International Journal of Sediment Research 36 (2021) 362e372

Contents lists available at ScienceDirect

International Journal of Sediment Research

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

Original Research

A grain-size correction for metal pollution indexes in river sediments

Thomas Vincent Gloaguen a, *, Paula Núbia Soares Dalto Motta a, Carolina Fonseca Couto b
a
Federal University of Reconcavo of Bahia, Cruz das Almas, Brazil
b
Federal University of Minas Gerais, Belo Horizonte, Brazil

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

Article history: According to the List of Hazardous Substances of the Agency of the Toxic Substances and Disease Registry
Received 15 March 2019 (ATSDR 2017), some metallic elements such as Pb or Cd are still considered as the most polluting ele-
Received in revised form ments in the world. These elements accumulate in sediments, and there are various methods available
14 October 2020
that differentiate lithogenic sources from anthropogenic sources. For that, the natural geochemical
Accepted 20 October 2020
Available online 26 October 2020
background is required, however, its definition is far from unanimous: it can be a global or local value,
single or statistically estimated value, depending on the studies. Our study is focused on the Subae
River
in the state of Bahia, Northeastern Brazil, which was historically contaminated by lead metallurgy. The
Keywords:
Enrichment factor
river sediments were sampled at 21 locations: one at the discharge point of the plant's rainwater basin,
Estimated background ten upstream, and ten downstream. The total contents of Fe, Ti, Mn, Pb, Zn, Cu, Cr, particle-size distri-
Particle-size distribution bution, and organic matter were analyzed. The conventional geochemical indexes, i.e., the pollution
degree (mCd), pollution load index, and enrichment factor indicated contamination by Zn, Pb, Cr, and Cu.
Then, a new enrichment factor is introduced, assuming that the sediments come from erosion of soils in
the watershed. After obtaining the natural concentrations of metals in the clay, silt, and sand fractions of
uncontaminated reference soils, we corrected the pollution indexes by calculating a new individual
background in each sediment sample, according to its grain size distribution. This new approach pro-
vided more precise indexes in the assessment of sediment pollution, by highlighting higher contami-
nation of Zn and Pb (around 50%) and at the same time the absence of Cr and Cu contamination, two
metals not involved with the metallurgical activity.
© 2020 International Research and Training Centre on Erosion and Sedimentation/the World Association
for Sedimentation and Erosion Research. Published by Elsevier B.V. All rights reserved.

1. Introduction 1980), modified degree of contamination (mCd), contamination

Despite the widespread emergence of organic pollution and
emerging pollutants, such as phthalates, pharmaceutical molecules
or endocrine disruptors, metallic trace elements remain among the
primary pollutants according to the 2017 ATSDR (Agency for Toxic
Substances and Disease Registry) Priority List of Hazardous Sub-
stances (As, Pb, Hg are in the top three positions).
The determination of the proportion of natural and anthropo-
genic sources of metals in sediments is essential. Pollution can be
eventually assessed by isotopic analyzes (Gao et al., 2008; Han
et al., 2015; Xu et al., 2017; Zaborska, 2014), but due to high costs
and time consuming, classic indexes are generally used (Table 1):
degree of contamination (Cd) (Abrahim & Parker, 2008; Hakanson,
* Corresponding author.
E-mail addresses: thomasgloaguen@ufrb.edu.br (T.V. Gloaguen), pnsd.motta@
gmail.com (P.N.S.D. Motta), carolf.couto@hotmail.com (C.F. Couto).
factor (CF) and Pollution Load Index (PLI) (Kalender & Çiçek Uçar,
2013; Pejman et al., 2015; Pen ~ a-Icart et al., 2016; Saeedi &
Jamshidi-Zanjani, 2015; Tomlinson et al., 1980), geoaccumulation
index (Igeo) (Abrahim & Parker, 2008; Aiman et al., 2016; Han et al.,
2017; Hanif et al., 2016; Hasan et al., 2013; Kalender & Çiçek Uçar,
2013; Muller, 1969; Pen ~ a-Icart et al., 2016; Usese et al., 2017;
Wang et al., 2015; Zahra et al., 2014; Zhang et al., 2009; Zhiyuan
et al., 2011), enrichment factor (EF) (Abrahim & Parker, 2008;
Aiman et al., 2016; Hanif et al., 2016; Hasan et al., 2013; Kalender &
Çiçek Uçar, 2013; Kaushik et al., 2009; Pen ~ a-Icart et al., 2016; Qi
et al., 2010; Sinex & Helz, 1981; Usese et al., 2017; Wang et al.,
2015; Zahra et al., 2014; Zhang et al., 2009) and potential ecolog-
ical risk index (PERI) (Aiman et al., 2016; Hakanson, 1980; Han et al.,
2017; Pejman et al., 2015; Saeedi & Jamshidi-Zanjani, 2015; Wang
et al., 2015; Zhang et al., 2016). These indices are based on a com-
parison between the concentration measured in the sample and the
concentration in a reference sample (natural background). The

https://doi.org/10.1016/j.ijsrc.2020.10.005
1001-6279/© 2020 International Research and Training Centre on Erosion and Sedimentation/the World Association for Sedimentation and Erosion Research. Published by
Elsevier B.V. All rights reserved.
 T.V. Gloaguen et al. / International Journal of Sediment Research 36 (2021) 362e372
critical issue is, therefore, the choice of the reference samples, i.e.,
the background values, irrespective of the choice of the index.
Reimann and de Caritat (2005) comment on the reliability of EF to
differentiate natural and anthropogenic sources; they question the
variability of the EF values, due to local lithology, biological
enrichment or sedimentary processes. However, the actual prob-
lem is not the EF itself but the choice of the background, whose
importance is sub-estimated in most of the studies. Global values
are generally used to characterize the background: either the
Earth's crust values or the average shale values (Aiman et al., 2016;
Hanif et al., 2016; Pen ~ a-Icart et al., 2016; Usese et al., 2017; Zhang
et al., 2009). The normalization with conservative elements such
Fe, Al or Ti in some pollution indexes (e.g., EF) reduces but does not
eliminate the effect of a broad range of geochemically different
materials; in addition, weathering (co-precipitation in plinthite)
and biosphere (root stabilization, absorption, or strong bound to
organic matter) can modify the EF values (Sucharova  et al., 2012).
Grygar & Popelka (2016) pointed to important variation of metal/Fe
ratios in different materials.
Detailed studies reported three different methods to define a
background value (Dung et al., 2013; Gałuszka, 2007): geochemical
direct methods, which are based on uncontaminated samples
(Abrahim & Parker, 2008; Han et al., 2017; Kalender & Çiçek Uçar,
2013; Qi et al., 2010), statistical undirect methods (Apitz et al.,
2009; Gałuszka & Migaszewski, 2011; Matschullat et al., 2000;
Reimann & Garrett, 2005; Zhao et al., 2007) and integrated methods

