Sie sind auf Seite 1von 13

Environ Monit Assess (2013) 185:6173–6185

DOI 10.1007/s10661-012-3015-0

Mobility and ecological risk assessment of trace metals


in polluted estuarine sediments using a sequential
extraction scheme
F. A. B. Canuto & C. A. B. Garcia & J. P. H. Alves &
E. A. Passos

Received: 14 April 2012 / Accepted: 20 November 2012 / Published online: 7 December 2012
# Springer Science+Business Media Dordrecht 2012

Abstract The three-stage sequential extraction proce- Introduction


dure for the fractionation of Cd, Cr, Cu, Ni, Pb, and Zn,
proposed by the Commission of the European Estuarine and coastal areas are often regions of high
Communities Bureau of Reference, was applied to sed- population density and intensive human activity. As a
iment five samples collected from the Sal estuary, result, elevated levels of trace metals in sediments can
Sergipe State, northeast Brazil, in September 2009. reflect the impacts of industrial activities and urban
The method showed satisfactory recoveries, detection development (Fang et al. 2005). Metal accumulation
limits, and standard deviations for determinations of in sediments poses an environmental problem due to
trace metals in the sediments. Cd and Pb were the metals possible metal transfer from the sediments to aquatic
most prevalent in the bioavailable fractions (carbonates, media (Filgueiras et al. 2002).
Fe and Mn oxides, organic matter, and sulfides), while The total sediment concentration of a metal does
Ni, Zn, Cu, and Cr showed higher percentages in the not provide information concerning its mobility, avail-
inert fraction. The order of mobility of the metals was ability, or toxicity (Rauret et al. 1999). Toxicity is
Cd (66 %) > Pb (65 %) > Zn (59 %) > Ni (57 %) = Cr dependent on the amount of metal available for bio-
(57 %) > Cu (56 %). Possible toxicity related to these accumulation (accumulation by biological organisms),
metals was examined using the risk assessment code, and is determined by those sediment properties that
and by comparing the chemical data with sediment affect its bioavailability (Ure et al. 1993). Hence, it is
quality guideline ERL-ERM values. Results obtained possible for a sediment to be metal-contaminated (to
using the two methods were in agreement, and showed have a metal content higher than the natural back-
low to medium risk for all metals, indicating that ad- ground), but not manifest any toxic effects, depending
verse effects on aquatic biota should rarely occur. on the geochemical processes that control the avail-
ability of the metal in the sediment (Passos et al. 2011;
Keywords Trace metal . Sediment . Sequential Silva et al. 2012).
extraction . Risk assessment code (RAC) . Sediment Sequential extraction is a well-established approach
quality guidelines (SQG) for the investigation of different forms of trace metals
in soils and sediments. Several sequential fractionation
F. A. B. Canuto : C. A. B. Garcia : J. P. H. Alves : procedures have been suggested to identify element
E. A. Passos (*) distributions in operationally defined pools that in-
Laboratório de Química Analítica Ambiental, Departamento
clude water-soluble species and recalcitrant forms
de Química, Universidade Federal de Sergipe,
49.100-000 São Cristóvão, SE, Brazil immobilized in mineral lattices (Rauret et al. 1999).
e-mail: elisapassos@gmail.com Many of these are variants on the scheme proposed by
6174 Environ Monit Assess (2013) 185:6173–6185

Tessier et al. (1979). However, it is difficult to com- is more recent. Locations where metals are significant-
pare the results obtained by procedures that employed ly associated with the oxidizable or reducible sediment
different sequences of reagents or different conditions. fractions are influenced by pollution that is less recent
For this reason, the Standards, Measurements and (Passos et al. 2010).
Testing Programme (SM&T), formerly known as the The risk assessment code (RAC) has been used to
European Community Bureau of Reference (BCR), assess environmental risks and estimate possible dam-
has proposed a sequential extraction procedure in or- age to benthic organisms caused by contaminated
der to harmonize and standardize the different techni- sediments (Arcega-Cabrera et al. 2009; Ishikawa et
ques used to fractionate metals in soils and sediments al. 2009; Trujillo-Cardenas et al. 2010; Passos et al.
(Ure et al. 1993). 2010; 2011). The RAC considers the metal fraction
The BCR protocol fractionates the metals into acid- that is exchangeable and associated with carbonates.
soluble/exchangeable, reducible, and oxidizable This fraction is most influenced by human activity,
phases. The acid-soluble/exchangeable fraction with the metals being weakly retained and able to
includes the metals that are precipitated (or co- equilibrate with the aqueous phase, hence becoming
precipitated) with carbonate, and is affected by pH more rapidly bioavailable. The RAC classification
changes. The reducible fraction contains metals asso- scheme defines risk levels as zero, low, medium, high,
ciated with Fe-Mn oxides, which can be dissolved by and very high, depending on the percentage of metal
changes in redox potential. In the oxidizable fraction, found in the exchangeable fraction (Perin et al. 1985;
metals may be associated, through complexation or Ikem and Adisa 2011).
bioaccumulation processes, with various forms of or- The Sediment Quality Guidelines (SQG) system,
ganic material including living organisms, detritus, or developed by Long and Morgan (1990), has been
coatings on mineral particles. In this fraction, the adopted as an informal tool to evaluate sediment
metals can remain in the sediment for lengthy periods, chemical data in relation to possible adverse effects
with mobilization occurring during decomposition un- on aquatic biota. ERL (effects range—low) and ERM
der oxidizing conditions (Filgueiras et al. 2002). (effects range—mean) concentrations have been estab-
The BCR procedure is one of the most popular lished for eight metals and metalloids (As, Cd, Cr, Cu,
extraction techniques, and has been widely applied to Pb, Ni, Ag, and Zn). These reflect the concentrations
soils, sediments, and standard reference materials at which toxicity could begin to be observed (ERL),
(Mossop and Davidson 2003; Yuan et al. 2004). The and above which adverse effects may occur (ERM)
method is reproducible, and provides good recoveries (Long and Morgan 1990; Amin et al. 2009; Garcia et
when compared to full acid dissolution. Sediment al. 2011).
reference materials (CRM 601 and 701) are available The indiscriminate release of untreated domestic
that are certified for metals extracted by the procedure and industrial wastewater constitutes one of the main
(Zemberyov et al. 2006). factors of degradation of aquatic ecosystems located
Fractionation studies are not only very useful for near major urban centers and may contribute to the
determining the degree of association of metals in increase of the concentrations of the trace metals in
sediments, and to what extent the metals may be these environments (Passos et al. 2005). The study
remobilized into the environment, but also for distin- area—the Sal River estuary is polluted by different
guishing those metals with lithogenic origins from types of industrial and agricultural drainage and do-
those with anthropogenic origins (Jain 2004). mestic wastewater from other resources of metal pol-
According to Rubio et al. (2000), metals with anthro- lution, such as car washes, pesticides from agricultural
pogenic origins are mainly found in the first three areas, runoff, and so on (Barbier et al. 2010).
extraction fractions (soluble in acid, associated with The main objectives of the present study were: (a)
Fe and Mn oxides, and associated with organic matter to determine the distributions of the trace metals Cd,
and sulfides), while metals with lithogenic origins are Cr, Cu, Ni, Pb, and Zn in surface sediments of the Sal
found in the residual fraction obtained in the last stage River estuary (Sergipe State, northeast Brazil), using
of the extraction process. Regions where the metals the optimized BCR sequential extraction protocol, and
are weakly associated with sediments, and show an hence to ascertain their mobility; (b) to define the
affinity for carbonate, have experienced pollution that natural and/or anthropogenic origins of the metals,
Environ Monit Assess (2013) 185:6173–6185 6175

