Artigo environ earth sci

ORIGINAL ARTICLE

150 years of anthropogenic metal input in a Biosphere Reserve:the case study of the Cananeia–Iguape coastal system,Southeastern Brazil

Michel Michaelovitch de Mahiques • Rubens Cesar Lopes Figueira •

Alexandre Barbosa Salaroli • Daniel Pavani Vicente Alves • Cristina Goncalves

Received: 7 February 2011 / Accepted: 18 June 2012

Ó Springer-Verlag 2012

Abstract The Cananeia–Iguape system consists of a com-

plex of estuarine and lagoonal channels located in the coastal

region of southeasternBrazil known as Lagamar, a Biosphere

Reserve recognized by the United Nations Educational,

Scientific andCulturalOrganization (UNESCO) in 1991. The

area suffered dramatic environmental changes along the last

ca. 150 years initiated by the 1852 opening of an artificial

channel, the Valo Grande, connecting the Ribeira de Iguape

River to the estuarine system. Due to Au, Ag, Zn, and Pb

mining activities that took place in the upstream regions of the

Ribeira de Iguape River since the seventeenth century, the

system has acted as a final destination of contaminated sed-

iments. Analysis of cores located along the estuarine system

revealed a history of contamination, with an increase of

anthropogenic metal input between the decades of 1930 and

1990. The anthropogenic influence can be traced in locations

as far as 20 km from the mouth of the artificial channel.

Keywords Heavy metals � Sedimentation � Man-induced

effects � Mining � Brazil

Introduction

Owing to their physicochemical and geological character-

istics, estuaries and lagoons are among the most susceptible

environments for heavy metal contamination. The input of

these metals often occurs as a product of mining activities

in the upland areas located a substantial distance from the

coast (Johnson et al. 2005; Price et al. 2005; Masson et al.

2006; Osher et al. 2006; Lorenzo et al. 2007; Freitas et al.

2008). In some cases, the effects of mining activities have

been recorded in the adjacent shelf (Corredeira et al. 2008)

and deeper environments (Jesus et al. 2010).

In the assessment of the contamination history of coastal

environments, the study of contaminant variability along

sedimentary cores is a valuable approach (Deely and Fer-

gusson 1994; Chan et al. 2001; Zourarah et al. 2007; Hosono

et al. 2010, among several others in the past decades). Along

withmeasurement of contaminants, there are two key aspects

thatmust be taken into account in these studies: establishment

of a reliable chronology (Cearreta et al. 2002) and compari-

son of contamination levels with a baseline taken from

unpolluted or pristine samples (Abrahim and Parker 2008).

The Cananeia–Iguape system consists of a complex of

estuarine and lagoonal channels, located in the region of

southeastern Brazil (Fig. 1) known as Lagamar, a Bio-

sphere Reserve recognized by UNESCO in 1991. The

channels are bordered by abundant mangrove vegetation,

which harbors oysters and mussels, and the region as a

whole is an important nursery ground or residence for

economically valuable species such as shrimp, anchovies,

snooks, king and acoupa weakfish and leatherjacks.

The area suffered dramatic environmental changes in the

last ca. 150 years, initiated by the 1852 opening of an artificial

channel, the Valo Grande, connecting the Ribeira de Iguape

River (Fig. 1) to the estuarine system. As a consequence, the

openingof theValoGrande affected both thephysicochemical

characteristics and the deposition of sediments in the area.Our

goal was to assess the geochemical record of the uppermost

layers of the sedimentary column of the Cananeia–Iguape

M. M. de Mahiques (&) � R. C. L. Figueira �A. B. Salaroli � D. P. V. AlvesOceanographic Institute, University of Sao Paulo,

Praca do Oceanografico, 191, Sao Paulo, SP 05508-120, Brazil

e-mail: [email protected]

C. Goncalves

Consultoria Planejamento e Estudos Ambientais,

Sao Paulo, SP, Brazil

123

Environ Earth Sci

DOI 10.1007/s12665-012-1809-6

Author's personal copy

system to evaluate the historical input of anthropogenic

metals in the area over the last 150 years, with a special

emphasis on the period of industrial mining activities.

