Environ Monit Assess (2010) 167:185–197

DOI 10.1007/s10661-009-1041-3

Distribution and temporal variation of trace metal

enrichment in surface sediments of San Jorge Bay, Chile
Jorge Valdés · Domingo Román ·
Marcos Guiñez · Lidia Rivera · Tomás Morales ·
Juan Ávila · Pedro Cortés

Received: 4 December 2008 / Accepted: 4 June 2009 / Published online: 18 June 2009
© Springer Science + Business Media B.V. 2009

Abstract Cu, Pb, and Hg concentrations were de- hand, Hg does not pose a contamination problem
termined in surface sediment samples collected in this bay. Cu and Pb concentrations showed sig-
at three sites in San Jorge Bay, northern Chile. nificant variations from 1 year to another. These
This study aims to evaluate differences in their variations seem to be a consequence of the combi-
spatial distribution and temporal variability. The nation of several factors, including changes in the
highest metal concentrations were found at the loading and/or storage of minerals in San Jorge
site “Puerto”, where minerals (Cu and Pb) have Bay, the dredging of bottom sediments (especially
been loaded for more than 60 years. On the other at Puerto), and seasonal changes in physical–
chemical properties of the water column that
modify the exchange of metals at the sediment–
water interface. Differences in the contamination
J. Valdés · M. Guiñez factor and geoaccumulation index suggest that
Laboratorio de Sedimentología y Paleoambientes, pre-industrial concentrations measured in marine
Instituto de Investigaciones Oceanológicas,
Facultad de Recursos del Mar, sediments of this geographical zone, were better
Universidad de Antofagasta, than geological values (average shale, continen-
Casilla 170, Antofagasta, Chile tal crust average) for evaluating the degree of
contamination in this coastal system. Based on
D. Román · L. Rivera · T. Morales ·
J. Ávila · P. Cortés these last two indexes, San Jorge Bay has a seri-
Departamento de Química, ous problem of Cu and Pb pollution at the three
Facultad de Ciencias Básicas, sampling locations. However, only Cu exceeds the
Universidad de Antofagasta, Antofagasta, Chile national maximum values used to evaluate ecolog-
M. Guiñez ical risk and the health of marine environments.
Programa de Doctorado en Ciencias Aplicadas, It is suggested that Chilean environmental legisla-
Facultad de Recursos del Mar, tion for marine sediment quality—presently under
Universidad de Antofagasta, Casilla 170, technical discussion—is not an efficient tool for
Antofagasta, Chile
protecting the marine ecosystem.
J. Valdés (B)
Instituto de Investigaciones Oceanológicas,
Facultad de Recursos del Mar,
Keywords Metals · Geoaccumulation index ·
Universidad de Antofagasta, Casilla 170,
Antofagasta, Chile Contamination factor · Marine sediment
e-mail: [email protected] quality · Chile
186 Environ Monit Assess (2010) 167:185–197