based on contents in the first three sediment fractions; are municipal and industrial wastewaters, agricultural
(c) to perform a risk assessment for each metal, based runoff, and especially metal industries (Barbieri et al.
on RAC values; and (d) to evaluate possible toxicity, 2007; Garcia et al. 2009).
based on ERL–ERM values.
Sample collection and pre-treatment

Materials and methods Sediment samples were collected during September


2009, at five sites located in industrial, residential,
Study area commercial, and rural zones of the Sal estuary, using
a core sampler composed of cellulose acetate butyrate
The Sal River, located in Sergipe State, northeast (Fig. 1). Site information is provided in Table 1. The
Brazil, is part of the Sergipe River hydrographic basin, undisturbed top 5 cm of the sediment was sampled and
which covers an area of 3,673 km2, drains approxi- placed in acid-rinsed polypropylene vessels using a
mately 16.7 % of the State, and has average flows of plastic spatula. Three samples were taken at each
560,000 and 70,000 m3 day−1 in the rainy and dry location. The sediments were oven-dried (at 50 °C
seasons, respectively. Since the 1990s, there has been for 12 h), homogenized in a porcelain mortar, sieved
rapid expansion of aquacultural, industrial, and agri- (using a 2-mm mesh size), and stored in plastic con-
cultural activities in the region, with simultaneous tainers until the analyses were performed.
developments in civil construction, transportation,
and tourism; such dramatic changes have adversely Reagents
affected the water quality in the estuary (Alves et al.
2007; Barbieri et al. 2007). All reagents were either analytical grade or Suprapur
The study area extended over 8 km, covering the quality (Merck, Darmstadt, Germany). Ultrapure wa-
lower part of the Sal River estuary (Fig. 1). The Sal is ter (18 MΩ cm) was supplied from a Millipore Milli-Q
formed after the confluence of the Sergipe river. The system. All glassware and plastic utensils were
main sources of trace metal contaminants in this area washed with 10 %v/v nitric acid for 48 h, and rinsed

Fig. 1 Locations of sampling sites in the Sal River estuary


6176 Environ Monit Assess (2013) 185:6173–6185

Table 1 Location, water depth,


temperature, and pH for each Site Longitude (E) Latitude (N) Water depth (m) Temperature (°C) pH TOC (%)
sampling site, and total organic
carbon (TOC) contents of the 1 10°51′50.6″ 37°05′0.6″ 5.60 26.5 7.79 1.24
sediment samples 2 10°52′13.2″ 37°03′45.8″ 11.4 27.5 7.69 3.49
3 10°52′03.8″ 37°03′41.2″ 5.90 27.3 7.70 1.19
4 10°51′43.5″ 37°03′0.5″ 3.30 27.0 7.89 0.82
5 10°52′03.6″ 37°02′12.3″ 14.0 27.3 7.97 2.52