Study area

Since Besnard (1950) originally proposed four stages of

evolution based on the geomorphological evidence, several

studies, spanning at least six decades, have analyzed

the geological and geomorphological characteristics of the

Cananeia–Iguape system. According to the author, the

process occurred during the Late Tertiary and Early Qua-

ternary periods and was associated with a slow sea level

regression that formed the coastal plain. After this first

work, the sedimentary evolution of this complex of estu-

arine and lagoonal channels and the associated coastal

plain was extensively analyzed in several papers, such as

Fig. 1 Location of the

Cananeia–Iguape coastal system

and of the cores analyzed in this

study

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those written by Petri and Suguio (1971, 1973) and Suguio

and Martin (1978). In addition, Martin and Suguio (1978)

proposed a five-stage model of evolution to explain the

origin of the Cananeia–Iguape system. Essentially, the

present lagoonal channels represent the drowning of the

paleo-river channels that developed after the transgressive

phase of Isotope Stage 5e, locally named the Cananeia

Transgression (120,000 years BP).

The Ribeira River forms the largest drainage basin of

the S–SE Brazilian coast (from 22° to 30°S), with an area

of about 25,000 km2. The outflow of the river in its lower

course varies from about 300 to more than 1,200 m3/s; this

variation is strongly controlled by the climatic regime.

According to the Koppen classification, the climate of

this system shows characteristics of a humid tropical cli-

mate, varying from humid tropical without a dry season to

humid tropical with a cool summer. The average rainfall

values are about 2,200 mm year-1, with a marked rainy

season between November and February (the austral

summer). Annual average temperatures vary from 16 to

19 °C, but temperatures as low as 0 °C and as high as

35 °C have been recorded.

Due to the climatic and geomorphologic characteristics,

vegetation cover is marked by the presence of salt marshes

and mangroves along mixohaline bodies of water and by

dune vegetation and Atlantic forests on the higher areas.

The opening of a 4-km long artificial channel linking the

Ribeira River to the Cananeia–Iguape lagoonal system

began in 1827 but was not finished until 1852 (Geobras

1966). The aim of this channel was both reduce shipping

distance and costs for agricultural goods (especially rice,

the main economic product of the region) from the coun-

tryside to the main export harbor of the region, Porto

Grande; located in Iguape City, it was, in the first half of

the nineteenth century, one of the most important harbors

of the former Brazilian Empire. After its opening, the

channel eroded laterally over the next 150 years by as

much as 4 m per year. The original dimensions of the

channel (4.4 m wide and 2 m deep) rapidly increased,

resulting in the current channel width of about 250 m with

depths of up to 7 m. Originally named Valo do Rocio, the

channel was renamed Valo Grande (‘‘Big Scour’’) in ref-

erence to the dimensions that the channel acquired a few

decades after it was opened. As a result of this erosion,

environmental changes in the Cananeia–Iguape system

were intensified, since about 60 % of the main flow of the

Ribeira River was transferred to the lagoonal system. In

addition, the input of sands and mud was dramatically

increased and an intralagoonal delta was developed in the

channel mouth, with a siltation phenomenon that can be

verified as far as 20 km away.

The Valo Grande channel was closed in 1978 by a dam

constructed of stones and sand; however, the dam was

destroyed in 1983, during a large El Nino event, by major

flooding of the Ribeira River, which affected the areas

located upstream and lead to financial losses for agriculture

in the area.

Mining activities in the upper course of the river began

in the seventeenth century, originally as manual mining of

Au and Ag. In 1945, industrial Pb and subsidiary Zn

mining and the associated foundry (Plumbum S/A) were

established but ceased activity in 1995 due to exhaustion of

reserves, technological difficulties and economic factors.

One aspect that must be stressed is the fact that, throughout

Plumbum’s operation, the slag was simply disposed,

apparently without any concern about contamination, along

the margins of the Ribeira River or its tributaries, such that

even after 1995, significant values of Pb can be measured

in river sediments. About 177,000 tons of slag materials

have been disposed along the river margins (Eysink 1988).

The first evaluation of the levels of heavy metals in the

sediments of the Ribeira de Iguape River and the Canan-

eia–Iguape system was done by Eysink (1988). The authors

measured levels of Cd, Cu, Hg, Pb and Zn in the surface

river and estuarine sediments and, with the exception of Pb,

found no evidence of contamination. Conversely, the levels

of Pb in the river sediments reached values as high as

4,000 mg kg-1, and seven of the twelve river sampling

stations presented Pb levels higher than 500 mg kg-1.