rez-Sirvent et al., 2009; Zhao et al., 2007). Geochemical methods
(Pe
are direct or empirical methods and use a single value. As discussed
above, most of the pollution assessments use global references such
as average Earth's crust values (Hanif et al., 2016; Hasan et al., 2013;
Pen~ a-Icart et al., 2016; Wang et al., 2015; Zhang et al., 2009) or
average shale values (Aiman et al., 2016; Pejman et al., 2015; Usese
et al., 2017; Zhiyuan et al., 2011). To improve the pollution assess-
ment, some authors have used background values from local sed-
iments (Abrahim & Parker, 2008; Qi et al., 2010; Silva et al., 2017) or
soils (Bhuiyan et al., 2010; Ji et al., 2008). This approach requires
access to local data on uncontaminated samples (preindustrial
values), sometimes unavailable (Pejman et al., 2015). The use of
local rocks is an alternative option (Kalender & Çiçek Uçar, 2013),
but the geochemical processes during pedogenesis can mask some
trends, such as differential behavior of major metals (Fe, Ti) and
trace metal (Acosta et al., 2011; Bini et al., 2011; Santos et al., 2017).
Therefore, the use of local soil and sediment values is recom-
mended, even though strong local variations can remain, because
soils and sediments can completely differ in clay, sand, oxides or
organic matter content.
The second approach consists of statistical methods, where the
geochemical background is not a single value but a range of values.
For several authors (Gałuszka & Migaszewski, 2011; Matschullat
et al., 2000; Reimann & Garrett, 2005), this geochemical back-
ground corresponds to fixed mean or preferably median ± 2s. It
requires a considerable number of samples for consistent statistical
analysis and exclusion of outliers; this method does not require
sampling exclusively in pristine areas, unlike direct or integrated
methods (see next paragraph). Another statistical consistent
method consists of multiple regressions obtained between the
concentration of an element and a set of physicochemical attributes
of the samples (clay, organic matter, Al, Fe, Mn). Grygar and Popelka
(2016) discussed this background issue in detail and directly used
[metal]/[metal]background ratios (“local enrichment factor”), where
[metal]background is calculated using regression from other elements
(Al, Ti, Fe). This method can be considered accurately, but for that a
sufficient quantity of samples is necessary. Finally, other advanced
statistical techniques, the fractal/multifractal models (Apitz et al.,
2009; Chen et al., 2017; Cheng, 1999; Li et al., 2003; Parsa et al.,
363
2017; Xie & Cheng, 2014) have recently been used to distinguish
geochemical anomalies from background. These fractal methods
establish a content surface derived from kriging of geochemical
data, in addition to geometrical properties and scale-independent
characteristics of anomalies (U-statistics).
The third approach, the integrated methods, combines both
direct and indirect methods (Bini et al., 2011; Pe
rez-Sirvent et al.,
2009; Zhao et al., 2007). The data necessary come from pristine
areasdas in direct methods, and they are then processed
statisticallydas in direct methods, for more consistency. According
to Gałuszka and Migaszewski (2011), this is the most interesting
approach.
In statistical and integrated methods, the factors controlling the
concentration of metals are considered. Particle-size distribution is
one of the main factors, due to the accumulation of metals in fine
particles (Acosta et al., 2009; Ajmone-Marsan et al., 2008;
Gloaguen & Passe, 2017; Gomes et al., 2016; Hardy & Cornu, 2006;
Santos et al., 2017). Some legislations have even included this
specificity to define variable threshold limit soil values. In the
Netherlands, the threshold is a function of clay content and organic
matter (Smith, 1995; Spijker, 2012); Flemish legislation adopts a
similar model (Baize, 2002), but includes pH for some elements
(VLAREBO, 2007).
The objective of this study is to determine the current impact on
river sediments of a lead smelter closed in the 1990's, using a new
method that corrects THE pollution index calculations based on the
particle size distribution.
2. Material and methods
2.1. Physical characterization of the watershed
The study was conducted in the Subae
River near an important
old lead smelter, in the city of Santo Amaro, Bahia, Brazil. The
metallurgical complex operated from 1960 to 1993 and produced
490,000 tons of highly concentrated metal slag (Pb, Zn, As, Cd). Two
sources of pollution are distinguishable: diffuse radial contamina-
tion by smoke emission and point source pollution from slag
disposal and use as a construction material in the surrounding
neighborhood (Andrade et al., 2017; Bomfim et al., 2015; de
Andrade Lima & Bernardez, 2011; de Souza Guerra et al., 2015;
Silvany-Neto et al., 1989). In the last decades, the high tropical
rainfall remobilized part of this pollution, producing contaminated
sediments in the Subae River (Bomfim et al., 2015; da Silva et al.,
2017; Motta et al., 2018; Santos & Jesus, 2014).
The mainspring of the river, in the Subae
lagoon of the city of
Feira de Santana, is 55 km from the estuary located in the city of Sa~o
Francisco do Conde, in the Bay of Todos os Santos. More details
about the watershed and pollution of the river are available in
previous studies (Motta et al., 2017, 2018). The rainy tropical cli-
matic conditions are as followed: average temperature of 26
C,
average evapotranspiration of 1,300 mm$y1, and average rainfall
of 1,600 mm$y1.
The geological basement (Asmus & Ponte, 1973; Milani et al.,
2007; Mohriak, 2003) is constituted by the Archean migmatized
orthogneisses, covered by Cretaceous sedimentary rocks, mainly
sandstones (Brotas Group) and shales (Santo Amaro Group). The
Terciary (Barreiras Group-Paleogene age) and Quaternary fluvial
sediments deposited over these units.
The principal soils are Dystrophic Red-Yellow Acrisols in the
central part of the watershed, with a high content of clay but low
fertility, and Vertisols, with clay texture, high fertility (Ca and Mg),
but low permeability (BRASIL, 1981). The associated soils are
Dystrophic Yellow Ferralsols, acid and highly weathered, Arenosols,
at the estuary, with high sand content, extremely poor, consisting
364 T.V. Gloaguen et al. / International Journal of Sediment Research 36 (2021) 362e372

Table 1
Main pollution indicators in river sediments.

Name Symbol Equation Metal Background normalization Source

Contamination factor CF ½MiSED Metal i No Hakanson (1980)

½MiBG
Degree of contamination Cd P n All metals No Hakanson (1980)
CFi
i¼1
Modified degree of contamination mCd Pn All metals No Abrahim and Parker (2008)
ð CFiÞ =n
i¼1
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Qn
Pollution load index PLI n All metals No Tomlinson et al. (1980)
i¼1 mCFi
Geoaccumulation index IGEO ½MiSED Metal i Yes Muller (1969)
log2
1:5½MiBG
Enrichment Factor EF ½MiSED =½Mref SED Metal i Yes Sinex and Helz (1981)
½MiSED =½Mref BG
Ecological Risk ER T:½MiSED Metal i No Hakanson (1980)
Potential Ecological Risk Index PERI P n All metals No Hakanson (1980)
ER
i¼1

[Mi]SED is the concentration of metal i in the sediment; [Mi]BG is the background concentration of metal i in pristine area; T is the toxicity coefficient of metal i.

predominantly of quartz materials, and the indiscriminate
mangrove soils, classified as Gleysols, with high content of salts and
sulfur, poorly drained and rich in organic matter (Bomfim et al.,
2015).
2.2. Sampling and analysis of river sediments
The 21 sampling sites were equally distributed before and after
the smelter (Fig. 1): one site close to the smelter (Sed0), ten up-
stream sites (Sed0-1 to Sed0-10) and ten downstream sites (Sed0-1
to Sed0-10). The distance between each sampling sites was 100 m
and the total distance was 2,000 m.
At each sampling site, we obtained a composite sample with
four subsamples along a cross-section, one subsample collected
near each margin (approximately 50 cm from the margin) and two
other subsamples collected transversely in the river bed, approxi-
mately equidistant. A 2.0 inch diameter core sampler was used to
collect a 15 cm deep core. In the laboratory, after air drying, the
samples were disaggregated and sieved in a 2 mm stainless steel
mesh.
For the particle-size analysis, the pipet method was used to
determine the clay and silt content: After chemical dispersion
(NaOH, 0.1 mol$L1), mechanical agitation and a specific time for
sedimentation, an aliquot is drawn with a 50 mL pipet at 10 cm,

Fig. 1. Location of the studied area.