with ultrapure water prior to use. Stock metal standard in 10 mL of 0.5 molL−1 HCl, and the final volume was
solutions (1,000 mgL−1) were prepared from standard made up to 50 mL (Passos et al. 2010). The solutions
vials (Tritisol, Merck) containing 1.000±0.002 g of were stored in polyethylene flasks for later determina-
metal in 2 % (v/v) nitric acid. Calibration standards of tion of metals using either flame or graphite furnace
each metal were obtained by suitable dilutions of the atomic absorption spectrometry.
stock solutions. Three certified reference materials, Calculation of the limit of detection (LOD) for each
NCS DC 75304 (China river sediment), NCS DC metal was based on the expression 3 s/b, where s is the
78301 (China marine sediment), and BCR-701 EUR standard deviation of the blank, and b is the slope of
19775 (river sediment), plus one reference material, the calibration graph (Miller and Miller 1993). Ten
LKSD-1 CCNRP (Canada lake sediment), were ana- extraction procedure blanks were analyzed. The LOD
lyzed for quality control purposes. values took into account the use of 1 g portions of
sample in the extractions, and any necessary dilutions.
Instrumentation The calibration curve correlation coefficients (r) were
better than 0.998 for all elements studied. The results
Sediment extractions were conducted using an end- showed that there was no significant analytical con-
over-end mechanical shaker (CINTEC CT 712–R). A tamination, and that LOD values varied from 0.002
centrifuge (Janetzsk T23) was used to obtain the su- (Cd) to 0.100 (Pb)μgg−1.
pernatant extracts. PTFE vessels were used throughout The efficiency of the sequential extraction method
the entire procedure. Additional items of equipment was determined by analysis of four replicates of river
were a pH meter (Digimed, DM20), a water bath sediment (NCS DC 75304/China) and marine sedi-
(Marconi, MA 156), and a digester block (Techal, ment (NCS DC 78301/China) certified reference mate-
TE007A). rials. The recoveries of the metals from the reference
Analyses were performed using an atomic absorp- materials were in the range 92–106 %.
tion spectrometer (Shimadzu AA6800) equipped with
both flame and graphite furnace atomization, D2 back- Partial metals extraction
ground correction, and an autosampler. All absorbance
readings were made in triplicate. The operating param- Partial metal concentrations were determined using US
eters for the individual metals were set as recommen- EPA Method 200.8. Samples (ca. 1 g) were treated in
ded in the manufacturer’s operating manual. The closed Teflon vessels using 4 mL of (1+1) HNO3 solu-
following wavelengths (nm) were used: Cd, 228.8; tion and 10 mL of (1+5) HCl solution. The mixtures
Cu, 324.8; Cr, 357.9; Ni, 232.0; Pb, 283.3; and Zn, were heated at 95 °C for 30 min. Following extraction,
213.9. the samples were filtered using quantitative filter paper,
transferred to 50-mL volumetric flasks, and the volumes
Total metals extraction were made up using ultra-pure water. The solutions were
stored in polyethylene flasks prior to the determination
For total metals extractions, samples (∼0.5 g) were of metals using flame or graphite furnace atomic absorp-
digested in closed Teflon vessels with 2 mL of HNO3, tion spectrometry (Garcia et al. 2009).
1 mL of HCl, and 4 mL of HF, heated to 140 °C for 2 h. Ten blank solutions were prepared in the same way
After cooling, the vessels were opened and heated at as samples during the digestion procedure, and for
210 °C to complete dryness. The residue was dissolved quality control purposes a lake sediment reference
Environ Monit Assess (2013) 185:6173–6185 6177

material (LKSD-1 CCNRP/Canada) was analyzed extracts was checked by analysis of four replicates of
alongside the samples. LOD values (in μgg−1) varied certified sediment reference material (BCR-701 EUR
from 0.001 (Cd) to 0.080 (Pb). Recoveries of the trace 19775). The BCR-701 analysis was performed as part
metals were in the range 97–103 %. of the batch, at the same time as the sample analyses.
The measured contents of the elements were compared
Sequential extraction procedure with the certified extractable contents of Cd, Cr, Cu,
Ni, Pb, and Zn. Recoveries of the trace metals varied
The optimized BCR sequential extraction procedure from 85 to 117 % for the first fraction (F1), from 93 to
was applied, in quadruplicate, to 1.00 g portions of dried 105 % for the second fraction (F2), from 95 to 114 %
sediment, using the reagents and experimental condi- for the third fraction (F3), and from 111 to 115 % for
tions briefly summarized in Table 2. Details of the the residual fraction (R).
optimized BCR extraction procedure can be found else-
where (Passos et al. 2010, 2011). This extraction proce- Statistical analysis
dure fractionates metals into: (a) an acid soluble fraction
(F1) consisting of exchangeable metals, and metals One-way analysis of variance and Tukey’s multiple
bound to carbonates, which are easily released to the comparison test were employed (using Origin v. 7.0)
water column; (b) a reducible fraction (F2) which con- to test for significant differences (p≤0.05) between the
sists of metals bound to iron and manganese oxyhydr- concentrations of metals in the different sediments. An
oxides, which can be released when redox conditions α value of 0.05 was adopted as the critical level for all
change; and (c) an oxidizable fraction (F3) that repre- statistical testing (giving a 95 % confidence level).
sents the metal bound to organic matter and sulfides,
which can be released under oxidizing conditions.
The optimized BCR protocol was used to obtain Results and discussion
information on the non-residual speciation of the metals.
The fourth fraction, obtained by digestion of the residue Partitioning of trace metals in the sediments
from the third fraction extraction, provides an indication
of the contents of metals associated with the residual Chemical fractionation is very useful for distinguish-
components of the sediment matrix (Rauret et al. 1999). ing metals with lithogenic origins from those with
A mixture of concentrated acids (as described in Total anthropogenic origins. Metals from anthropogenic
metals extraction section) was used to leach all the sources are mainly contained in the earlier extractions,
metals remaining in the residue (Passos et al. 2010). while those from lithogenic sources are present in the
For each extraction stage, the limits of detection residual fraction (Rubio et al. 2000; Passos et al.
were determined from the standard calibration curves 2010).
of each element. The LOD values varied from Table 3 provides the extract contents of Cd, Cr, Cu,
0.001 μgg−1 (Cd, first fraction) to 0.100 μgg−1 (Pb, Ni, Pb, and Zn (as μgg−1, on a dry mass basis) for
residual fraction). The accuracy of the analytical pro- each step of the BCR sequential extraction procedure,
cedures for metal determination in the different the sum of contents for four fractions (ΣF1+F2+F3+

Table 2 Summary of the optimized BCR sequential extraction protocol

Step Fraction Reagents/conditions Extracted phases

1 F1: exchangeable and Acetic acid (0.11 mol/L); pH 2.85; 16 h Soluble forms, exchangeable metals,
acid soluble and metals bound to carbonates
2 F2: reducible Hydroxyl ammonium chloride (0.5 mol/L); pH 1.5 Metals bound to iron and manganese
oxyhydroxides
3 F3: oxidizable Hydrogen peroxide (8.8 mol/L); 2 h at 85 °C; Metals bound to iron and manganese
ammonium acetate (1 M) at pH 2.0 oxyhydroxides
4 R: residuala Acid mixture: HCl/HNO3/HF Metals bound in lithogenic minerals
a
Digestion of the residual material is not specified in the BCR protocol
6178 Environ Monit Assess (2013) 185:6173–6185

Table 3 Average concentrations of Cd, Cr, Cu, Ni, Pb, and Zn in different fractions of surface sediments from the Sal River estuary (n=4)