Only one (82.0 mg kg-1) of the ten estuarine sediment

samples presented Pb values above the detection limit

(20.0 mg kg-1); however, it must be noted that none of

these estuarine samples were collected close to the mouth

of the Valo Grande channel.

Methods

Four cores were collected along the main channel of the

lagoonal system, in April 2008, with the aid of a Rossfelder

VT-1 vibracorer, using liners of pre-cleaned PVC tubes

(Fig. 1; Table 1). The location of the cores was determined

to create a gradient of progressive distance from the Valo

Grande mouth with the following sequence: CAN02, about

2 km east of the Valo Grande mouth towards the entrance

to the lagoonal system; CAN04, 200 m west of the Valo

Grande mouth; CAN05, approximately 7.5 km west of

Table 1 Position and length of the cores analyzed in this study

Sample Lat (S) Long (W) Length (m) Water depth (m)

CAN02 24°42.477 47°32.787 1.44 3.0

CAN04 24°43.418 47°33.858 1.50 \1.0

CAN05 24°45.245 47°37.370 2.00 \1.0

CAN07 24°48.895 47°41.612 1.27 \1.0

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the Valo Grande mouth towards the internal part of the

lagoonal system; and CAN07, about 20 km west of

the Valo Grande mouth towards the internal part of the

lagoonal system. With exception of core CAN02, collected

at a water depth of 3 m, all of the other cores have been

collected at the margins of the channel.

The cores were opened immediately after collection and

sampled continuously at intervals of 2 cm. Samples for

chemical analyses were immediately frozen for later ele-

mental analysis. All of the samples have been used in the

chemical analyses in this work.

To evaluate the depth limits for sedimentation rates

determination as well as to establish correlations between

grain size and metal contents, the decarbonated samples

have been analyzed, using a Malvern Mastersizer 2000

Laser analyzer. For the purpose of this study, only the

contents of clay ? silt have been considered.

Owing to conspicuous changes in the grain-size char-

acteristics, the calculation of sedimentation rates has been

determined only for the sections of the cores which shown

relatively homogeneous silt ? clay contents. Determina-

tion of sedimentation rates was obtained via 210Pb gamma

spectrometry, analyzing its photopeak of 47 keV using a

low background Ge detector (EG&G Ortec model GMX

25190P), as described in Figueira et al. (2007). The cal-

culation of the sedimentation rate based on the unsupported

Pb has been made via the CIC (Concentration Initial

Constant) Model (Appleby and Oldfield 1978; Joshi and

Shukla 1991). The sedimentation rate was calculated using

the formulae:

S ¼ k � Dð Þ=Ln C2100 Pb

ÿ �

= C210Pb

ÿ ��

where S is the sedimentation rate in cm year-1, k is the

radioactive decay constant of the 210Pb (equal to

0.31076 year-1), D is the distance between the core-top

and the measured stratum (cm), C0210Pb is the count of the

unsupported 210Pb at the core-top, and C210Pb is the count

of the unsupported 210Pb at the measured stratum. The

reliability of the radiochronological technique was verified

by the utilization of IAEA standard materials. In addition,

the opening of the Valo Grande, as determined by the 210Pb

chronology showed compatibility with abrupt changes in

the foraminiferal record observed in core CAN05 (Mahi-

ques et al. 2009), in which the calcareous foraminifer

assemblage has been totally substituted by agglutinant

species and thecamoebians at the depth of 130 cm.

Elemental analysis (Cu, Cr, Fe, Pb, Sc and Zn) was

performed using the ICP-OES technique with a Varian

Vista MPX. The analysis followed the procedures descri-

bed in the Method 3050B of the SW-846 series (USEPA

(United States Environmental Protection Agency) 1996).

Approximately 2 g of dry sediment was digested with

10 mL of 1:1 HNO3 at 95 °C for 15 min. After cooling,

another 5 mL of concentrated HNO3 was added and the

solution was heated for 30 min. This second procedure was

repeated until the digestion of the sample was complete.