 T.V. Gloaguen et al. / International Journal of Sediment Research 36 (2021) 362e372 365

dried and sediments are weighted. Coarse and fine sand was area (11 sampling sites), according to Eq. (3) (Tomlinson et al.,
determined by mechanical sieving (Empresa Brasileira de 1980).
Pesquisa Agropecua
ria, 2011). The organic matter was deter- qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ffi
Yn
mined by weighing after 12 h in an oven at 440±3
C (NBR 13600, PLIS ¼
n
mCd (1)
k¼1 k
1996).
The chemical analyses were performed on the air-dried samples.
The concentrations of Pb, Cr, Zn, Cu, Fe, Al, and Si were obtained by ½MS
mCd ¼ (2)
energy-dispersive X-ray spectroscopy (EDX) on a Shimadzu ½MR
EDX8000 spectrometer using the quantification method with
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
external calibration. All samples were triplicated to check the ho- Y11
11

mogeneity of the sample and provide more consistent data. The PLIm ¼ S¼1
PLIS (3)
quality of the analysis (precision and accuracy) was ensured by
analyzing the NIST soil standard reference material SRM2709a San where mCd is the contamination level, n is the number of metallic
Joaquin Soil (https://www.nist.gov/sites/default/files/documents/ pollutant, [M]S is the concentration of the metal in the studied
srm/SP260-172.pdf). The accuracy values were 0.5%, 0.9%, 1.7%, sediment and [M]R is its concentration in the reference sediment
2.4%, 5.2% and 6.5% for Fe, Ti, Zn, Cu, Cr, and Pb, respectively, and the (background value), in mg$kg1;
precision values were 0.6%, 1.2%, 2.1%, 2.6%, 7.4% and 7.8% for Fe, Ti, The reference sediment (background values) used in this study
Zn, Cu, Cr, and Pb, respectively. was obtained by (Silva et al., 2017), in a pristine area of the river, far
from cities and intense human activity, about 14.3 km upstream
2.3. Assessment of pollution index from the smelter.
To minimize the matrix effect, we also calculated the enrich-
The concentrations of metals were compared to Brazilian ment factors (Sinex & Helz, 1981), according to Eq. (4). Titanium, a
guideline values (prevention value, PV, and investigation value, IV) conservative element in such a tropical environment, was used as
established by (CONAMA - Conselho Nacional do Meio Ambiente, the reference element.
2009, p. 81) (Table 2). We also compared the results with the
½MS =½TiS
Threshold effect concentration (TEC) and probable effect concen- EF ¼ (4)
½MR =½TiR
tration (PEC) defined by Mac Donald et al. (2000).

Table 2
Physical and chemical attributes of sediments of the Subae river and guideline values for freshwater.

Sample Sand (g$kg1) Silt (g$kg1) Clay (g$kg1) OMa Fe (%) Ti (%) Mn (mg$kg1) Pb (mg$kg1) Zn (mg$kg1) Cr (mg$kg1) Cu (mg$kg1)

S-10 750 35 214 14.7 2.44 0.28 300 36.8 142.7 122.0 33.0
S-9 778 98 124 17.4 2.13 0.27 355 19.4 56.9 109.8 33.4
S-8 605 75 320 20.9 2.23 0.36 314 55.8 295.5 77.7 35.3
S-7 812 124 65 18.4 1.81 0.33 278 132.1 582.0 112.4 34.6
S-6 764 176 60 13.2 2.06 0.31 336 18.3 57.1 103.6 33.5
S-5 737 203 60 21.8 1.92 0.45 301 58.6 127.1 63.8 35.0
S-4 762 164 74 19.7 1.94 0.43 307 69.3 110.5 103.4 32.2
S-3 948 13 39 8.5 1.31 0.21 234 37.2 180.0 74.4 30.0
S-2 551 226 223 38.3 2.51 0.27 253 18.5 80.4 72.3 34.4
S-1 935 45 20 7.5 2.09 0.30 283 24.0 90.8 121.5 32.7
S 866 58 76 10.5 2.26 0.23 287 29.3 88.7 182.1 34.7
Sþ1 732 183 85 18.0 2.55 0.23 288 50.7 260.0 127.6 33.3
Sþ2 816 84 100 14.8 2.08 0.17 260 34.2 104.7 151.1 33.0
Sþ3 867 125 9 31.9 2.81 0.19 316 2506.9 4867.2 134.9 42.7
Sþ4 809 122 70 16.8 1.76 0.23 177 57.3 366.5 106.1 32.0
Sþ5 907 23 70 13.2 1.59 0.19 182 20.7 54.6 126.1 32.4
Sþ6 937 27 36 1.6 1.19 0.14 201 22.1 101.9 85.5 33.3
Sþ7 707 78 215 21.6 2.34 0.27 271 61.1 224.4 147.7 34.4
Sþ8 684 206 110 19.8 2.18 0.30 324 45.4 170.0 74.8 34.2
Sþ9 770 80 150 22.8 2.04 0.24 352 56.0 324.2 85.1 34.7
Sþ10 755 125 120 18.0 1.96 0.30 329 26.6 120.5 76.0 33.7
MEANb 785 108 107 18.0 2.06 0.27 283 46.2 167.8 107.5 33.9
PVc d d d d d d d 72 60 75 60
IVc d d d d d d d 180 450 150 200
TECd d d d d 2.00 d 460 36 120 43 32
PECd d d d d 4.00 d 1100 130 460 110 150
a
Organic Matter.
b
Geometric mean for log-normal distributed element (Pb, Zn).
c
Prevention Value (PV) ¼ limit value in soil such that it is capable of sustaining its primary functions/Investigation Value (IV) ¼ limit value in soil above which there are
potential direct or indirect risks to human health (CETESB, 2005).
d
Threshold Effect Concentration/Probable Effect Concentration ¼ lower and upper effect level at which toxicity to benthic-dwelling organisms are predicted to be unlikely
and probable, respectively (Mac Donald et al., 2000).

The degree of pollution on each site S was first assessed by where [M] and [Ti] are the concentrations of the studied metal and
calculating the Pollution Load Index (PLIS) at a single sampling site, titanium, in the studied sediment (S) and reference sediment (R),
for all the studied metallic contaminants, according to Eqs. (1) and respectively, in mg$kg1.
(2). The geometric mean PLIm was calculated for the entire studied
366 T.V. Gloaguen et al. / International Journal of Sediment Research 36 (2021) 362e372