Cd Cr Cu Ni Pb Zn

Fraction 1 (μgg−1) 1 0.04 0.42 0.71 1.56 1.35 5.09


2 0.07 2.10 2.07 2.55 3.33 6.04
3 0.05 1.03 0.70 0.69 0.75 3.48
4 0.06 1.68 0.75 0.76 1.03 3.36
5 0.07 1.99 1.51 2.25 2.40 6.83
Mean±SD % 15±1 7±2 8±1 14±2 12±2 12±3
1 0.05 2.16 1.60 1.21 2.34 7.90
2 0.06 7.75 3.22 2.01 3.67 11.5
Fraction 2 (μgg−1) 3 0.04 2.88 1.11 0.78 1.51 4.04
4 0.06 3.86 1.49 0.84 1.76 6.32
5 0.06 5.46 2.99 2.45 4.06 12.1
Mean ± SD % 14±1 22±2 14±1 13±1 19±2 21±2
1 0.12 2.72 3.75 3.11 4.40 10.8
2 0.18 11.1 8.91 4.75 6.97 16.1
−1
Fraction 3 (μgg ) 3 0.11 3.34 2.65 1.41 2.62 5.23
4 0.15 4.80 2.77 2.16 3.35 6.61
5 0.17 6.67 7.77 5.20 5.80 13.6
Mean ± SD % 37±3 28±2 34±4 30±2 34±2 26±1
1 0.10 4.07 4.86 4.23 4.64 18.5
2 0.15 17.0 11.4 6.78 8.35 24.1
Residual (μgg−1) 3 0.12 5.14 2.75 2.25 2.90 7.32
4 0.13 6.26 4.69 2.79 3.30 10.2
5 0.13 12.6 9.21 7.34 5.21 24.3
Mean ± SD % 32±2 43±4 44±4 43±1 35±3 41±3
1 66 57 55 58 64 56
ΣF1+F2+F3(%) 2 67 55 55 58 63 58
3 59 59 62 56 63 63
4 66 62 52 57 65 62
5 70 53 62 57 70 57
Mean ± SD % 66±4 57±4 56±5 57±1 65±5 59±5
1 0.32 9.37 10.9 10.1 12.7 42.3
ΣF1+F2+F3+R (μgg−1) 2 0.46 37.9 25.6 16.1 22.3 57.7
3 0.34 12.4 7.22 5.13 7.80 20.1
4 0.41 16.6 9.70 6.56 9.40 26.4
5 0.43 26.7 19.7 17.2 17.5 56.8
Mean % 100 100 100 100 100 100
1 0.32 9.28 11.5 8.54 10.8 41.3
Total metal (μgg−1) 2 0.46 39.9 26.8 15.6 20.7 51.7
3 0.29 10.8 6.55 4.55 6.80 17.3
4 0.34 14.3 8.31 5.58 8.10 23.5
5 0.41 23.5 19.1 14.9 17.6 53.4
Recovery ± SD % 109±10 108±9 104±9 114±6 111±8 110±5
Environ Monit Assess (2013) 185:6173–6185 6179

R), the sum of contents for three fractions (ΣF1+F2+ The oxidizable (F3) and residual (R) fractions were
F3), and the total metal contents. The standard devia- generally the largest, and the environmentally mobile
tions of the four replicates ranged from 1 to 10 %, (F1) and reducible (F2) fractions the least significant.
indicating good repeatability. This can be seen in Fig. 2, which illustrates the metal

Fig. 2 Fractionation of a Cd, b Cr, c Cu, d Ni, e Pb, and f Zn in sediments from the Sal River estuary
6180 Environ Monit Assess (2013) 185:6173–6185

percentages extracted in each fraction, for the five (34 %), reducible (14 %), and acid soluble (8 %) frac-
different sediments. The percentage of metal extracted tions. Cu showed a greater content in the residual frac-
was calculated from the ratio between the concentra- tion compared to the other metals. In this fraction, the
tion of the element in each fraction, and the sum of metals are bound to silicates and are therefore unavail-
concentrations in all fractions. The metal distribution able to the aquatic system (Passos et al. 2010). The inert
in the sediment fractions was similar along the estuary, fraction of this metal in the sediments was probably
indicating that the elements had similar origins and derived from natural sources, with the high percentage
deposition mechanisms. being indicative of low levels of pollution (Cuong and
According to the results obtained for Cd fraction- Obbard 2006). Hence, Cu was less available to aquatic
ation (Table 3, Fig. 2), the oxidizable fraction was the fauna, and less likely to enter the food chain than the
most abundant (37 % of the total content), followed by other metals. The results obtained here are in agreement
the residual (32 %), acid soluble (15 %), and reducible with those reported in the literature (Jain 2004; Ren-
(14 %) fractions. Cd was the metal with the greatest Ying et al. 2007; Passos et al. 2011), where Cu was also
percentage in the labile fraction. The metals in this mainly found in the residual fraction.
fraction are weakly bound with the sediment, so it is An internal check on the sequential extraction proce-
therefore considered to be the most unstable and reac- dure was performed by comparing the sum of the four
tive phase, which has greater potential for adverse fractions (Σacid-soluble + reducible + oxidizable +
effects on the aquatic environment than the other residual) with the total measured concentrations. The
fractions (Li et al. 2007). Other studies have also recovery of the sequential extraction was calculated as
reported that in sediments Cd is associated with the follows: recovery = [(ΣF1+F2+F3+R)/full digestion]×
labile fraction (Jain 2004; Cuong and Obbard 2006; 100. The results are given in Table 3. There was good
Passos et al. 2010; Rodrigues et al. 2010). agreement between the sums of the fractions and the
Cr and Zn were found mainly in association with the total metal contents, with recoveries of between 104 and
residual (44 and 41 %, respectively) and oxidizable (28 114 %, which is within the range of other reports
and 26 %, respectively) fractions, followed by the re- (Martin et al. 1998; Li et al. 2007; Yuan et al. 2004).
ducible (22 and 21 %, respectively) and acid soluble (7
and 12 %, respectively) fractions. Of all the metals, Cr Identification of natural and anthropogenic sources
and Zn showed the greatest percentages in the reducible
fraction (>20 % of the total content), where the elements Chemical fractionation differentiates metals of natural
are associated with manganese and iron oxides and origin from those derived from anthropogenic sources
hydroxides. Significant associations between trace met- (Passos et al. 2010). Elevated concentrations of metals
als and Fe and Mn oxides and hydroxides in sediments in the residual fraction indicate that sediments are
have been found for regions that receive discharges of relatively unpolluted, and that the elements derive
industrial effluents (Relic et al. 2005; Sakan et al. 2007; mainly from lithogenic origins (Chandra Sekhar et al.
Li et al. 2007; Kirkelund et al. 2010). 2003). Anthropogenic metals are predominantly found
Ni and Pb were found mainly in association with the in the most labile sediment fractions (carbonates, Fe
residual (43 and 35 %, respectively) and oxidizable (30 and Mn oxides, organic matter, and sulfides), which
and 34 %, respectively) fractions, followed by the reduc- are vulnerable to small changes in environmental con-
ible (13 and 19 %, respectively) and acid soluble (14 and ditions, such as those caused by human activity
12 %, respectively) fractions. These metals showed high (Pempkowiak et al. 1999).
contents (greater than 30 %) in the oxidizable fraction. In Table 3 lists the percentages of each metal extracted
this sediment fraction, the metals are strongly com- in the most labile fractions (ΣF1+F2+F3). The order
plexed, and are released following either degradation of of mobility (from most to least bioavailable) was: Cd
organic matter, or oxidation of sulfides to sulfates (66 %) > Pb (65 %) > Zn (59 %) > Ni (57 %) = Cr
(Passos et al. 2011). This is consistent with the results (57 %) > Cu (56 %).
reported by other investigators (Yuan et al. 2004; Morillo Cd and Pb showed the greatest amounts in the
et al. 2004; Cuong and Obbard 2006; Passos et al. 2010). bioavailable fractions, with 15 % (Cd) and 34 % (Pb)
Finally, for Cu the residual fraction was predominant of the total contents in the first and third fractions,
(44 % of the total content), followed by the oxidizable respectively. It has been found previously that Cd was
Environ Monit Assess (2013) 185:6173–6185 6181

