments métalliques du système fluvio-
lagunaire dos Patos - Flux et Devenir (Brésil). Thèse de Doctorat,
Université de Bordeaux
Baisch PRM, Wasserman JC (1998) Chemistry and distribution of trace
elements in the Patos Lagoon, South Brazil. In: Wasserman JC,
Silva-Filho EV, Villas-Boas R (eds.) Environmental Geochemistry
in the Tropics. Niteroi, Rio de Janeiro, pp 97–126
Barwise AJG (1990) Role of nickel and vanadium in petroleum classifi-
cation. Energ Fuels 4:647–652. https://doi.org/10.1021/
ef00024a005
Birch GF (2017) Determination of sediment metal background concen-
trations and enrichment in marine environments—a critical review.
Sci Total Environ 580:813–831. https://doi.org/10.1016/j.scitotenv.
2016.12.028
Buchman MF (1999) NOAA screening quick reference tables. NOAA
Hazmat Report, 99–1, Seattle, Coastal protection and restoration
division, National Oceanic and Atmospheric Administration.
http://response.restoration.noaa.gov/sites/default/files/SQuiRTs.pdf.
Accessed 08 July 2016
Calliari LJ, Winterwerp JC, Fernandes E, Cuchiara D, Vinzon SB, Sperle
M, Holland KT (2009) Fine grain sediment transport and deposition
in the Patos Lagoon-Cassino beach sedimentary system. Cont Shelf
Res 29:515–529. https://doi.org/10.1016/j.csr.2008.09.019
Cesar A, Choueri RB, Riba I, Morales-Casales C, Pereira CDS, Santos AR,
Abessa DMS, Delvalls TA (2007) Comparative sediment quality assess-
ment in different littoral ecosystems from Spain (Gulf of Cadiz) and
Brazil (Santos and São Vicente estuarine system). Environ Int 33:429–
435. https://doi.org/10.1016/j.envint.2006.11.007
Chiffoleau JF, Chauvaud L, Amoroux D, Barats A, Dufour A, Pecheyran
C, Roux N (2004) Nickel and vanadium contamination of benthic
invertebrates following the Erika wreck. Aquat Living Resour 17:
273–280. https://doi.org/10.1051/alr:2004032
Chiu SW, Ho KM, Chan SS, So OM, Lai KH (2006) Characterization of
contamination in and toxicities of a shipyard area in Hong Kong.
Environ Pollut 142:512–520. https://doi.org/10.1016/j.envpol.2005.
10.038
Costa LDF, Wallner-Kersanach M (2013) Assessment of the labile frac-
tions of copper and zinc in marinas and port areas in southern Brazil.
Environ Monit Assess 185:6767–6781. https://doi.org/10.1007/
s10661-013-3063-0
Costa CSB, Seeliger U, Kinas PG (1988) The effect of wind velocity and
direction on the salinity regime in the Patos Lagoon estuary. Ciênc e
Cult 40:909–912 (in Portuguese)
Costa LDF, Casartelli MRO, Wallner-Kersanach M (2013) Labile copper
and zinc fractions under different salinity conditions area in the
lagoon estuary, south of Brazil. Quím Nov 36(8):1089–1095.
https://doi.org/10.1590/S0100-40422013000800002
Costa LDF, Mirlean N, Wasserman JC, Wallner-Kersanach M (2016)
Variability of labile metals in estuarine sediments in areas under
the influence of antifouling paints Southern Brazil. Environ Earth
Sci 75:580. https://doi.org/10.1007/s12665-016-5355-5
Environmental Protection Agency (EPA) (2015) Sediment benchmarks
for aquatic life. Accessed 09 June 2015
Förstner U, Wittman G (1979) Metal pollution in the aquatic environ-
ment. Springer-Verlag, Berlin
Freret-Meurer RNV, Andreata JV, Meurer BC, Manzano FV, Baptista
MGS, Teixeira DE, Longo MM (2010) Spatial distribution of metals
in sediments of the Ribeira Bay, Angra dos Reis, Rio de Janeiro,
Brazil. Mar Pollut Bull 60:627–629. https://doi.org/10.1016/j.
marpolbul.2010.01.023
Garcia FAP, Mirlean N, Baisch PR (2010) Marcadores metálicos como
avaliação do impacto crônico de emissões petroquímicas em zona
urbana. Quím Nov 33(3):716–720. https://doi.org/10.1590/S0100-
40422010000300040.(in Portuguese)
González-Macías C, Schifter I, Lluch-Cota DB, Méndez-Rodríguez L,
Hernández-Vásquez S (2006) Distribution, enrichment and accumu-
lation of heavy metals in coastal sediments of Salina Cruz Bay,
México. Environ Monit Assess 118:211–230. https://doi.org/10.
1007/s10661-006-1492-8
Harris DC (2007) Quantitative Chemical Analysis, 7th edn. China Lake,
California, W.H. Freeman and Company, New York
Hong YS, Kinney KA, Reible DD (2011) Effects of cyclic changes in pH
and salinity on metals release from sediments. Environ Tox and
Chem 30(8):1775-1784. https://doi.org/10.1002/etc.584
Huntingford EM, Turner A (2011) Trace metals in harbour and slipway
sediments from the island of Malta central Mediterranean. Mar
Pollut Bull 62:1557–1561. https://doi.org/10.1016/j.marpolbul.
2011.05.015
Kjerfve B (1986) Comparative oceanography of coastal lagoons.