Fig. 2. Modified (mCd) and grain-size corrected (gCd) degree of contamination in the sediments of the Subae river downstream and upstream the Pb smelter.
 T.V. Gloaguen et al. / International Journal of Sediment Research 36 (2021) 362e372
The normality of the distribution was checked by the Shapiro
Wilk test, which is more suitable for a dataset smaller than 50.
When necessary, log transformation was applied.
3. Results
Some material can remain heterogeneous even after quartering,
particularly in an environment polluted by dense material such as
Pb scoria. In this study, the 2-mm sieved sediments showed high
homogeneity among the three sub-samples (quality of the anal-
ysis), particularly for Fe and Ti (mean variability of 0.47 and 0.94%).
Trace metal also presented low variability: 1.65%, 2.38%, 5.20% and
6.05% for Zn, Cu, Cr, and Pb, respectively. The intra-sample vari-
ability of the highest contaminated sample ([Pb] ¼ 2,506 mg$kg1)
was only 0.35%, indicating the reliability of the data.
Medium and coarse sand predominate in all samples (Table 2),
with an average of 184 ± 101 g$kg1 of fine sand and
602 ± 166 g$kg1 of coarse and medium sand. Some sites contain
more clay sediments (S-10/S-8/S-2/Sþ7).
The sediments present an average sand fraction of 60%, except
for the sample S0-2 with about 45% of silt-clay particles. In some
sites, bedrock was observed, particularly in sites whose water flux
was notably higher. Between sites S-10 to S-7 and Sþ6 to Sþ9, the
river is shallow (max. 50 cm).
The mean concentrations of metals were relatively low (Table 2).
Most of the metals have similar concentrations along the river, such
as Fe, Mn, Ti, Cu and Cr (only 7%e30% of variation among the 21
sites). On the other hand, high variability was observed in the Pb
and Zn concentrations, indicating a point source pollution in this
river, 375 m after the discharge of the effluent coming from the
plant. At this sampling site (Sþ3), Fe and Cu also have the highest
concentrations (Table 2). These data indicate a possible 300 m
displacement of the pollution after the end of metallurgical activ-
ities. The density of the pollutants (dense Pb slag) might explain the
slowness of the displacement.
The grain size of the sediments plays a significant role in the
dispersion of metals in aquatic ecosystems (Kalender & Çiçek Uçar,
2013). Several studies reported that metal content is higher in the
fine fraction of the sediment (silt þ clay, <0.063 mm) as compared
with the sandy fraction (Acosta et al., 2009; Ajmone-Marsan et al.,
2008; Hardy & Cornu, 2006; Silva et al., 2017). However, in our
study, no clear correlation was observed between the concentra-
tions of the metals and the grain-size distribution or the organic
matter concentration (coefficients of correlation always <0.3). The
presence of dense metals in the form of slag fragment residues in
the sandy fraction (visible at the naked eye) can explain it.
The national guideline values PV and IV (CONAMA, 2009, p. 81)
or sediment quality guidelines (SQG), i.e., probable effect concen-
tration (PEC) and threshold effect concentration (TEC) (Mac Donald
et al., 2000) are reference values. The concentrations of Cu are al-
ways lower than PV or IV, which are less restrictive. On the other
hand, the concentrations of Cr and Pb are generally (Cr) or some-
times (Pb) above the PV. The lithology, an essential factor in the
concentration of metals in soils (Gloaguen & Passe, 2017; Taghipour
et al., 2011), is not taken into consideration in these general values
of CONAMA. Regional effects such as the presence of chromic rocks
(Amorosi, 2012; L. M. R. dos Santos et al., 2017) may explain these
high Cr values. On the other hand, local pollution explains the peak
concentration of Pb (2506.9 mg$kg1) much higher than IVPb
(180 mg$kg1). Both situations exist in the case of Zn: Maximum
367
concentration at the same site as for Pb (pollution) and relatively
high values in the region. Since no significant background value for
Zn has been reported in the region, this suggests more extensive Zn
contamination. When compared to TEC and PEC, the previous
conclusions about Cu and Zn are the same, but in the case of Cr and
Pb, even higher contamination (anthropogenic or not) is detected.
In conclusion, regarding the toxicity of metals in the sediments,
comparisons with PV, VI, TEC and PEC values show similar results
with the exception at some sites, probably due to the different
databases used by CONAMA (2009, p. 81) and Mac Donald et al.
(2000). Although they provide a general idea of the possible
toxicity of the metals in sediments, these values do not consider the
natural geochemical background of the region, and so may over-
estimate or underestimate the geogenic or anthropogenic sources.
4. Discussion
4.1. Pollution load index and enrichment factor
We cannot use global values such as PV or TEC to quantify the
degree of pollution in a given region, because these values do not
represent a local geochemical background. They indicate a possible
effect of contamination on an ecosystem, but this contamination
can be anthropogenic as well as geogenic. Quantification of pollu-
tion is more accurate with a local natural geochemical background.
As previously explained, we used river sediments in the most
preserved area as the reference sample. After analyzing, we verified
that pollutant loads of Cu and Cr vary around 2.5 (up to 4 for Cr).
Pollutant loads are generally close to 10 for Zn and Pb, and some-
times above 100 (moderate to very high contamination).
In all the sites, the global pollution load index (PLIm) is always
greater than 1, with a maximum value of 23.3 (considering Pb, Zn,
Cr, and Cu) or 175.5 (considering Pb and Zn only). The PLIm of the
entire study area is 3.64, indicating that the Subae
River in this area
is moderate to highly contaminated (EF ¼ 5 to 10). Thus, the
contamination remained 20 years after the end of the smelting
activities. However, even using a local geochemical background, the
mCd or PLI does not precisely depict the situation, since the
mineralogy and geochemical variation of the sediments may
partially explain the observed variations. The approach by the
enrichment factor is therefore essential.
The enrichment factor can minimize the contribution of the
geological source: The normalization with a stable metal (e.g., Al)
allows to compare sandy sediments (with low aluminum content
and low metal adsorption capacity) and clay sediments (enriched in
aluminum and with higher adsorption capacity). For example, this
calculation reduces the effect of the natural enrichment of metals in
the clays. With this approach, most of the sites were classified as
low to moderately enriched by Pb (EF < 3, Fig. 3). With regard to Zn,
42% of the sites were classified as moderately enriched or more
(EF > 3). The correlation between EFPb and EFZn (coefficient: 0.87)
comes from the similar behavior of the two metals. In all of the
sites, except for two (moderate enrichment), sediments are not
enriched in Cu and Cr. The EF of the metals were as follows:
Zn > Pb > Cr > Cu. According to Zhang and Liu (2002), the EF values
below 1.5 indicate that the metal comes from natural geological
materials. EF values above 1.5 indicate that the sources of enrich-
ment may originate from an anthropogenic impact on the levels of
metals in the river. It was the case for Zn, with EF values generally
higher than 1.5.
368 T.V. Gloaguen et al. / International Journal of Sediment Research 36 (2021) 362e372

Fig. 3. Conventional (EF) and grain-size corrected (gEF) enrichment factors in the sediments of the Subae river downstream and upstream the Pb smelter.
 T.V. Gloaguen et al. / International Journal of Sediment Research 36 (2021) 362e372 369