Introduction latitude, the linearity of the northern Chilean

coast is interrupted by two bay systems: one
Coastal marine systems are influenced by heavy oriented to the north (Mejillones) and another
anthropogenic pressure, since most human activ- oriented to the south (San Jorge). Local oceano-
ities are concentrated along the coast. The geog- graphical conditions are controlled by the influ-
raphy of Chile augments this situation, not only ence of the Humboldt Current, one of the most
because of the location of urban centers along the productive systems in the world (Strub et al. 1998).
coast, but also because the sea is the principal The principal characteristic at this latitude is the
route for exporting industrial products from the permanent upwelling cell (Punta Angamos) that
entire national territory. supports important pelagic fisheries (Strub et al.
Pollutants are input into the ocean mainly 1998). This area borders one of the world’s most
through domestic sewage and harbor and indus- arid regions, and continental input to the ocean
trial activities. As a result, large extensions of is restricted to minimal atmospheric transport of
the world’s coastal areas are contaminated. Man- lithogenic particles (Vargas 2002). For this reason,
agement and conservation strategies require an upwelling seems to be one of the most impor-
understanding of ecosystem behavior. Unfortu- tant natural processes influencing the chemical
nately, scientific knowledge on marine pollution is composition of the water column and bottom
patchy, constituting a major obstacle for introduc- sediments.
ing effective management strategies for pollution The city of Antofagasta, the most important
control (Shahidul and Tanaka 2004). urban center in northern Chile, is located on San
Contaminating substances in coastal zones Jorge Bay. Founded in 1866, Antofagasta cur-
include persistent organic pollutants, nutrients, rently has a population of 345,000 and its principal
oils, radionuclides, pathogens, heavy metals, etc. commercial activity is the loading onto ships of
(Cobelo-García and Prego 2004). Many studies minerals (mainly copper) produced in this region.
have focused on heavy metal contents in ma- The bay has two ports: one at “Coloso” (Fig. 1),
rine systems (Pekey et al. 2004; Alagarsamy 2006; where concentrated copper has been loaded since
Buccolieri et al. 2006; McCready et al. 2006; and 1991, and the other at “Puerto” (Fig. 1), where
others). All metals present in the marine envi- copper, lead, and other products have been loaded
ronment are found in dissolved and particulate since 1943. The bay also has three oil-loading
forms. Many of these trace metals are classified terminals and one effluent for the discharge of
as micronutrients because they are essential for domestic waters after a secondary treatment
phytoplankton growth (Libes 1992). The concen- (Fig. 1).
tration of these metals can vary due to changing Very few efforts have been made to understand
inputs and/or seasonal effects involving biologi- the environmental conditions of San Jorge Bay.
cal, geochemical, and physical interactions (Hatje Rather, studies tend to focus on oceanographic
et al. 2001). topics like temperature pattern variability and
Marine sediments can be sensitive to pollution seasonal growth of marine copepods (Escribano
monitoring (Atgin et al. 2000) because they are et al. 1995), phytoplankton ecology (Rodriguez
the most important reservoir for metals and other and Escribano 1996), physical–biological inter-
pollutants in aquatic systems. The problem is that actions (Escribano et al. 2002), surface circula-
heavy metals also have natural sources that reach tion (Escribano et al. 2004), plankton behavior
the coastal zone through the same biogeochemi- (Castilla et al. 2002), and Cu, Pb, and Zn distribu-
cal pathways as the anthropogenic sources. The tions in near-shore waters (Salamanca et al. 2000).
combination of these factors complicates the un- In this work, we studied the distribution of
derstanding of heavy metal spatial and temporal Cu, Pb, and Hg in the marine sediment, con-
distribution patterns (Salamanca et al. 2000). sidering spatial differences (three different sites
San Jorge Bay (Fig. 1) is located at 23.5◦ S, in the bay) and temporal variability (2 years).
on the boundary of the Atacama Desert. At this Moreover, we used different approaches to eval-
Environ Monit Assess (2010) 167:185–197 187

70° 31’ 70° 28’

20 74°W Perú 66°W
Bolivia
20°S
23°33’ Iquique
LA CHIMBA

Pacific ocean
100
Mejillones
Antofagasta

Argentina
Chile
PUERTO

30°S
Coquimbo

23°45’ 700 km
N
COLOSO
Santiago

Fig. 1 Location of sampling stations (black points) in represent surface circulation patterns and the cyclonic gyre
San Jorge Bay. Major oceanographic characteristics are according to Escribano et al. (2002). Stars indicate the
indicated. Dashed lines correspond to bathymetry. Arrows location of domestic effluents and oil-loading terminals

uate the environmental conditions of this coastal Analytical procedure

system.
Cu, Pb, and Hg were determined in the particle
size fraction (<63 μm) of the marine sediments
Materials and methods because this fraction is nearly equivalent to the
material carried in suspension, the most impor-
Sample collection tant system for sediment transport (Salomons and
Förstner 1984).
Two oceanographic cruises were done in San For Cu and Pb analyses, 400–600 mg of ho-
Jorge Bay: one at the end of winter 2003 and mogenized dry fine fractions of sediments and
another at the end of summer 2004. During each MESS-2 (marine sediment, NRC-CNRC) stan-
cruise, samples of surface sediments for metal dard reference material were accurately weighed,
analyses were collected with a Van Veen bottom placed in Teflon digestion bombs, and subjected
dredge sampler at three points in the bay: from to a chemical attack with 12 mL of aqua regia,
north to south, La Chimba, Puerto, and Coloso 4 mL of Perhydrol (H2 O2 to 30%), and 4 mL
(Fig. 1). All the material used in sampling and of perchloric acid, all reagents of special quality
sample storage was treated with nitric acid. Sam- for trace element analysis. Once the evolution of
pling and the marine field work were done using the gases was completed, the bombs were closed
standard operating procedures (Cooper and Rees and placed in a ceramic oven with an internal
2002); due to the intrinsic manipulation required temperature probe and external temperature con-
for such studies, we implemented the most rig- trol; a rigorous heating program was applied for
orous precautions in order to keep the samples 2 h until reaching 150◦ C. Once the bombs had
contamination-free. cooled, the residuals were eliminated by filtration
188 Environ Monit Assess (2010) 167:185–197