weakly adsorbed (retained on the sediment surface by The fractions that are most influenced by human ac-
weak electrostatic interaction), and that the release of tivity include the exchangeable and carbonate-bound
Pb under oxidizing conditions could be explained by fractions, in which metals are weakly retained and can
binding to a mineral fraction (such as sulfides) that become more bioavailable due to equilibration with
was unstable under oxidizing conditions (Jain 2004; the aqueous phase (Rath et al. 2009). The reactivity of
Cuong and Obbard 2006; Passos et al. 2010). Ni, Zn, sediments was evaluated by applying the criteria of the
Cu, and Cr showed higher percentages in the inert risk assessment code.
fraction. Similar results have been reported previously The RAC is a scale used to assess potential mobil-
for these metals (Yuan et al. 2004; Ren-Ying et al. ity and risk, based on the percentage of exchangeable
2007; Passos et al. 2011). and carbonate-bound metal in the sediment (Perin et
Lithogenic metals are predominantly found in the al. 1985; Jain 2004; Ghrefat and Yusuf 2006; Karak et
residual sediment fraction, where high percentages al. 2011). Sediments can be classified as presenting no
indicate that the sediments are relatively unpolluted. risk (<1 %), low risk (1–10 %), medium risk (11–
Elevated concentrations of metals in the most labile 30 %), high risk (31–50 %), and very high risk
sediment fractions are indicative of pollution, and that (>50 %) to the ecosystem (Ikem and Adisa 2011;
the elements derive mainly from anthropogenic sour- Perin et al. 1985; Jain 2004).
ces. Hence, the significant amount of metals in the Figure 3 illustrates the results of the risk factor
most bioavailable fractions probably resulted from the analysis, with values for the six trace metals given as
presence of anthropogenic material (Passos et al. percentages for the fraction soluble in acid (%F1). In
2010). The Sal estuary receives discharges from mu- general, the sediments showed low to medium risk for
nicipal and industrial wastewaters, agricultural runoff, all metals. The code as applied to the present study
and particularly from metal industries (Garcia et al. revealed that 13–16 % of Cd, 4–10 % of Cr, 7–10 % of
2011). These effluents contribute to the inputs of met- Cu, 12–16 % of Ni, 10–15 % of Pb, and 10–17 % of
als into the region’s aquatic systems. Zn were present in exchangeable fractions. Cr and Cu
showed a low risk at most of the sites (RAC <10 %),
Environmental implications while Cd, Ni, Pb, and Zn showed a medium risk (RAC
>10 %). Small variations in environmental conditions,
The fractionation of metals is of critical importance for such as pH or salinity, could therefore increase avail-
their potential toxicity and mobility (Maiz et al. 2000). ability of the elements to the aquatic system.
Fig. 3 Risk assessment
codes (RAC) for Cd, Cr, Cu,
Ni, Pb, and Zn in surface
sediments from the Sal
River estuary
6182 Environ Monit Assess (2013) 185:6173–6185