4.2. Grain-size-corrected enrichment factor
For the assessment of environmental pollution, the choice of a
reference sample is the most critical parameter. The conclusion if
the sediment is or not polluted depends exclusively on it.
The use of a reference site in an unpolluted area, and sufficiently
close to the study area (similar geological setting), as in this study, is
a coherent approach. However, due to the dynamics of water and
sediments, the effect of season, and changes in land-use, finding a
local with no impact in a river can be questionable. Moreover, this
approach is a direct geochemical method (Dung et al., 2013;
Gałuszka, 2007) with only one reference. The use of global values
such as average Earth's crust or shale values (Aiman et al., 2016;
Hanif et al., 2016; Hasan et al., 2013; Pen~ a-Icart et al., 2016; Usese
et al., 2017; Wang et al., 2015; Zhang et al., 2009) guarantees un-
polluted data but they still are single values.
Grygar and Popelka (2016) proposed an alternative to obtain a
normalized reference sample and minimize the estimation error of
the enrichment factor, by calculating multiple regressions between
metal and other major and minor elements in pre-established non
impacted samples. Such integrated methods (combining
geochemical and statistical methods) are efficient but time-
consuming because of the requirement of a large dataset in pris-
tine areas where soils and concentrations are diversified.
On another way, high correlations between the natural concen-
tration of metals and texture in soils and sediments have been
related, as previously explained. Metals even appear to be more
dependent on soil texture than on soil taxonomic class (Gloaguen &
Passe, 2017; Kabata-Pendias et al., 1992; McGrath & Loveland, 1992).
So we calculated another enrichment factor, called grain-
corrected enrichment factor (gEF). In this integrated method, the
background is estimated for each sample (Table 3). This background
is established with the natural concentrations of metals in different
particle-size fractions of non-impacted soils under primary forest
(geochemical background), assuming that the bed river sediments
originate from the laminar erosion of the surrounding soils in the
Table 3
Individual geochemical background of Rio Subae sediments after grain-size
correction.
Sample Fe Ti Pb Zn Cr
watershed. We used the background concentrations of metals in
the sandy, silty and clayey soils of the watershed (Eq. (5)), obtained
in a previous study about natural background in this region
(Gloaguen & Passe, 2017). The authors sampled soils under native
vegetation in the main five geological sedimentary units, with ten
subsamples at 0e20 cm. Further details on the procedures of
sampling and analysis refer to the paper mentioned above.
The use of uncontaminated reference sediments instead of soils
may seem more appropriate, but, as explained previously, river
sediments accumulate all the contaminations of the watershed, so
finding a pristine area is usually a difficult task.
We compared the concentrations of metals in the samples with
these estimated backgrounds, by calculating CF, PLI, and Igeo. The
direct ratio [metal]sample/[metal]estimated background, called Local
Enrichment Factor by Grygar and Popelka (2016) is already a good
indicator. However, we still normalized with Ti and then calculated
EF, assuming that the accelerated geochemical cycles in humid
tropical environments could have differential effects on the dy-
namics of majors and trace elements, between the source (soils)
and the deposit (sediments).
The grain-corrected enrichment factor was calculated according
to Eq. (5):
½MS =½TiS
gEF ¼ (5)
½MREFEST =½TiREFEST
½MREFEST ¼ ½MSa :%sand þ ½MSi :%silt þ ½MC :%clay
where [M]S and [Ti]S are the concentrations of metal and titanium
in the river sediment; [M]REF-EST and [Ti]REF-EST are the reference
concentrations of metal and titanium, estimated from natural
concentrations in particle-size fractions from references non-
impacted soils in the watershed; [M]Sa is the concentration in the
sand fraction of reference soils (0.075e2 mm); [M]Si is the con-
centration in the silt fraction of reference soils (0.002e0.075 mm);
[M]C is the concentration in the clay fraction of reference soils
(<0.002 mm). The same corrected index can be used for mCd-
Cu
modified degree of contamination (Eq. (6)) and consequently PLI.

% % mg kg1

S-10 2.21 0.28 9.4 27.1 98.2 32.7 ½MS

S-9 2.00 0.25 8.5 25.1 95.8 32.3 gCd ¼ (6)
½MREFEST
S-8 2.75 0.35 11.3 33.2 104.8 33.6
S-7 1.83 0.23 7.8 23.3 93.7 32.0 This methodology provides more reliable results (Figs. 2 and 3).
S-6 1.95 0.24 8.2 24.9 95.2 32.2
S-5 2.02 0.25 8.4 25.8 96.1 32.3
A significant difference appears between the classic indexes and
S-4 1.97 0.25 8.3 25.1 95.5 32.3 the corrected indexes (Table 4 and Fig. 4). Corrected EF's and Cd's
S-3 1.43 0.17 6.5 18.4 88.7 31.4 are much closer to 1 for Cu and Cr, indicating no impact by these
S-2 2.75 0.35 11.1 33.9 105.0 33.6 two metals. These results are very reliable, and confirm the reality
S-1 1.43 0.17 6.5 18.6 88.8 31.4
of the context, because these two metals are found in low con-
S 1.70 0.21 7.4 21.6 92.1 31.8
Sþ1 2.07 0.26 8.6 26.2 96.7 32.4 centrations in the slag (de Andrade Lima & Bernardez, 2011). In
Sþ2 1.87 0.23 8.0 23.5 94.1 32.1 addition, there are no mines or industries involving metal pollution
Sþ3 1.60 0.19 7.0 20.8 90.9 31.6 in the study area (tens of kilometers). Thus, no contamination was
Sþ4 1.84 0.23 7.9 23.5 93.9 32.0 expected. The classic indexes overestimated the enrichment for
Sþ5 1.58 0.19 7.0 20.1 90.6 31.6
Sþ6 1.45 0.17 6.6 18.7 89.0 31.4
non-polluting metals: þ51% for Cu and þ49% for Cr. On the other
Sþ7 2.32 0.29 9.7 28.5 99.7 32.9 hand, it underestimated the impact of the polluting metals: The EF
Sþ8 2.23 0.28 9.2 28.1 98.7 32.7 values increased by 112% for Zn and by 19% for Pb after correction of
Sþ9 2.06 0.26 8.8 25.7 96.5 32.4 particle size distribution.
Sþ10 2.06 0.26 8.7 25.8 96.5 32.4
These results highlight the importance and accuracy of such a
Mean (SD) 1.96 (0.37) 0.24 (0.05) 8.3 (1.3) 24.7 (4.2) 95.3 (4.5) 32.2 (0.6)
Clayed soilsa 5.33 0.71 21.1 61.4 136.3 38.0 method, which could improve the assessment of pollution of fluvial
Silty soilsa 3.89 0.51 14.2 50.0 119.8 35.4 sediments. When calculating based on the natural concentrations
Sandy soilsa 1.23 0.14 5.8 16.2 86.3 31.0 in the surrounding soils, the real PLI is found to be higher (þ41%) if
a
Reference uncontaminated soils in the same geological units (Gloaguen & Passe, only Pb and Zn are considered, but lower (21%) if Cr and Cu are
2017). SD, standard deviation. included.
370 T.V. Gloaguen et al. / International Journal of Sediment Research 36 (2021) 362e372

Table 4
Pollution indexes (geometric mean) before correction (BC) and after correction (AC), and differences in % (D) between the indexes.

Cu Cr Zn Pb

BC AC D BC AC D BC AC D BC AC D
a
EF 2.03 1.00 51 2.04 1.04 49 3.10 6.58 þ112 4.48 5.34 þ19
mCdb 2.41 1.01 58 2.42 1.09 55 3.68 6.90 þ88 5.32 5.61 þ6

PLIc (Pb þ Zn) PLI (Pb þ Zn þ Cu þ Cr)

BC AC D BC AC D
4.42 6.22 þ41 3.27 2.58 21
a
Enrichment factor.
b
Modified contamination degree.
c
Pollution load index.

Fig. 4. Correlations between grain-size corrected EF and conventional EF.