Table 1 Analytical validation of the techniques for the Cu,

Pb, and Hg analyses in marine sediments For the Hg analysis, 600 mg of sediments were
introduced into Teflon bombs and subjected to
Element Technique RSDa REb CL c
(± %) (± %) (ng/ml)
a chemical attack with 6 mL of nitric acid and
Cu FAAS 1.1 0.7 (MESS-2) 2.7
6 mL of sulfuric acid. Once the gas evolution
Pb FAAS 3.1 1.2 (MESS-2) 1.5 was concluded, the bombs were closed and put
HHPN – inside the ceramic oven, where they underwent a
FF – AAS 2.5 3.5 (MESS-2) 1.0 rigorous heating program for 2 h until reaching
Hg CVAAS 5.0 1.5 (MESS-2) 0.1 140◦ C. Once the bombs had cooled, the resid-
For techniques see “Analytical procedure” chapter uals were eliminated by filtration through glass
a Relative standard deviation Whatman GF/F microfiber filters and then the
b Relative errors acid solution samples were introduced into 25-
c Detection limit mL flasks, completing the volumes with deionized
water. When it was necessary to make dilutions,
a mixed solution of 2 M in HNO3 and 2 M in
H2 SO4 was used. Blanks and MESS-2 marine
through glass microfiber Whatman GF/F filters standard reference material were used to carry
and the acid solution samples were introduced out analytical quality control measurements. The
into 100-mL flasks, completing the volume with Hg measurements were performed by CVAAS
1 M nitric acid. The “analytical blanks” were also (Welz and Melcher 1985; Jones and Laslett 1994;
prepared by this procedure. The metal measure- Ghaedi et al. 2006a, b) at 253.7 nm HCl in the
ments were made using flame atomic absorption factor extended height peak signal on a GBC
spectrometry (FAAS; Jones and Laslett 1994) 909 PBT atomic absorption spectrometer coupled
and hydraulic high-pressure nebulization flame with the standard GBC HG-900 mercury gen-
furnace atomic absorption spectrometry (HHPN- erator. Multiple standard addition methodology
FF-AAS; Román et al. 2003; Ghaedi et al. 2005, was applied. The Hg additions were made from
2006a, b) on a GBC 909 PBT atomic absorption a diluted solution prepared from Hg (II) Titrisol,
spectrometer (Australia), applying multiple stan- Merck ampoule. Moreover, 5% Sn (II) chloride
dard addition methodology. in 3 M HCl was used as a reducing agent; this was

Table 2 Descriptive Metal Year Statistical Coloso Puerto Chimba

statistics of metal
parameters
concentrations (mg kg−1 )
measured in coastal Cu 2003 Range 109.6–230.4 520.2–1212.1
sediments of San Mean 155.27 856.9 70.3
Jorge Bay SD 37.7 280.6
2004 Range 194.2–507.9 867–3166.6 379–841.8
Mean 316.2 2321.7 587.6
SD 96.9 921.5 200.9
Pb 2003 Range 19.2–82.9 209–421
Mean 47.6 321.15 44.1
SD 23.4 69.1
2004 Range 11.6–105.1 38.6–68.4 9.69–73.2
Mean 58.6 56.6 32.09
SD 39.01 10.2 24.25
Hg 2003 Range 0.337–0.605 0.226–0.606
Mean 0.48 0.404 0.54
SD 0.1 0.15
2004 Range 0.259–0.799 0.437–1.069 0.373–1.21
Mean 0.51 0.82 0.66
SD 0.19 0.19 0.36
Environ Monit Assess (2010) 167:185–197 189

3250 Table 3 ANOVA test for each cruise, comparing the

3000 2003
sampled sites
2004
2750
2500 Cruise year Cu Pb Hg
Cu (mg kg-1)

2250
2000 2003 F 49.1 121.37 0.97
1750
1500 p 0.000 0.000 0.343
1250 2004 F 26.94 1.43 2.7
1000
750 p 0.000 0.269 0.097
500
250 Only Coloso and Puerto were compared in 2003. p < 0.01
0
Coloso Puerto Chimba
440
400
360
Results and discussion
320
Pb (mg kg-1)