Then, 2 mL of water and 3 mL of 30 % H2O2 were added

under heating until the elimination of the organic matter

was complete. After this step, 10 mL of concentrated HCl

was added and the solution was kept under heating for

15 min. The solution was filtered through a Whatman 41

filter and 10 mL of concentrated HCl was added to the

digestate. Finally, the solution was filtered again through a

Whatman 41 filter and the filtrate was collected in a

100 mL volumetric flask. The volume was completed to

100 mL and the solution analyzed in a Varian Vista MPX

ICP-OES following the procedure described in the Method

6010C (USEPA (United States Environmental Protection

Agency) 2007). Measurement precision for all elements

was better than 5 %. Method accuracy was obtained by

analyzing the reference materials SS-1 and SS-2 (soil from

EnviroMATTM

). The analytical accuracy was in agreement

with certified values for the metals in each material ana-

lyzed and are presented in Table 2.

Table 2 Obtained values, in

mg kg-1, in reference materials

(SS-1 and SS-2)

Element Obtained

value (n = 18)

Certified

value

Confidence

value

Tolerance

value

SS-1

Cr 54 ± 12 64 55–73 13–115

Cu 631 ± 80 690 657–723 503–877

Fe 20,724 ± 4,805 20,406 19,037–21,775 12,645–28,167

Pb 185 ± 11 233 219–247 152–314

Zn 4,150 ± 1,010 6,775 6,467–7,083 5,066–8,484

SS-2

Cr 30 ± 3 34 30–38 14–54

Cu 177 ± 9 191 182–200 139–243

Fe 19,708 ± 9,362 21,064 19,597–22,495 12,831–29,261

Pb 99 ± 8 126 116–136 68–184

Zn 431 ± 16 467 444–490 337–597

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It is important to mention that this is a very strong acid

digestion which dissolves the minerals (including galena)

(Aydogan et al. 2007) which in fact, are present in forms

which have potential mobility and bioavailability.

Enrichment factor (EF) and sediment pollution index

(SPI)

An excellent analysis of different parameters for determi-

nation of background levels and contamination of sedi-

ments was recently published by Abrahim and Parker

(2008). With respect to the background levels, the authors

stress the importance of getting values of uncontaminated

sediments in deeper layers of cores. This aspect is partic-

ularly important for the sediments of the region since the

potential sources of sediments are Pb-mineralized rocks;

thus, the utilization of average shale or crust values might

be not applicable in our study.

When concerning the assessment of the degree of con-

tamination of sediments, Abrahim and Parker (2008)

evaluate the utilization of the values of the geoaccumula-

tion index (Igeo, Muller 1969), the enrichment factor (EF,

Grant and Middleton 1990), the degree of contamination

(Cd, Hakanson 1980) and the modified degree of contam-

ination (mCd, Abrahim and Parker 2008).

In the case of our study, the choice for the utilization of

the EF for determination of the contamination was related

to the fact that this parameter is least sensitive to grain-size

variations along the core. Therefore, the EF with respect to

the normalized value of Sc has been calculated using the

formula:

EF ¼ Me½ �i= Sc½ �

i

ÿ �

= Me½ �0= Sc½ �0ÿ �

Fig. 2 Variations of silt ? clay contents (%) a core CAN04; core CAN02, c core CAN05; core CAN07

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where [Me]i is the metal concentration value in the sample,

[Me]0 is the metal background value, [Sc]i is the Sc

concentration in the sample, and [Sc]0 is the Sc background

value.

The normalizing element must be an important con-

stituent of one or more of major fine-grained trace metal

carrier and reflect their grain-size variability in the sedi-

ments. It must be conservative and must have a uniform

flux from crystalline rock sources in order to compensate

for changes in the input rates of various diluents or

variations in sedimentation rates (UNEP 1995). In this

work, elemental values were normalized to levels of

scandium which is structurally combined in clay minerals;

moreover, anthropogenic sources of Sc are seldom and Sc

is stable in the environment and it can be accurately

measured by the ICP technique (UNEP 1995; Lin et al.