5. Conclusions precise diagnostic, by revealing a higher contamination by Pb and

In the Subae river watershed, Northeastern Brazil, a lead smelter
has contaminated the entire environment (soil, air, water, fluvial
and estuarine sediments, food, population) from 1960 to 1993. We
show that stream sediments collected upstream or downstream
the smelter still have high concentrations of metals, primarily Pb
and Zn. The conventional approach for the assessment of contam-
ination, such as the estimation of pollution load index and
enrichment factor, revealed contamination by Pb and Zn but also by
Cu and Cr, in most of the studied area. This conventional first
approach consisted of a geochemical method, based on a single
background value of a presumed non impacted sediment. The new
integrated method, where the background value is estimated for
each sample, based on three particle-size fractions, allowed a more
Zn and at the same time by excluding the contamination by Cu and
Cr (these metals were not involved in the metallurgical process).
This new definition of backgrounds emphasized both an under-
estimated contamination of Pb (19%) and Zn (112%) and an over-
estimated contamination of Cu (51%) and Cr (49%). When data are
available, such an integrated approach could be applied for further
assessments of sediment and soil pollution.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
 T.V. Gloaguen et al. / International Journal of Sediment Research 36 (2021) 362e372 371

References Gloaguen, T. V., & Passe, J. J. (2017). Importance of lithology in defining natural
background concentrations of Cr, Cu, Ni, Pb and Zn in sedimentary soils,
northeastern Brazil. Chemosphere, 186, https://doi.org/10.1016/
Abrahim, G. M. S., & Parker, R. J. (2008). Assessment of heavy metal enrichment
j.chemosphere.2017.07.134
factors and the degree of contamination in marine sediments from Tamaki
Gomes, P., Valente, T., Braga, M. A. S., Grande, J. A., & De La Torre, M. L. (2016).
Estuary, Auckland, New Zealand. Environmental Monitoring and Assessment, 136,
Enrichment of trace elements in the clay size fraction of mining soils. Envi-
227e238, https://doi.org/10.1007/s10661-007-9678-2
ronmental Science and Pollution Research, 23(7), 6039e6045.
Acosta, J. A., Cano, A. F., Arocena, J. M., Debela, F., & Martínez-Martínez, S. (2009).
Grygar, T. M., & Popelka, J. (2016). Revisiting geochemical methods of distinguishing
Distribution of metals in soil particle size fractions and its implication to risk
natural concentrations and pollution by risk elements in fluvial sediments.
assessment of playgrounds in Murcia City (Spain). Geoderma, 149(1), 101e109,
Journal of Geochemical Exploration, 170, 39e57, https://doi.org/10.1016/
https://doi.org/10.1016/j.geoderma.2008.11.034
j.gexplo.2016.08.003
Acosta, J. A., Martínez-Martínez, S., Faz, A., & Arocena, J. (2011). Accumulations of
Hakanson, L. (1980). An ecological risk index for aquatic pollution control.a sedi-
major and trace elements in particle size fractions of soils on eight different
mentological approach. Water Research, 14(8), 975e1001, https://doi.org/
parent materials. Geoderma, 161(1e2), 30e42, https://doi.org/10.1016/
10.1016/0043-1354(80)90143-8
j.geoderma.2010.12.001
Han, D., Cheng, J., Hu, X., Jiang, Z., Mo, L., Xu, H., … Wang, H. (2017). Spatial dis-
Aiman, U., Mahmood, A., Waheed, S., & Malik, R. N. (2016). Enrichment, geo-
tribution, risk assessment and source identification of heavy metals in sedi-
accumulation and risk surveillance of toxic metals for different environ-
ments of the Yangtze River Estuary, China. Marine Pollution Bulletin, 115(1e2),
mental compartments from Mehmood Booti dumping site, Lahore city,
141e148, https://doi.org/10.1016/J.MARPOLBUL.2016.11.062
Pakistan. Chemosphere, 144, 2229e2237, https://doi.org/10.1016/
Han, L., Gao, B., Wei, X., Gao, L., Xu, D., & Sun, K. (2015). The characteristic of Pb
J.CHEMOSPHERE.2015.10.077
isotopic compositions in different chemical fractions in sediments from Three
Ajmone-Marsan, F., Biasioli, M., Kralj, T., Gr cman, H., Davidson, C. M.,
Gorges Reservoir, China. Environmental Pollution, 206, 627e635, https://doi.org/
Hursthouse, A. S., … Rodrigues, S. (2008). Metals in particle-size fractions of the
10.1016/j.envpol.2015.08.030
soils of five European cities. Environmental Pollution, 152(1), 73e81, https://
Hanif, N., Eqani, S. A. M. A. S., Ali, S. M., Cincinelli, A., Ali, N., Katsoyiannis, I. A., …
doi.org/10.1016/j.envpol.2007.05.020
Bokhari, H. (2016). Geo-accumulation and enrichment of trace metals in sedi-
Amorosi, A. (2012). Chromium and nickel as indicators of source-to-sink sediment
ments and their associated risks in the Chenab River, Pakistan. Journal of
transfer in a Holocene alluvial and coastal system (Po Plain, Italy). Sedimentary
Geochemical Exploration, 165, 62e70, https://doi.org/10.1016/
Geology, 280, 260e269, https://doi.org/10.1016/j.sedgeo.2012.04.011
J.GEXPLO.2016.02.006
de Andrade Lima, L. R. P., & Bernardez, L. A. (2011). Characterization of the lead
Hardy, M., & Cornu, S. (2006). Location of natural trace elements in silty soils using
smelter slag in Santo Amaro, Bahia, Brazil. Journal of Hazardous Materials,
particle-size fractionation. Geoderma, 133(3e4), 295e308, https://doi.org/
189(3), 692e699, https://doi.org/10.1016/j.jhazmat.2011.02.091

, P., Zurbrick, C. M., Boyle, E. A., & Santos, W. P. C. 10.1016/j.geoderma.2005.07.015
Andrade, R. L. B., Hatje, V., Masque
Hasan, A. B., Kabir, S., Selim Reza, A. H. M., Nazim Zaman, M., Ahsan, A., & Rashid, M.
(2017). Chronology of anthropogenic impacts reconstructed from sediment
(2013). Enrichment factor and geo-accumulation index of trace metals in sed-
records of trace metals and Pb isotopes in Todos os Santos Bay (NE Brazil).
iments of the ship breaking area of Sitakund Upazilla (BhatiaryeKumira),
Marine Pollution Bulletin, 125(1e2), 459e471, https://doi.org/10.1016/
Chittagong, Bangladesh. Journal of Geochemical Exploration, 125, 130e137,
j.marpolbul.2017.07.053
https://doi.org/10.1016/J.GEXPLO.2012.12.002
Apitz, S. E., Degetto, S., & Cantaluppi, C. (2009). The use of statistical methods to
Ji, Y., Feng, Y., Wu, J., Zhu, T., Bai, Z., & Duan, C. (2008). Using geoaccumulation index
separate natural background and anthropogenic concentrations of trace ele-
to study source profiles of soil dust in China. Journal of Environmental Sciences,
ments in radio-chronologically selected surface sediments of the Venice
20(5), 571e578, https://doi.org/10.1016/S1001-0742(08)62096-3
Lagoon. Marine Pollution Bulletin, 58(3), 402e414, https://doi.org/10.1016/
Kabata-Pendias, A., Dudka, S., Chlopecka, A., & Gawinowska, T. (1992). Background
J.MARPOLBUL.2008.10.007
levels and environmental influences on trace metals in soils of the temperate
Asmus, H. E., & Ponte, F. C. (1973). The Brazilian marginal basins. In The south
humid zone of Europe. In D. C. Adriano (Ed.), Biogeochemistry of trace metals
atlantic (pp. 87e133). Boston, MA: Springer US, https://doi.org/10.1007/978-1-
(pp. 61e84). Boca Raton: Lewis Publisher.
4684-3030-1_3

glementation Kalender, L., & Çiçek Uçar, S. (2013). Assessment of metal contamination in sedi-
Baize, D. (2002). Examen critique des valeurs limites ‘sols’ de la re
ments in the tributaries of the Euphrates River, using pollution indices and the
française. In INRA. In Les
el