280
Trace metals in San Jorge Bay
240
200
160 Copper
120
80
40 The range of Cu in the San Jorge Bay sediments
0
Coloso Puerto Chimba was between 70 mg kg−1 and 3,167 mg kg−1
1.6 (Table 2). The average values at Coloso, Puerto,
1.4
and Chimba were 236 mg kg−1 , 1,589 mg kg−1 ,
1.2
and 364 mg kg−1 , respectively. The concentration
Hg (mg kg-1)

1.0
was higher in 2004 than in 2003. The highest con-
0.8
centrations of Cu were found at the Puerto site
0.6
0.4
in both years (Fig. 2). The ANOVA test showed
0.2
significant differences ( p < 0.01) in Cu content
0.0
when comparing sampling sites in each year
Coloso Puerto Chimba (Table 3) and when comparing different years in
Location
the cases of Coloso and Puerto (Table 4). Tem-
Fig. 2 Mean trace metal concentrations in the surface poral variations of Cu content in the Coloso and
sediments of San Jorge Bay for both sampling cruises. Puerto sediments may be related to higher load-
Standard deviations are shown ing activities and/or dredging activities of bottom
sediments (especially at the Puerto site). Also,
the higher organic matter flux through the water
column in summer (Escribano et al. 2004) could
play an important role in the precipitation of Cu.
prepared from SnCl2 ·2H2 O ACS reagent suitable The mean Cu concentration for San Jorge Bay
for mercury determinations and HCl. was 774 mg kg−1 , which is significantly higher than
Table 1 shows the analytical validation data in similar environments along different coasts of
to support the suitability and efficiency of the the world (Table 5). Other subtidal environments
analytical techniques applied to determine the in Chilean harbors with important industrial ac-
Cu, Pb, and Hg in the sedimentary samples used tivities registered maximum Cu concentrations of
herein. Detection limits were calculated in ac-
cordance with IUPAC criteria (Winefordner and
Long 1983; Currie 1999). Table 4 ANOVA test for each sampled site, comparing
Results were analyzed with a one-factor both years
ANOVA test (α = 0.01), after examining the Site Cu Pb Hg
homogeneity of variance and removing hetero- Coloso F 19.97 0.28 0.25
geneity by a Log (x + 1) transformation. For p 0.000 0.607 0.624
this analysis, we used the statistical program Puerto F 13.7 85.73 15.26
Minitab 14. p 0.004 0.000 0.003
190 Environ Monit Assess (2010) 167:185–197

Table 5 Comparison of the metal levels (mg kg−1 dry weight) in surface sediments from different coastal environments,
average shale, continental crust, and sediment cores from Mejillones (pre-industrial levels)
Location Cu Pb Hg Depositional Reference
environment
San Jorge Baya 774.1 94.2 0.59 Subtidal This study
San Jorge Baya 37.8 – – Sandy beach Lepez et al. (2001)
San Vicente Baya 27.7 17.4 – Subtidal Salamanca et al. (1988)
Concepción Baya 41.0 40.1 – Subtidal Salamanca et al. (1988)
Chañaral Beacha 1659 21.2 – Sandy beach Ramirez et al. (2005)
Izmit Bay, eastern Marmara Sea 89.4 94.9 – Subtidal Pekey et al. (2004)
Izmir Bay, eastern Aegean Sea – – 0.312 Subtidal Kontas (2006)
Kastela Bay, Adriatic coast – – 2.85 Subtidal Kljakoviċ-Gaspic et al. (2006)
Average shalesb 45 20 1.4 Turekian and Wedepohl (1961)
Continental crustb 75 8 0.08 Taylor (1972)
Sediment core (Mejillones Bay)a,b 53.5 4.7 0.3 Unpublished data
a Chilean coast
b Background level