2008). The background values corresponded to the aver-

age element concentrations of the five bottommost sam-

ples of core CAN05; these were samples of the sediments

that clearly corresponded to those deposited prior to the

opening of the Valo Grande, as determined by the 210Pb

chronology. The five-category pollution index (Andrews

and Sutherland 2004) was used for the pollution assess-

ment: EF\ 2, minimal pollution; EF 2–5, moderate

pollution; EF 5–20, significant pollution; EF 20–40, high

pollution and EF[ 40, extreme pollution. On the other

Fig. 3 Plot of Ln210Pbxs activity versus depth of the cores analyzed in this study

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hand, Rubio et al. (2000) consider the EF[ 1 as the limit

for polluted sediments.

A second approach for the assessment of contaminated

sediments was the utilization of the sediment pollution

index (SPI) proposed by Singh et al. (2002). SPI is a multi-

metal approach for assessment of sediment quality with

respect to trace metal concentrations and metal toxicity

(Lin et al. 2008). The SPI is expressed as

SPI ¼ R EFm �Wmð Þ=RWm

where EFm is the enrichment factor of a metal m, Wm is the

toxicity weight of the metal, assigned as 1 for Zn and Cr, 2

for Cu and 5 for Pb (Singh et al. 2002).

The same authors proposed a classification based on five

levels, defined as: SPI0—natural sediments, (with values of

SPI ranging from 0 to 2), SPI1—low polluted sediments

(SPI ranging from 2 to 5), SPI2—moderately polluted

sediments (SPI ranging from 5 to 10), SPI3—highly pol-

luted sediments (SPI ranging from 10 to 20), SPI4—dan-

gerous sediments (SPI higher than 20).

Fig. 4 a Variations of content

of Cr, Cu, Pb, Zn, and Sc along

core CAN04. b Variations of

enrichment factors of Cr, Cu, Pb

and Zn, and sediment pollution

index, along core CAN04

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Results

The plots of silt ? clay versus depth and 210Pbxs activity versus

depth of the cores are shown respectively in Figs. 2 and 3.

Core CAN04

Core CAN04 (150 cm long) was the closest to the Valo

Grande mouth. From the base up to 40 cm, it presents a

coarsening upward inwhich the silt ? clay content decreases

from 70 to 20 %, followed by a fining upward in which the

values increase up to 60 % (Fig. 2a). Its core-top presented an

average sedimentation rate of 0.72 ± 0.01 cm year-1, as

determined by 210Pb spectrometry (Fig. 3a).

From this rate, it has been assumed that the base of

the core corresponds to the beginning of the nineteenth

century, close to the initiation of the opening of the Valo

Grande. The core exhibits the highest measured values

in Cu (46 mg kg-1), Pb (197 mg kg-1) and Zn

(135 mg kg-1) at the depth of 42 cm (Fig. 4a). This

depth, corresponding to the year of 1948, represents the

highest EFs of the same metals (Cu = 7, Pb = 20,







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Zn = 3.5) and the highest SPI value (13), indicating

highly polluted sediments (Fig. 4b). In this sense, this

enrichment could be directly associated with the begin-

ning of the industrial mining activities and the disposal

of slag along the margins of the river. Conversely, the

enrichment of Cu and Zn observed prior to 1910 may be

associated with the previous non-mechanized mining

activities, which had been occurring in the Ribeira valley

since the seventeenth century.

Core CAN02

Core CAN02 (140-cm long) was sampled approximately

2 km from themouth of theValoGrande channel towards the

northernmost mouth of the lagoon (Fig. 1). From its base

until 110 cm, it presents a muddy facies, with silt ? clay

content as high as 80 %. From this depth up to the core-top,

there is an oscillation of values, ranging from 20 to 60 %

(Fig. 2b).Based on the 210Pb chronology,withmeasurements







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until 70 cmCoreCAN02 exhibited an average sedimentation

rate of 1.00 ± 0.06 cm year-1 (Fig. 3b).

Assuming a constant sedimentation rate, we may assume

that its base corresponded approximately to the third

quarter of the nineteenth century, indicating that all of the

sediments deposited in the core were potentially under the

influence of the Valo Grande opening effect. With the

exception of Pb, the metal content was relatively constant

along the core, showing a trend of higher values between

the depths of 80 and 40 cm (Fig. 5a), which roughly

corresponds to the period between 1930 and 1970. Higher

EFs were clearly observed for Pb and, to a much lesser

extent, Cu in this time interval. SPI values higher than 5

(moderately polluted sediments) were essentially con-

trolled by the higher input of Pb (Fig. 5b).