ements traces m
etalliques dans les sols. Approches
determination of the pollution source, Turkey. Journal of Geochemical Explora-
fonctionnelles et spatiales (p. 570). Paris: INRA.
tion, 134, 73e84, https://doi.org/10.1016/J.GEXPLO.2013.08.005
Bhuiyan, M. A. H., Parvez, L., Islam, M. A., Dampare, S. B., & Suzuki, S. (2010). Heavy
Kaushik, A., Kansal, A., Santosh, M., Kumari, S., & Kaushik, C. P. (2009). Heavy metal
metal pollution of coal mine-affected agricultural soils in the northern part of
contamination of river yamuna, Haryana, India: Assessment by metal enrich-
Bangladesh. Journal of Hazardous Materials, 173(1e3), 384e392, https://doi.org/
ment factor of the sediments. Journal of Hazardous Materials, 164(1), 265e270,
10.1016/J.JHAZMAT.2009.08.085
https://doi.org/10.1016/j.jhazmat.2008.08.031
Bini, C., Sartori, G., Wahsha, M., & Fontana, S. (2011). Background levels of trace
Li, C., Ma, T., & Shi, J. (2003). Application of a fractal method relating concentrations
elements and soil geochemistry at regional level in NE Italy. Journal of
and distances for separation of geochemical anomalies from background.
Geochemical Exploration, 109(1e3), 125e133, https://doi.org/10.1016/
Journal of Geochemical Exploration, 77(77), 167e175, https://doi.org/10.1016/
J.GEXPLO.2010.07.008
~o, V. S0375-6742(02)00276-5
Bomfim, M. R., Santos, J. A. G., Costa, O. V., Otero, X. L., Boas, G., da, S. V., Capela
Mac Donald, D. D., Ingersoll, C. G., & Berger, T. A. (2000). Development and evalu-
da S., … Nacif, P. G. S. (2015). Genesis, characterization, and classification of

river basin, Bahia, Brazil. Revista Brasileira de ation of consensus based sediment quality guidelines for fresh water ecosys-
mangrove soils in the Subae
tems. Archives of Environmental Contamination and Toxicology, 39(20e31),
Ci^encia do Solo, 39(39), 1247e1260, https://doi.org/10.1590/
20e31. 39.
01000683rbcs20140555
Matschullat, J., Ottenstein, R., & Reimann, C. (2000). Geochemical backgrounddcan
BRASIL. (1981). Ministerio das minas e energia. In Secretaria geral. Projeto radam-
we calculate it? Environmental Geology, 39(9), 990e1000.
brasil. Folha SD.24 salvador: Geologia, geomorfologia, pedologia, vegetacao, uso
McGrath, S. P., & Loveland, P. J. (1992). The soil geochemical Atlas of England and
portencial da terra.
wales (blackie Ac). Blackie Academic & Professional.
Chen, Z., Chen, J., Tian, S., & Xu, B. (2017). Application of fractal content-gradient
Milani, E. J., Rangel, H. D., Bueno, G. V., Stica, J. M., Winter, W. R., Caixeta, J. M., &
method for delineating geochemical anomalies associated with copper occur-
Neto, O. da C. (2007). Brazilian sedimentary basins - stratigraphic charts.
rences in the Yangla ore field, China. Geoscience Frontiers, 8(1), 189e197, https://
Boletim de Geociencias da Petrobras, 1, 183e205.
doi.org/10.1016/J.GSF.2015.11.010
Mohriak, W. U. (2003). Sedimentary basins of the Brazilian continental margin. In
Cheng, Q. (1999). Spatial and scaling modelling for geochemical anomaly separa-
L. A. Bizzi, C. Schobbenhaus, & W. U. Mohriak (Eds.), Geologia, Tecto ^nica e
tion. Journal of Geochemical Exploration, 65(3), 175e194, https://doi.org/10.1016/
Recursos Minerais do Brasil (pp. 87e94). CPRM.
S0375-6742(99)00028-X
~o CONAMA Motta, P. N. D. S., Gloaguen, T. V., Couto, C. F., Merdy, P., & Lucas, Y. (2018).
CONAMA - Conselho Nacional do Meio Ambiente. (2009). Resoluça
Hydrogeochemistry of the Subae
River impacted by lead smelting activities ,
No420. pub. L. No. 420. Brazil: Dia
rio Oficial da Uni~ ao no 249.
Bahia state , Brazil: Geochemical characterization and fluxes of metals. Water,
Dung, T. T. T., Cappuyns, V., Swennen, R., & Ky Phung, N. (2013). From geochemical
Air, and Soil Pollution, 229, 387.
background determination to pollution assessment of heavy metals in sedi-
Motta, P. N. S. D., Gloaguen, T. V., Santos, M. S. T., Ferreira, A. T. da S., & Motta, T. O.
ments and soils. Reviews in Environmental Science and Biotechnology, 12,
(2017). Morphometric analysis of river basin of Subae
, Bahia, brasil. Ambi^
encia,
335e353, https://doi.org/10.1007/s11157-013-9315-1
13(2), 470e485, https://doi.org/10.5935/ambiencia.2017.02.14
Gao, B., Liu, Y., Sun, K., Liang, X., Peng, P., Sheng, G., & Fu, J. (2008). Precise
Muller, G. (1969). Index of geoaccumulation in sediments of the rhine river. Geo-
determination of cadmium and lead isotopic compositions in river sediments.
journal, 2(3), 108e118.
Analytica Chimica Acta, 612(1), 114e120, https://doi.org/10.1016/
Parsa, M., Maghsoudi, A., Yousefi, M., John, E., & Carranza, M. (2017). Multifractal
J.ACA.2008.02.020
interpolation and spectrumearea fractal modeling of stream
Gałuszka, A. (2007). A review of geochemical background concepts and an example
sediment geochemical data: Implications for mapping exploration targets.
using data from Poland. Environmental Geology, 52, 861e870, https://doi.org/
Journal of African Earth Sciences, 128, 5e15, https://doi.org/10.1016/
10.1007/s00254-006-0528-2
j.jafrearsci.2016.11.021
Gałuszka, A., & Migaszewski, Z. M. (2011). Geochemical background e an envi-
Pejman, A., Nabi Bidhendi, G., Ardestani, M., Saeedi, M., & Baghvand, A. (2015).
ronmental perspective. Mineralogia, 42(1), 7e17, https://doi.org/10.2478/
A new index for assessing heavy metals contamination in sediments: A case
v10002-011-0002-y
372 T.V. Gloaguen et al. / International Journal of Sediment Research 36 (2021) 362e372
study. Ecological Indicators, 58, 365e373, https://doi.org/10.1016/
j.ecolind.2015.06.012
Pen~ a-Icart, M., Pereira-Filho, E. R., Lopes Fialho, L., No
brega, J. A., Alonso-
Herna
ndez, C., Bolan ~ os-Alvarez, Y., & Pomares-Alfonso, M. S. (2016).
Combining contamination indexes, sediment quality guidelines and multivar-
iate data analysis for metal pollution assessment in marine sediments
of Cienfuegos Bay, Cuba. Chemosphere. , https://doi.org/10.1016/
j.chemosphere.2016.10.053