41 mg kg−1 (Salamanca et al. 1988). Particularly, the Pb content at Puerto decreased drastically
a study conducted by Lepez et al. (2001), also in from 1 year to the next (from 321 mg kg−1 in 2003
San Jorge Bay but on the sandy beaches of this to 57 mg kg−1 in 2004; Fig. 2). This could be due
coastal environment, recorded only 38 mg kg−1 to the change in the Pb storage location; originally
(Table 5). Differences in metal contents between at Puerto, this was moved 30 km inland at the end
sand (beach environment) and mud fractions of the 1900s. As in the case of Cu, dredging ac-
(subtidal environment) are expected, because the tivities of bottom sediments (especially at Puerto)
latter has more affinity with metals due to its may be an important factor in the changes in the
more equivalent surface of particles. However, Pb concentrations observed in the bay’s marine
the beaches of Chañaral Bay (350 km south sediments. However, we cannot discard a seasonal
of San Jorge) showed a mean concentration of effect such as the remobilization of sediments into
1,659 mg kg−1 (Ramirez et al. 2005), which is sig- the water column due to changes in the physical–
nificantly higher than that registered for the sandy chemical properties of the sediment–water inter-
beaches (Lepez et al. 2001) and even subtidal face. A definitive explanation of this occurrence
environments (this study) of San Jorge Bay. requires further studies.
Copper found in the coastal marine sediments San Jorge Bay registered higher concentrations
of this bay is related principally to mining activ- than other Chilean bays, comparing both subti-
ities, especially at the Puerto site, which is the dal and sandy beach environments (Table 5). In
principal and oldest Cu loading site of the bay. San Jorge Bay, specifically at the Puerto site, Pb
concentrate has been stored and loaded for more
or less 30 years, which explains the levels of this
Lead
metal found in the bottom sediments.
The mean Pb concentration in San Jorge Bay
was 94 mg kg−1 , ranging between 9 mg kg−1 and Mercury
421 mg kg−1 (Table 2). Differences in lead concen-
trations between sites were significant only in 2003 The mean concentration of Hg increased from
(ANOVA, p < 0.01, Table 3), and only Puerto 2003 to 2004 at the three sites studied (Fig. 2):
showed significant differences ( p < 0.01) in Pb at Coloso from 0.48 to 0.51 mg kg−1 , at Puerto
content when comparing both years of sampling from to 0.4 to 0.82 mg kg−1 , and at Chimba from
(Table 4). Whereas the values of Pb content at 0.54 to 0.66 mg kg−1 (Table 2). No significant
Coloso and Chimba were similar for both years, differences in Hg content were found between
Environ Monit Assess (2010) 167:185–197 191

sites in both years (ANOVA, p < 0.01, Table 3) concentrations (Pekey et al. 2004; Buccolieri et al.
and only Puerto showed significant differences in 2006; Alagarsamy 2006). In this work, we used
Hg concentrations when comparing 2003 and 2004 these concentration references as well as pre-
(Table 4). In general, the subtidal environment industrial metal values measured in the bottom
of San Jorge Bay presented similar Hg concen- sediments of Mejillones Bay, which is located
trations as the other bays in the world, which 50 km north of San Jorge Bay (Fig. 1). Both bays
range between 0.02 mg kg−1 and 2.85 mg kg−1 are located in the same continental geological for-
(Table 5). The highest Hg concentration in mation (Vargas 2002) and, thus, are subjected to
Table 5 is from Kastela Bay (Adriatic Sea), where the same continental influence in the marine sedi-
mercury contents in the sediments varied widely mentation process. Previous studies have demon-
(0.143–11 mg kg−1 ) in association with indus- strated that laminated marine sediments are
trial waste from a chlor-alkaly plant that closed preserved in Mejillones Bay (Ortlieb et al. 2000;
15 years ago but is still a source of contamination Valdés 2004; Vargas et al. 2007) without signs of
(Kljakoviċ-Gaspic et al. 2006). vertical mixing. Signal preservation in sediments
Differences in Hg concentrations between like those of Mejillones Bay are the best source of
years can be attributed to sediment remobiliza- pre-industrial levels of all substances allowing the
tion due to seasonal differences in the phys- reconstruction of ancient sedimentary conditions
ical and chemical characteristics of the water with high chronological certainty (Sainz and Ruiz
column. The most common mercury species in 2006). In this case, we used values of metal con-
the marine environment are Hg+2 compounds centrations measured at the base (below 20 cm)
dissolved and bound to suspended matter and of a sediment core (Table 5); given a sedimen-
mercury (II) associated with humic matter and tation rate of 156 cm ky−1 (Vargas et al. 2007)
sulfide (Wallschlager et al. 1998). Only 74% of and considering that human occupation in this
the deposited mercury is retained in the sediments bay began in the early twentieth century (Panadés
(Horvat et al. 1999) and one of the reasons for et al. 1995), these metal concentrations represent
this situation is the redox condition of the bottom the pre-industrial condition (before 1872).
waters (Beldowski and Pempkowiak 2003). In San
Jorge Bay, the winter biological productivity is
low and the water column becomes more oxy- Contamination factor
genated whereas in summer, the biological pro-
ductivity and consequent flux of organic matter To describe the contamination of a given toxic
to the sea bottom increases and the water column substance in a basin, Håkanson (1980) proposed
becomes less oxygenated (Escribano et al. 2004), the contamination factor (Cf ), which is expressed
altering the redox condition of the sediment– as:
water interface. Hence, we suggest that in sum-
mer, Hg in the water column is bound to organic Cf = Co /Cb
matter and carried efficiently to the bottom sed-
iments, increasing the mercury concentration, as where Co is the mean content of the substance
found in this study. in the sample and Cb is the background level
value for the substance. The evaluation of this
factor uses the following terminology: Cf < 1
Assessment of sedimentary conditions related low contamination; 1 ≤ Cf < 3 moderate conta-
to trace metal contents mination; 3 ≤ Cf < 6 considerable contamination;
Cf ≥ 6 very high contamination.
Pre-industrial metal concentrations Results of Cf for the three metals measured in
San Jorge Bay are shown in Fig. 3. In the case of
Normally “average shale” values (Turekian and Cu, all the sampling sites showed similar trends of
Wedepohl 1961) or “continental crust average” environmental conditions when we used the three
abundances (Taylor 1972) are used as background different pre-industrial reference values. Chimba
192 Environ Monit Assess (2010) 167:185–197