In an earlier study in the same region (Garcia et al. Cabrera et al. (2009) for the mine-impacted Taxco
2011), it was shown that sediments from sites 2 and 5, River in Mexico. Bioavailable Pb percentages greater
located in areas directly influenced by effluent inputs, than 50 % in the river bed sediments indicated a very
were vulnerable to enrichment by anthropogenic met- high potential environmental risk, according to the
als. Concentrations of Cd exceeded the probable nat- RAC.
ural background of the region, which was indicative of
enrichment. There was no evidence of anthropogenic ERL–ERM predictions
pollution for the other metals studied; however, in the
earlier work total elemental concentrations were used The ERL (effects range—low) and ERM (effects
to calculate possible enrichment. It is acknowledged range—mean) concentrations presented in the
that the total concentration of an element only reflects Sediment Quality Guide, developed by Long and
the amount stored in the system, and provides no Morgan (1990), have been adopted as an informal tool
information concerning availability. to evaluate sediment chemical data in relation to pos-
Similar studies conducted by Passos et al. (2010), sible adverse effects on aquatic biota. ERL and ERM
using sediments from the Poxim River (northeast values indicate concentrations at which toxicity could
Brazil), which is highly polluted due to discharges of start to be observed, and above which adverse effects
domestic and industrial effluents, showed that the might occur, respectively (Long and Morgan 1990;
sediments generally presented a medium risk for Cd, Amin et al. 2009; Garcia et al. 2011). The SQG criteria
Cr, Cu, Ni, Pb, and Zn. RAC values greater than 11 % were derived and validated using data of test of toxic-
indicated a substantial risk of metal mobilization from ity in sediments only for coastal regions of the USA
sediments across the entire study region. For the same (Long and Morgan 1990), but despite this limitation
locations, Zn showed a high to very high risk (RAC have been used to interpret data for sediments from
>30 %), while Ni showed a low risk (RAC <10 %). various global regions (Birch and Taylor 2002; Muniz
Passos et al. (2011) identified low to medium risks for et al. 2004; Mora et al. 2004; Hyun et al. 2007; Gomes
Cd, Cr, Cu, Ni, Pb, and Zn in sediments from the et al. 2010).
Sergipe River (also in northeast Brazil). In an environ- In order to allow assessment of toxicity based on
mental risk assessment of metals in sediments from SQG criteria, partial trace metal concentrations were
lakes formed by the Cambé stream (Paraná State, determined following extraction using nitric and
Brazil), Ishikawa et al. (2009) identified low to medi- hydrochloric acids, which is a procedure compatible
um risks for Cu and Pb, and a very high risk for Zn. with that used in the development of the SQG. Table 4
Chemical fractionation of metals in Lake Chapala shows the partial concentrations obtained for each
sediments (Mexico) showed that Cd, Pb, and Cr were metal, together with the respective ERL and ERM
present in the exchangeable and carbonate fractions, values (Long and Morgan 1990).
and that there was a very high risk of pollution of the The ranges of metal concentrations found were (μg
water column due to metal transfer (Trujillo-Cardenas g−1): 0.04–0.11 (Cd); 6.55–26.8 (Cr); 9.28–39.9 (Cu);
et al. 2010). Similar results were reported by Arcega- 4.55–15.6 (Ni); 6.78–20.7 (Pb); and 17.3–53.4 (Zn).

Table 4 Partial metals concentrations in surface sediments from the Sal River Estuary (mean ± standard deviation, n=3)

Station Cd (μgg−1) Cu (μgg−1) Cr (μgg−1) Ni (μgg−1) Pb (μgg−1) Zn (μgg−1)

1 0.10±0.02 11.4±0.2 9.28±0.1 8.54±0.1 10.8±0.1 41.3±0.5


2 0.08±0.01 26.8±0.3 39.9±0.2 15.6±0.2 20.7±0.2 51.7±0.5
3 0.04±0.01 6.55±0.1 10.8±0.1 4.55±0.1 6.78±0.1 17.3±0.2
4 0.06±0.01 8.31±0.1 14.2±0.2 5.58±0.1 8.14±0.1 23.4±0.3
5 0.11±0.02 19.1±0.2 23.5±0.2 14.9±0.2 17.6±0.2 53.4±0.6
ER-L 1.20 34.0 81.0 20.9 46.7 150
ER-M 9.60 270 370 51.6 218 410

ER-L effects range low, ER-M effects range mean (Long and Morgan 1990)
Environ Monit Assess (2013) 185:6173–6185 6183

For all the metals studied, the values were well below samples. The results suggested that fluctuations in
the ERL, indicating that adverse effects on aquatic pH or salinity might cause mobilization of metals from
biota should rarely occur. Ni showed concentrations the sediments to the water column. Possible metal-
nearest to the ERL (20.9 μgg−1) at sites 2 (15.6 μgg−1) related toxicity was investigated by comparing sedi-
and 5 (14.9 μgg−1), however the ability of ERL to ment chemical data with ERL–ERM values. It was
predict adverse effects is lower for Ni than for the found that adverse effects on aquatic biota should
other metals (Long and Morgan 1990). rarely occur. Despite agreement between the two
It must be emphasized that SQG criteria should be methods, further validation of these results should be
used with caution, as there cannot be any guarantee of undertaken using toxicity tests in benthic organisms.
a complete absence of toxicity at concentrations lower
than the ERL, or that samples where the ERM is Acknowledgments The authors thank Coordenação de
exceeded must necessarily be toxic, particularly con- Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and
sidering that the SQG were not specifically developed Fundação de Apoio à Pesquisa e à Inovação Tecnológica do
for the biogeochemistry of the region under study. For Estado de Sergipe (FAPITEC) for studentships. We are also
grateful to the Environmental Analytical Chemistry Laboratory
greater confidence, it is important that the results of Sergipe Federal University for technical support.
obtained here should be validated using toxicity tests
(Garcia et al. 2009).