rez-Sirvent, C., Martínez-Sa
Pe
nchez, M. J., García-Lorenzo, M. L., Molina, J., &
Tudela, M. L. (2009). Geochemical background levels of zinc, cadmium and
mercury in anthropically influenced soils located in a semi-arid zone (SE,
Spain). Geoderma, 148(3e4), 307e317, https://doi.org/10.1016/
J.GEODERMA.2008.10.017
Qi, S., Rueckert, P., & Di, Z. (2010). Geochemical sources, deposition and enrichment
of heavy metals in short sediment cores from the Pearl River Estuary, Southern
China. Journal of Marine Systems, 82, S28eS42, https://doi.org/10.1016/
J.JMARSYS.2010.02.003
Reimann, C., & de Caritat, P. (2005). Distinguishing between natural and anthro-
pogenic sources for elements in the environment: Regional geochemical sur-
veys versus enrichment factors. The Science of the Total Environment, 337(1),
91e107, https://doi.org/10.1016/j.scitotenv.2004.06.011
Reimann, C., & Garrett, R. G. (2005). Geochemical background concept and reality.
The Science of the Total Environment, 350, 12e27, https://doi.org/10.1016/
j.scitotenv.2005.01.047
Saeedi, M., & Jamshidi-Zanjani, A. (2015). Development of a new aggregative
index to assess potential effect of metals pollution in aquatic sediments.
Ecological Indicators, 58, 235e243, https://doi.org/10.1016/J.ECOLIND.2015.05.
047
dos Santos, L. M. R., Gloaguen, T. V., Fadigas, F. de S., Chaves, J. M., & Martins, T. M. O.
(2017). Metal accumulation in soils derived from volcano-sedimentary rocks,
Rio Itapicuru Greenstone Belt, northeastern Brazil. The Science of the Total
Environment, 601e602, 1762e1774, https://doi.org/10.1016/j.scitotenv.2017.06.
035
de OliveiraSantos, L. T. S., & Jesus, T. B. (2014). Caracterizaç~ao de metais pesados das


aguas superficiais da bacia do Rio Subae
(Bahia). Geochimica Brasiliensis, 28(2),
137e148.
Silva, G. S., Gloaguen, T. V., Couto, C. F., & Motta, P. N. S. D. (2017). Persistence and
mobility of metals in an estuarine environment 25 years after closure of a lead
smelter, Bahia State, Brazil. Environmental Earth Sciences, 76(16), https://doi.org/
10.1007/s12665-017-6886-0
Silvany-Neto, A. M. M., Carvalho, F. M. M., Chaves, M. E. C. E. C., Branda ~o, A. M. M., &
Tavares, T. M. M. (1989). Repeated surveillance of lead poisoning among chil-
dren. The Science of the Total Environment, 78(C), 179e186, https://doi.org/
10.1016/0048-9697(89)90032-6
da Silva, Soares, G., Gloaguen, T. V., Couto, C. F., & Motta, P. N. S. D. (2017). Persis-
tence and mobility of metals in an estuarine environment 25 years after closure
of a lead smelter, Bahia State, Brazil. Environmental Earth Sciences, 76(16),
https://doi.org/10.1007/s12665-017-6886-0
Sinex, S., & Helz, G. (1981). Regional geochemistry of trace elements in Chesapeake
bay sediments. Environmental Geology, 3(6), 315e323.
Smith, H. (1995). Pollution prevention policies for agricultural soils in The
Netherlands. In INRA (Ed.), III int. Conf. Biogeochim. Trace elements. Paris.
Empresa Brasileira de Pesquisa Agropecua
ria. (2011). In E. Solos (Ed.), Manual de
m
etodos de ana
lises de solos (2nd ed.). Rio de Janeiro: Embrapa Solos.
de Souza Guerra, C., Magna, G. A. M., Machado, S. L., De Capitani, E. M., Ramos, J.,
Peixoto, I. T. A., … de Fa
tima Carvalho, M. (2015). Lead concentrations in whole
blood, serum, saliva and house dust in samples collected at two time points (12
months apart) in Santo Amaro, BA, Brazil. Environmental Research, 142,
337e344, https://doi.org/10.1016/j.envres.2015.05.023
Spijker, J. (2012). The Dutch soil type correction - an alternative approach.
Sucharova , J., Suchara, I., Hola, M., Marikova, S., Reimann, C., Boyd, R., …
Englmaier, P. (2012). Top-/bottom-soil ratios and enrichment factors: What do
they really show? Applied Geochemistry, 27(1), 138e145, https://doi.org/10.1016/
j.apgeochem.2011.09.025
Tomlinson, D. C., Wilson, J. G., Harris, C. R., & Jeffery, D. W. (1980). Problems in the
assessment of heavy metals levels in estuaries and the formation of a pollution
index. Helgola €nderWissenschaftliche Meeresuntersuchungen, 33, 566e575.
Usese, A., Chukwu, O. L., Rahman, M. M., Naidu, R., Islam, S., & Oyewo, E. O. (2017).
Enrichment, contamination and geo-accumulation factors for assessing arsenic
contamination in sediment of a Tropical Open Lagoon, Southwest Nigeria.
Environmental Technology & Innovation, 8, 126e131, https://doi.org/10.1016/
J.ETI.2017.06.006
VLAREBO. (2007). Order of the flemish government of 14 december 2007 establishing
the flemish soil remediation and protection regulations title.
Wang, Z., Wang, Y., Chen, L., Yan, C., Yan, Y., & Chi, Q. (2015). Assessment of metal
contamination in coastal sediments of the Maluan Bay (China) using
geochemical indices and multivariate statistical approaches. Marine Pollution
Bulletin, 99(1e2), 43e53, https://doi.org/10.1016/J.MARPOLBUL.2015.07.064
Xie, X., & Cheng, H. (2014). Sixty years of exploration geochemistry in China. Journal
of Geochemical Exploration, 139, 4e8, https://doi.org/10.1016/
j.gexplo.2013.06.013
Xu, Y., Sun, Q., Ye, X., Yin, X., Li, D., Wang, L., … Li, Y. (2017). Geochemical analysis of
sediments from a semi-enclosed bay (Dongshan Bay, southeast China) to
determine the anthropogenic impact and source. Chemosphere, 174, 764e773,
https://doi.org/10.1016/j.chemosphere.2017.01.081
Zaborska, A. (2014). Anthropogenic lead concentrations and sources in Baltic Sea
sediments based on lead isotopic composition. Marine Pollution Bulletin, 85(1),
99e113, https://doi.org/10.1016/J.MARPOLBUL.2014.06.013
Zahra, A., Hashmi, M. Z., Malik, R. N., & Ahmed, Z. (2014). Enrichment and geo-
accumulation of heavy metals and risk assessment of sediments of the Kur-
ang Nallahdfeeding tributary of the Rawal Lake Reservoir, Pakistan. The Science
of the Total Environment, 470e471, 925e933, https://doi.org/10.1016/
J.SCITOTENV.2013.10.017
Zhang, W., Feng, H., Chang, J., Qu, J., Xie, H., & Yu, L. (2009). Heavy metal contam-
ination in surface sediments of Yangtze River intertidal zone: An assessment
from different indexes. Environmental Pollution, 157(5), 1533e1543, https://
doi.org/10.1016/j.envpol.2009.01.007
Zhang, Z., Juying, L., Mamat, Z., & QingFu, Y. (2016). Sources identification and
pollution evaluation of heavy metals in the surface sediments of Bortala River,
Northwest China. Ecotoxicology and Environmental Safety, 126, 94e101, https://
doi.org/10.1016/J.ECOENV.2015.12.025
Zhang, J., & Liu, C. L. (2002). Riverine composition and estuarine geochemistry of
particulate metals in Chinadweathering features, anthropogenic impact and
chemical fluxes. Estuarine. Coastal and Shelf Science, 54(6), 1051e1070, https://
doi.org/10.1006/ECSS.2001.0879
Zhao, F. J., McGrath, S. P., & Merrington, G. (2007). Estimates of ambient background
concentrations of trace metals in soils for risk assessment. Environmental
Pollution, 148(1), 221e229, https://doi.org/10.1016/J.ENVPOL.2006.10.041
Zhiyuan, W., Dengfeng, W., Huiping, Z., & Zhiping, Q. (2011). Assessment of soil
heavy metal pollution with principal component analysis and geoaccumulation
index. Procedia Environmental Sciences, 10, 1946e1952, https://doi.org/10.1016/
J.PROENV.2011.09.305