Fig. 3 Contamination 40
factor (Cf ) by metal and 38
location, calculated 36
according to three 34
32
background levels.
30
Dashed lines represent

Contamination factor
28
reference values 26
according to the following 24
terminology: Cf < 1 = 22 Coloso
low contamination; 20 Puerto
1 ≤ Cf < 3 = moderate 18 Chimba
16
contamination;
14
3 ≤ Cf < 6 = 12
considerable 10
contamination; Cf ≥ 6 = 8
very high contamination 6
4
2
0
Average Continental Mejillones Average Continental Mejillones Average Continental Mejillones
shale crust background shale crust background shale crust background

Cupper Lead Mercury

Metal

and especially Puerto showed sediments with very tion in aquatic sediments by comparing current
high Cu contamination; Puerto had the highest concentrations with pre-industrial levels. The for-
concentration for all of San Jorge Bay. In the mula used for the calculation is:
case of Coloso, the Cf indicated that the sediments
were considerably contaminated by Cu. Igeo = log2 (Cn /1.5Bn )
The three approaches used to calculate the
where Cn is the measured content of element n
Cf for Pb showed differences between the sites
in the sediment and Bn is the geochemical back-
studied in the bay. Only Puerto showed the
ground value of metal n. A factor of 1.5 represents
same environmental condition regardless of the
possible variations in the background values for
methodological approach used, evidencing high
a given metal in the environment, as well as very
contamination by Pb. Given the Mejillones back-
small anthropogenic influences (Buccolieri et al.
ground level, all three sites showed very high Pb
2006). Sediment quality was evaluated accord-
contamination.
ing to the Igeo classification proposed by Müller
The Cf of Hg differed according to the pre-
(1979), which is shown in Table 6.
industrial levels. Whereas, in the case of the
Mejillones background level, all the sites pre-
sented moderate contamination, in the case of the Table 6 Description of sediment quality according to Igeo
Cf based on the continental crust, the three sites classification (Müller 1979)
showed very high Hg contamination. However, in Igeo Igeo class Description of sediment quality
the case of the average shale background level, the >5 6 Extremely contaminated
three sites showed low contamination. 4–5 5 Strongly to extremely
contaminated
3–4 4 Strongly contaminated
Index of geoaccumulation 2–3 3 Moderately to strongly
contaminated
The geoaccumulation index (Igeo ) is usually used 1–2 2 Moderately contaminated
to evaluate possible sediment enrichment by met- 0–1 1 Uncontaminated to
als. This index was proposed by Müller (1979) in moderately contaminated
order to determine and define metal contamina- <0 0 Uncontaminated
Environ Monit Assess (2010) 167:185–197 193