References
Conclusions
Alves, J. P. H., Passos, E. A., & Garcia, C. A. B. (2007). Metals
Sequential extraction procedures enable evaluation of and acid volatile sulfide in sediment cores from the Sergipe
River Estuary, Northeast, Brazil. Journal of the Brazilian
the different chemical forms of metals present in sedi-
Chemical Society, 18, 748–758.
ments. For over three decades, these techniques have Amin, B., Ismail, A., Arshad, A., Yap, C. K., & Kamarudin, M.
been applied to environmental matrices including soils, S. (2009). Anthropogenic impacts on heavy metal concen-
sediments, atmospheric particulates, and sewage sludge. trations in the coastal sediments of Dumai, Indonesia.
Environmental Monitoring and Assessment, 148, 291–305.
Fractionation of Cd, Cr, Cu, Ni, Pb, and Zn in
Arcega-Cabrera, F., Armienta, M. A., Daesslé, L. W., Castillo-
sediments was performed for samples collected from Blum, S. E., Talavera, O., & Dótor, A. (2009). Variations of
five locations in the Sal River estuary. A significant Pb in a mine-impacted tropical river, Taxco, Mexico: use of
amount of Cd was present in the soluble fraction, geochemical, isotopic and statistical tools. Applied Geo-
chemistry, 24, 162–171.
while the greatest percentages of Cr and Zn were in
Barbier, E., Passos, E. A., Aragão, K. A. S., Santos, D. B., &
the reducible fraction. Ni and Pb showed high contents Garcia, C. A. B. (2010). Assessment of trace metal levels
in the oxidizable fraction, and Cu was present in the in catfish (Cathorops spixii) from Sal River Estuary,
residual fraction. Aracaju, State of Sergipe, Northeastern Brazil. Water
Environment Research, 82, 2301–2305.
The mobility of the metals was in the order Cd > Pb >
Barbieri, E., Garcia, C. A. B., Passos, E. A., Aragão, K. A. S., &
Zn > Ni = Cr > Cu. Cd and Pb, preferentially associated Alves, J. P. H. (2007). Heavy metal concentration in tissues
with the more labile fractions (exchangeable, reducible, of Puffinus gravis sampled on the Brazilian Coast. Revista
and oxidizable), could be used as indicators for inputs Brasileira de Ornitologia, 15, 69–72.
Birch, G. F., & Taylor, S. E. (2002). Assessment of possible
from anthropogenic sources, while Zn, Ni, Cr, and Cu
sediment toxicity of contaminated sediments in Port
were associated to a greater extent with the inert frac- Jackson, Sydney, Australia. Hydrobiology, 472, 19–27.
tion, indicative of natural origins. Chandra Sekhar, K., Chary, N. S., Kamala, C. T., Suman Raj, D.
All of the sediment samples showed evidence of S., & Sreenivasa Rao, A. (2003). Fractionation studies and
bioaccumulation of sediment-bound heavy metals in
anthropogenic enrichment, so that the metal concentra-
Kolleru lake by edible fish. Environmental International,
tions measured were not representative of natural con- 29, 1001–1008.
ditions in this estuarine region. Around 40 % of the metal Cuong, D., & Obbard, J. P. (2006). Metal speciation in coastal
content was present in the residual fraction, similar to the marine sediments from Singapore using a modified BCR-
sequential extraction procedure. Applied Geochemistry, 21,
proportion found for contaminated regions worldwide.
1335–1346.
Risk assessment code evaluation indicated low to Fang, T., Li, X., & Zhang, G. (2005). Acid volatile sulfide and
medium environmental risk for all metals in most simultaneously extracted metals in the sediment cores of
6184 Environ Monit Assess (2013) 185:6173–6185

the Pearl River Estuary, South China. Ecotoxicology and Miller J.C., & Miller J.M. (1993). Statististc for anaytical chem-
Environmental Safety, 61, 420–431. istry. Printed in Great Britain, 11–120.
Filgueiras, A. V., Lavilla, I., & Bendicho, C. (2002). Chemical Mora, S., Sheikholeslami, M. R., Wyse, E., Azemard, S., &
sequential extraction for metal partitioning in environmen- Cassi, R. (2004). An assessment of metal contamination
tal solid samples. Journal of Environmental Monitoring, 4, in coastal sediment of the Caspian Sea. Marine Pollution
832–857. Bulletin, 48, 61–77.
Garcia, C. A. B., Barreto, M. S., Passos, E. A., & Alves, J. P. H. Morillo, J., Usero, J., & Gracia, I. (2004). Heavy metal distri-
(2009). Regional geochemical baselines and controlling bution in marine sediments from the southwest coast of
factors for trace metals in sediments from the Poxim River, Spain. Chemosphere, 55, 431–442.
Northeast Brazil. Journal of the Brazilian Chemical Soci- Mossop, K. F., & Davidson, C. M. (2003). Comparison of
ety, 20, 1334–1342. original and modified BCR sequential extraction proce-
Garcia, C. A. B., Passos, E. A., & Alves, J. P. H. (2011). dures for the fractionation of copper, iron, lead, manganese
Assessment of trace metals pollution in estuarine sediments and zinc in soils and sediments. Analytica Chimica Acta,
using SEM-AVS and ERM-ERL predictions. Environmen- 478, 111–118.
tal Monitoring and Assessment, 181, 385–397. Muniz, P., Danulat, E., Yannicelli, B., Garcia-Alonso, J.,
Ghrefat, H., & Yusuf, N. (2006). Assessing Mn, Fe, Cu, Zn, and Medina, G., & Bícego, M. C. (2004). Assessment of con-
Cd pollution in bottom sediments of Wadi Al-Arab Dam, tamination by heavy metals and petroleum hydrocarbons in
Jordan. Chemosphere, 65, 2114–2121. sediments of Montivedeo Harbour (Uruguay). Environ-
Gomes, M. V. T., Costa, A. S., Garcia, C. A. B., Passos, E. A., & mental International, 29, 1019–1028.
Alves, J. P. H. (2010). Concentrações e associações geo- Passos, E. A., Barbieri, E., Garcia, C. A. B., & Alves, J. P. H.
químicas de Pb e Zn em sedimentos do rio São Francisco (2005). Contaminação das águas do estuário do Rio do Sal,
impactados por rejeitos da produção industrial de zinco. Sergipe e Poxim. O Mundo da Saúde, 29, 226–237 (In
Quimica Nova, 33, 2088–2092 (In Portuguese). Portuguese).
Hyun, S., Lee, C., Lee, T., & Choi, J. (2007). Anthropogenic Passos, E. A., Alves, J. C., Santos, I. S., Alves, J. P. H., Garcia,
contributions to heavy metal distributions in the surface C. A. B., & Costa, A. C. S. (2010). Assessment of trace
sediments of Masan Bay, Korea. Marine Pollution Bulletin, metals contamination in estuarine sediments using a se-
54, 1059–1068. quential extraction technique and principal component
Ikem, A., & Adisa, S. (2011). Runoff effect on eutrophic lake analysis. Microchemical Journal, 96, 50–57.
water quality and heavy metal distribution in recent littoral Passos, E. A., Alves, J. P. H., Garcia, C. A. B., & Costa, A. C. S.
sediment. Chemosphere, 82, 259–267. (2011). Metal fractionation in sediments of the Sergipe
Ishikawa, D. N., Noale, R. Z., Ohe, T. H. K., Souza, E. B. R., River, Northeast. Brazil. Journal of the Brazilian Chemical
Scarmínio, I. S., Barreto, W. J., & Barreto, S. R. G. (2009). Society, 22, 828–835.
Avaliation of the environmental risk by metal distribution Pempkowiak, J., Sikora, A., & Biernacka, E. (1999). Speciation
in sediments from lakes formed by Cambé Stream at of heavy metals in marine sediments vs their bioaccumu-
Londrina. Quimica Nova, 32, 1744–1449. lation by mussels. Chemosphere, 39, 313–321.
Jain, C. K. (2004). Metal fractionation study on bed sediments Perin, G., Craboledda, L., Lucchese, M., Cirillo, R., Dotta, L.,
of River Yamuna, India. Water Research, 38, 569–578. Zanette, M., & Orio, A. (1985). Heavy metals speciation in
Karak, T., Abollino, O., Bhattacharyya, P., Das, K. K., & Paul, the sediments of Northern Adriatic Sea—a new approach
R. K. (2011). Fractionation and speciation of arsenic in for environmental toxicity determination. In: Lekkas, T.D.
three tea gardens soil profiles and distribution of As in (Ed.), Heavy Metal in the Environment 2, (pp. 454–456).
different parts of tea plant (Camellia sinensis L.). Chemo- Edinburg: CEP Consultants.
sphere, 85, 948–960. Rath, P., Panda, U. C., Bhatta, D., & Sahu, K. C. (2009). Use of
Kirkelund, G. M., Ottosen, L. M., & Villumsen, A. (2010). sequential leaching, mineralogy, morphology and multivar-
Investigations of Cu, Pb and Zn partitioning by sequential iate statistical technique for quantifying metal pollution in
extraction in harbour sediments after electrodialytic reme- highly polluted aquatic sediments—a case study: Brahmani
diation. Chemosphere, 79, 997–1002. and Nandira Rivers, India. Journal of Hazardous Materi-
Li, Q., Wu, Z., Chu, B., Zhang, N., Cai, S., & Fang, J. (2007). als, 163, 632–644.
Heavy metals in coastal wetland sediments of the Pearl River Rauret, G., Lopez-Sanchez, J. F., Sahuquillo, A., Rubio, R.,
Estuary, China. Environmental Pollution, 149, 158–164. Davidson, C., Ure, A., & Quevauviller, P. (1999). Improve-
Long, E. R., & Morgan, L. G. (1990). The potential for biolog- ment of the BCR three step sequential extraction procedure
ical effects of sediment-sorbed contaminantes tested in the prior to the certification of new sediment and soil reference
Naticional Status and Trends Program. NOAA Technical materials. Journal of Environmental Monitoring, 1, 57–61.
Memorandum NOS OMA 52 (p. 346). Seattle: National Relic, D., Dordevic, D., Popovic, A., & Blagojevic, T. (2005).
Oceanic an Atmospheric Administration. Speciations of trace metals in the Danube alluvial sedi-
Maiz, I., Arambarri, I., Garcia, R., & Millan, E. (2000). Evalu- ments within an oil refinery. Environmental International,
ation of heavy metal availability in polluted soils by two 31, 661–669.
sequential extraction procedures using factor analysis. En- Ren-Ying, L., Hao, Y., Zhi-Gaol, Z., Jun-Jiel, L., Xiao-Hua, S., &
vironmental Pollution, 110, 3–9. Fengl, J. (2007). Fractionation of heavy metals in sediments
Martin, R., Sanchez, D. M., & Gutierrez, A. M. (1998). Sequential from Dianchi Lake, China. Pedosphere, 17, 265–272.
extraction of U, Th, Ce, La and some heavy metals in sedi- Rodrigues, S. M., Henriques, B., Coimbra, J., Ferreira, S. E.,
ments from Ortigas river, Spain. Talanta, 46, 1115–1121. Pereira, M. E., & Duarte, A. C. (2010). Water-soluble
Environ Monit Assess (2013) 185:6173–6185 6185