Estuarine Variability Acad Press, New York, pp 63–81
Liu BL, Hu K, Jiang ZL, Yang J, Luo XM, Liu AH (2011) Distribution
and enrichment of heavy metals in a sediment core from the Pearl
River Estuary. Environ Earth Sci 62:265–275. http://doi.org/10.
1007/s12665-010-0520-8
Magallanes-Ordonez VR, Marmoleio-Rodriguez AJ, Rodriguez-
Figueroa GM, Sanchez-Gonzales A, Aguinia-Garcia S, Arreguin-
S a n c h e z F, Z e t i n a - R ej o n M , Tr i p p - Va l d e z A ( 2 0 1 5 )
Characterization of lithogenic and biogenic zones and natural en-
richment of nickel in sediments of the Terminos Lagoon, Campeche,
Mexico. Estuar Coast Shelf Sci 156:116–123. https://doi.org/10.
1016/j.ecss.2014.11.007
Mokhart MB, Awaluddin AB, Yusof ABBM, Bakar BB (2002) Lead in
blood and hair of shipyard workers. Bull Environ Contam Toxicol
69:8–14
Möller OO Jr, Lorenzetti JA, Stech JL, Mata MM (1996) Patos Lagoon
summertime circulation and dynamics. Cont Shelf Res 16(3):335–
351. https://doi.org/10.1016/0278-4343(95)00014-R
Muller G (1969) Index of geoaccumulation in sediments of the Rhine
river. Geol J 2(3):108–118
Nemr AE, Khaled A, Sikaily AE (2006) Distribution and statistical anal-
ysis of leachable and total heavy metals in the sediments of the Suez
Gulf. Environ Monit Assess 118:89–116. https://doi.org/10.1007/
s10661-006-0985-9
Neşer G, Kontas A, Ünsalan D, Uluturhan E, Altay O, Darılmaz E,
Küçüksezgin F, Tekoğul N, Yercan F (2012) Heavy metals contam-
inations levels at the Coast of Aliağa (Turkey) ship recycling zone.
Mar Pollut Bull 64:882–887. https://doi.org/10.1016/j.marpolbul.
2012.02.006
Nielsen KE, Dittmer J, Malmendal A, Nielsen NC (2008) Quantitative
analysis of constituents in heavy fuel oil by 1H nuclear magnetic

resonance (NMR) spectroscopy and multivariate data analysis.
Energy Fuel 22:4070–4076. https://doi.org/10.1021/ef800539g
Niencheski LFH, Baraj B, França RG, Mirlean N (2002) Lithium as a
normalizer for assessment of anthropogenic metal contamination of
sediments of the southern area of Patos Lagoon. Aquat Ecos Health
and Manag 5(4):473–483. https://doi.org/10.1080/
14634980290001977
Pasquini AI, Nienscheski LFH, Depetris PJ (2012) The ENSO signature
and other hydrological characteristics in Patos and adjacent coastal
lagoons, south-eastern Brazil. Estuar Coast Shelf Res 111:139–146.
https://doi.org/10.1016/jecss201207004
R Core Team (2016). R: A language and environment for statistical com-
puting. R Foundation for Statistical Computing, Vienna, Austria.
http://www.R-project.org/
Reddy MS, Basha S, Kumar VGS, Joshi HV, Ramachandraiah G (2004)
Distribution, enrichment and accumulation of heavy metals in coast-
al sediments of Alang-Sosiya ship scrapping yard, India. Mar Pollut
Bull 48:1055–1059. https://doi.org/10.1016/j.marpolbul.2003.12.
011
Reyes MNM (2003) Estudos para a determinação de Ni e Pb em líquidos
orgânicos estabilizados na forma de microemulsão por
espectrometria de absorção atômica com forno de grafite.
Dissertation, Pontifícia Universidade Católica do Rio de Janeiro
(in Portuguese)
View publication stats
Environ Sci Pollut Res
Santos IR, Baisch P, Lima G, Mirlean N, Griep G, Silva-Filho EV (2004)
Análise estatística multivariada de parâmetros geoquímicos em
sedimentos do estuário da Laguna dos Patos. Geochem 18(1):038–
045 (in Portuguese)
Soldi T, Rolo C, Alberti G, Gallorini M, Peloso GF (1996) Environmental
vanadium distribution from an industrial settlement. Sci Total
Environ 181:45–50. https://doi.org/10.1016/0048-9697(95)04958-4
Suguio K (1973) Introdução a sedimentologia. São Paulo (in Portuguese)
Turner A (2010) Marine pollution from antifouling paint particles. Mar
Pollut Bull 60:159–171. https://doi.org/10.1016/j.marpolbul.2009.
12.004
Turner A, Millward GE, Roux SM (2004) Significance of oxides and
particulate organic matter in controlling trace metal partitioning in
a contaminated estuary. Mar Chem 88:179–192. https://doi.org/10.
1016/j.marchem.2004.03.008
Wallner-Kersanach M, Mirlean N, Baumgarten MGZ, Costa LDF, Baisch
P (2016) Temporal evolution of the contamination in the southern
area of the Patos Lagoon estuary, RS, Brazil. JICZM 16(3):263–279.
https://doi.org/10.5894/rgci596
Zimmermann CF, Keef CW, Baske J (1997) Determination of carbon and
nitrogen in sediments and particulates of estuarine/coastal waters
using elemental analysis. U.S. Environ Protect Ag, Method 440.0:
9. https://cfpub.epa.gov/si/si_public_record_report.cfm?
dirEntryId=309418 Accessed 10 June 2015