The Igeo for San Jorge sediments based on three the individual country’s degree of development,
pre-industrial concentration values (Table 5) is which may result in more restrictive laws to pro-
shown in Fig. 4. The three approaches used to tect the health of natural environments.
evaluate the environmental condition in terms of In this study, we used the sediment quality
the Cu levels in San Jorge Bay sediments showed guidelines (SQG) to evaluate the environmental
similar trends at all the sites. Elevated Igeo val- condition of the bottom sediments of San Jorge
ues (class 3 and 4) identified at Puerto indicated Bay. The SQG is a numerical approach developed
strongly contaminated (Cu) surface sediments, to provide tools for assessing the biological signif-
whereas contamination at Coloso was low. On icance of individual chemical substances (Mucha
the other hand, in the case of Pb, all the sam- et al. 2003). The chemical concentrations indi-
pling sites showed different environmental con- cated in the SQG that correspond to the 10th and
ditions depending on the pre-industrial reference 50th percentiles of adverse biological effects were
values used to calculate the Igeo . According to the called the effects-range-low (ERL) and effects-
Mejillones background value, all the sites showed range-medium (ERM), respectively (Long et al.
a high degree of Pb contamination. Moreover, in 1995). Based on this classification, it is possible
all cases, Puerto was found to be moderately to to distinguish three ranges of chemical concentra-
strongly contaminated (Igeo of Pb). When using tions: adverse effects that were observed rarely
the average shale reference values, the Igeo for (<ERM), occasionally (values between ERL
Hg indicated that the three locations were uncon- and ERM), and frequently (>ERM; McCready
taminated. However, the other two approaches et al. 2006). However, these values can only be
showed moderate to strong contamination at all used for screening approaches or in weight-of-
three sites. evidence methods (Pekey et al. 2004), as they are
only two points on a continuum of bulk chemical
National and international sediment concentrations in the sediments that roughly re-
quality guidelines late to sediment toxicity (O’Connor 2004).
According to the ERM values for Cu, Pb, and
Normally, each country enacts its own legisla- Hg of Canada, Australia, and the USA, along
tion related to environmental management, partly with the equivalent Chilean legislation (presently
due to environmental heterogeneity but mostly to in the phase of technical discussion), we evaluated

Fig. 4 Geoaccumulation 5
index by metal and
location calculated 4
according to three
background levels.
3
Dashed lines represent
reference values (see
Table 6 for details) 2
Igeo

-1

Coloso
-2 Puerto
Chimba
-3
Average Continental Mejillones Average Continental Mejillones Average Continental Mejillones
shale crust background shale crust background shale crust background

Cupper Lead Mercury

Metal
194 Environ Monit Assess (2010) 167:185–197

Fig. 5 Metal 1300

concentrations in the 1200
surface sediments of San 1100
Jorge Bay, measured in 1000
900

Cu (mg Kg )
this study. Dashed line

-1
800
corresponds to standard 700
concentrations in marine 600
environments used by 500
different environmental 400
legislations; a is the 300 b, c
200 a, d
effect-range-medium
100
(ERM of 200 mg kg−1 for 0
Cu, 200 mg kg−1 for Pb, Coloso Puerto Chimba
1.5 mg kg−1 for Hg) 220 b, c
indicated in the Chilean 200 a
legislation (Universidad 180
de Playa Ancha 2002), b 160
is the ERM (270 mg kg−1
Pb (mg Kg )
-1

140
for Cu, 218 mg kg−1 for 120
Pb, 0.71 mg kg−1 for Hg) 100
d
indicated in the 80
Australian legislation 60
(McCready et al. 2006), c 40
is the ERM (270 mg kg−1 20
for Cu, 220 mg kg−1 for 0
Pb, 0.71 mg kg−1 for Hg) Coloso Puerto Chimba
indicated in the USA 1.6
a
legislation (Long et al. 1.4
1995), and d is the
1.2
maximum probable effect
Hg (mg Kg )
-1

level (PEL, equivalent to 1.0

ERM; 197 mg kg−1 for
0.8
Cu, 91.3 mg kg−1 for Pb, b, c
0.49 mg kg−1 for Hg) 0.6
indicated in the Canadian 0.4
d
legislation (Canadian
Council of Ministers of 0.2
the Environment 1999) 0.0
Coloso Puerto Chimba