fraction of mercury, arsenic and other potentially toxic Trujillo-Cardenas, J. L., Saucedo-Torres, N. P., Del Valle, P. F.
elements in highly contaminated sediments and soils. Che- Z., & Donato, R. (2010). Speciation and sources of toxic
mosphere, 78, 1301–1312. matals in sedimetn of lake Chapala, Mexico. Journal of the
Rubio, B., Nombela, M. A., & Vilas, F. (2000). Geochemistry of Mexican Chemical Society, 54, 79–87.
major and trace elements in sediments of the Ria de Vigo (1993). Speciation of heavy-metals in soils and sediments—an
(NW Spain): an assessment of metal pollution. Marine account of the improvement and harmonization of extrac-
Pollution Bulletin, 40, 968–980. tion techniques undertaken under the auspices of the BCR
Sakan, S., Gržetić, I., & Đorđević, D. (2007). Distribution and of the Commission-of-the-European-Communities. Inter-
fractionation of heavy metals in the Tisa (Tisza) River national Journal of Environmental Analytical Chemistry,
sediments. Environmental Science and Pollution Research 51, 135–151.
International, 14, 229–236. Yuan, C. G., Shi, J. B., He, B., Liu, J. F., Liang, L. N., &
Silva, A. F., Lima, G. R. S., Alves, J. C. A., Santos, S. H., Jiang, G. B. (2004). Speciation of heavy metals in
Garcia, C. A. B., Alves, J. P. H., Araújo, R. G. O., & marine sediments from the East China Sea by ICP-
Passos, E. A. (2012). Evaluation of trace metal levels in MS with sequential extraction. Environmental Interna-
surface sediments of the Sergipe River Hydrographic tional, 30, 769–783.
Basin, Northeast Brazil. Journal of the Brazilian Chemical Zemberyov, M., Bartekov, J., & Hagarov, I. (2006). The utiliza-
Society, 23, 1669–1679. tion of modified BCR three-step sequential extraction pro-
Tessier, A., Campbell, P. G. C., & Bisson, M. (1979). Sequential cedure for the fractionation of Cd, Cr, Cu, Ni, Pb and Zn in
extraction procedure for the speciation of particulate trace soil reference materials of different origins. Talanta, 70,
elements. Analytical Chemistry, 51, 844–851. 973–978.