Core CAN05

Core CAN05 (168-cm long) was sampled about 7.5 km

from the Valo Grande mouth. This core has been the only







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which has shown a conspicuous abrupt sedimentological

contact, at 130 cm (Fig. 2c). The base is essentially com-

posed by sandy sediments with silt ? clay contents not

higher than 20 %. From 130 cm until the top the core is

marked by mudy sedimentation, with silt ? clay contents

ranging from 70 to 80 %. Nevertheless, only the topmost

70 cm show a constant sedimentation rate of

1.52 ± 0.11 cm year-1 (Fig. 3c).

Based on its characteristics, including its microfaunal

records cited above, it has been assumed that Core CAN05

was the only core that exhibited sure indications of basal

sediments deposited prior to the opening of the artificial

channel; therefore, these basal sediments were the only

samples that could be used as background levels.

As a rule, anthropogenic metals exhibit levels that are

not significantly lower than those observed in the vicinity

of the Valo Grande; however, the peak of higher Pb input is

not clearly visible, as it was in the previous cores (Fig. 6a).

On the other hand, it was observed that EF values signifi-

cantly decreased despite the fact that Pb still presented

levels of moderately polluted sediments (Fig. 6b).

Core CAN07

Core CAN07 was collected approximately 20 km from the

mouth of the Valo Grande. It is characterized by the

prevalence of sands, with a general trend of fining upward

and two peaks of higher contents in silt ? clay at 80 cm

Fig. 8 XY plots of a Pb versus Sc on Core CAN04, b Pb versus Sc on Core CAN07, c Cr versus Sc on Core CAN04, d Cr versus Sc on Core

CAN07

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and in its core-top. The average sedimentation rate for the

core was calculated as 0.67 ± 0.05 cm year-1 (Fig. 3d).

The increase in anthropogenic metals in this core was

seen only after 20 cm (beginning of the 1980s) (Fig. 7a, b).

Discussion

In all of the cores, it is possible to use the anthropogenic

metals (Pb, Zn and Cu) to recognize the beginning of the

influence of the Valo Grande flow in the Cananeia–Iguape

system. It is also possible to recognize the beginning of the

industrial mining activities as observed in Fig. 4. Second-

ary spikes can be attributed to variations in the river dis-

charge and a peak in the Enrichment Factor of Pb and Cu in

core CAN07 (Fig. 7b) may be attributed to the destruction

of the dam that blocked the flow of the Valo Grande,

between 1978 and 1983.

One aspect seen only in core CAN07 was related to the

behavior of Cr, a non-anthropogenic metal in the area. The

change in contents prior to and after the opening of the

Valo Grande (Fig. 7b) was a clear indication of the change

in the source rocks of the local sediments. This change in

the origin of the sediments was also seen in the XY plots of

Pb (anthropogenic) and Cr (non-anthropogenic) versus Sc

(normalizer), in the cores located closest to and farthest

from the Valo Grande (CAN04 and CAN07, respectively)

(Fig. 8).

Furthermore, this finding indicates that, even in low

quantities, it has been assumed that the input of anthro-

pogenic metals can be traced at least up to the site of core

CAN07.

A correlation analysis among the metals (Table 3)

showed a progressive increase in correlation between Pb

and the other elements, especially Sc, with the distance

from the Valo Grande mouth.

This trend is likely related to the grain size in which Pb

is being carried to the coastal system, other than as a

suspended material. When reaching the low hydrodynamic,

microtidal estuary, it is likely that the coarse grains of

galena are rapidly deposited; thus, only the finer fractions

can be transported and redistributed along the estuarine

channel. Figure 9 presents the XY plots between Pb content

and clay ? silt contents in which it is possible to recognize

the progressive increase of correlation between Pb and

grain size, in the cores located farther than the Valo Grande

mouth. The lack of correlation between anthropogenic

metals and grain size has already been observed in several

Table 3 Pearson correlation

coefficients (R) among the

different metals in each core

Significant values (a B 0.05)