Location

the environmental condition of the three sampling that this site is contaminated by all three metals
points in San Jorge Bay (Fig. 5). In the case of analyzed in this work.
Cu, values at Puerto and Chimba were higher
than the ERM, evidencing contamination prob-
lems and probable adverse biological effects. On Conclusions
the other hand, Cu concentrations at Coloso were
only higher than the ERM of the Chilean and The study of Cu, Pb, and Hg in the surface
Canadian SQG. Pb concentrations were higher sediments of San Jorge Bay showed significant
than the ERM only at Puerto and in terms of the differences at the three sampling sites analyzed.
Canadian SQG, whereas Hg exceeded the ERM Puerto had the highest concentrations, associated
only for the Canadian SQG at all sampling sites with the historic loading of metals for more than
in San Jorge Bay. Note that whereas only Cu 60 years. Cu concentrations in this bay were supe-
exceeded the Chilean SQG at the Puerto site, Cu, rior to the subtidal environments of other bay sys-
Pb, and Hg exceeded at least one ERM, indicating tems, whereas Pb was in the concentration range
Environ Monit Assess (2010) 167:185–197 195

measured in different contaminated bays. Hg con- Buccolieri, A., Buccolieri, G., Cardellicchio, N., Dell Atti,
centrations were lower than the values reported in A., Di Leo, A., & Maci, A. (2006). Heavy metals in
the marine sediments of Taranto Gulf (Ionian Sea,
other bays. Southern Italy). Marine Chemistry, 99, 227–235.
The high temporal variability of metal concen- Canadian Council of Ministers of the Environment (1999).
trations (especially Cu and Pb) observed herein Protocol for the derivation of Canadian sediment
seems to be a consequence of a combination of quality guidelines for the protection of aquatic life
(35 pp.).
different factors, such as changes in loading and/or
Castilla, J., Lagos, N., Guiñez, R., & Laglier, J. (2002).
mineral storage in San Jorge Bay, dredging activi- Embayment and nearshore retention of plankton: The
ties of bottom sediments (especially at the Puerto Antofagasta bay and others examples. In J. Castilla &
site), and seasonal changes in physical and chem- J. Larger (Eds.), The oceanography and ecology of the
nearshore and bays in Chile (pp. 179–203). Santiago:
ical properties of the water column that modify
Universidad Católica de Chile Press.
the exchange of metals at the sediment–water Cobelo-García, A., & Prego, R. (2004). Influence of point
interface. source on trace metal contamination and distribution
Noteworthy differences were found in the pol- in a semi-enclosed industrial embayment: The Ferrol
Ria (NW Spain). Estuarine, Coastal and Shelf Science,
lution indicators used in this work (Cf , Igeo ) de-
60, 695–703.
pending on the pre-industrial values used for the Cooper, K., & Rees, H. (2002). Review of standard op-
calculations. We suggest using the pre-industrial erating procedures (SOPs). Sci. Ser., Aquat. Environ.
concentrations of Mejillones Bay rather than Prot.: Analyt. Meth., CEFAS Lowestoft, (13), 57 pp.
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Bay presented serious pollution problems by Cu Escribano, R., Marín, V., Hidalgo, P., & Olivares, G.
(2002). Physical—biological interactions. In the
and Pb at the three sampling sites studied.
pelagic ecosystem of the nearshore zone of the
When comparing Chilean environmental legis- northern Humboldt current system. In J. Castilla &
lation for marine sediment quality (presently un- J. Larger (Eds.), The oceanography and ecology of the
der discussion) with other international standards, nearshore and bays in Chile (pp. 145–175). Santiago:
Universidad Católica de Chile Press.
the former seems to be less restrictive because
Escribano, R., Rodriguez, L., & Irribarren, C. (1995).
only Cu exceeded the maximum values used to Temporal variability of sea temperature in bay of
evaluate ecological risk and the health of marine Antofagasta, Northern Chile. Estudios Oceanologicos,
environments. 14, 39–47.
Escribano, R., Rosales, S., & Blanco, L. (2004). Under-
standing upwelling circulation off Antofagasta (north-
Acknowledgements This work was supported by scien- ern Chile): A three-dimensional numerical-modeling
tific grant 1344 from Escondida Mine. We also thank approach. Continental Shelf Research, 24, 37–53.
anonymous reviewers for their comments and for signifi- Ghaedi, M., Asadpour, E., & Vafaie, A. (2006a). Simul-
cantly improving this manuscript. taneous preconcentration and determination of cop-
per, nickel, cobalt, lead, and iron content using a
surfactant-coated alumina. Bulletin of the Chemical
Society of Japan, 79(3), 432–436.
Ghaedi, M., Fathi, M., Marahel, F., & Ahmadi, F. (2005).
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