are bold

Cr Cu Pb Zn Sc

CAN04

Cr

Cu 0.5605

Pb 0.1109 0.71721

Zn 0.67985 0.89351 0.72135

Sc 0.99618 0.57143 0.12607 0.68922

CAN02

Cr

Cu 0.93695

Pb -0.18285 0.078356

Zn 0.92512 0.97158 0.16117

Sc 0.98405 0.94655 -0.14783 0.93575 0

CAN05

Cr

Cu 0.91618

Pb 0.49988 0.75346

Zn 0.98953 0.94153 0.5749

Sc 0.99014 0.92644 0.53493 0.97429

CAN07

Cr

Cu 0.79107

Pb 0.78756 0.94856

Zn 0.90286 0.94454 0.90599

Sc 0.96322 0.83173 0.80595 0.90565

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other papers, such as Krumgalz et al. (1992), Zhang et al.

(2001), Che et al. (2003), and Pereira et al. (2007). In all of

these studies, this unusual pattern was used to identify the

areas under the direct influence of an anthropogenic

impact.

Two other factors have to be taken into consideration

when analyzing the data presented here, the area is non-

industrialized and it is distant from the contaminant sour-

ces. As stated before, the Cananeia–Iguape system is

considered as a Biosphere Reserve, and the local economic

activities are based mainly on artisanal fisheries and small-

scale agriculture. Nevertheless, the contents of Cu and Zn

(as subsidiary mining products) and especially Pb (and

corresponding enrichment factors) present at the same

order of magnitude as those of heavily populated or

industrialized areas (Hornberger et al. 1999; Cearreta et al.

2002). The second factor, that the mining activities were

located at least 300 km from the Valo Grande area, indi-

cates that the fluvial processes of the Ribeira River were

not effective at retaining the contaminated sediments. This

distance makes the Valo Grande area a unique case, dif-

ferent from other studies in which the mining activities

were located close to the estuarine systems (Price et al.

2005; Osher et al. 2006).

Conclusions

The cores retrieved from the Cananeia–Iguape coastal

system, a Biosphere Reserve, showed a record of about

150 years of anthropogenic metal input, especially Pb,

originating from mining activities that took place at least

Fig. 9 XY plots of: a Pb versus %clay ? silt on Core Can04, b Pb versus %clay ? silt on Core CAN02, c Pb versus %clay ? silt on Core

CAN05, d Pb versus %clay ? silt on Core CAN07

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300 km from the Valo Grande. The highest contamination

levels occurred between the decades of 1940 and 1990,

corresponding to the period of industrialized mining.

In areas located under direct discharge of the Valo

Grande Channel, the lack of correlation between Pb con-

centrations and grain size indicates that the suspended load

may not be the only factor in controlling the anthropogenic

metal distribution.

The contents of metals and corresponding enrichment

factors have the same order of magnitude as those of

industrialized areas; the EF of Pb reached values of up to

20 in the vicinity of the Valo Grande mouth. Although

present in fewer quantities, the input of anthropogenic

metals could be detected in a core located 20 km from the

Valo Grande mouth.

Acknowledgments The authors are indebted to Mr. Clodoaldo

Tolentino and Mr. Edilson Faria, for the help in the sampling survey

and core sub-sampling. Financial support has been provided by the

Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP),

grant no. 06/04344-2.

References

Abrahim GMS, Parker RJ (2008) Assessment of heavy metal factors

and degree of contamination in marine sediments from Tamaki

Estuary, Auckland, New Zealand. Environ Monit Assess

136:227–238

Andrews S, Sutherland RA (2004) Cu, Pb and Zn contamination in

Nuuanu watershed, Oahu, Hawaii. Sci Total Environ

324:173–182

Appleby PG, Oldfield F (1978) The calculation of Lead-210 dates

assuming constant rate of supply 210Pb to sediment. Catena

5:1–8

Aydogan S, Erdemoglu M, Ucar G, Aras A (2007) Kinetics of galena

dissolution in nitric acid solutions with hydrogen peroxide.

Hydrometallurgy 88:52–57

Besnard W (1950) Consideracoes gerais em torno da regiao lagunar

de Cananeia e Iguape I. Bol Inst Paulista Oceanogr 1:9–26

Cearreta A, Irabien MJ, Leorri E, Yusta I, Quintanilla A, Zabaleta A

(2002) Environmental transformation of the Bilbao estuary, N.

Spain: microfaunal and geochemical proxies in the recent

sedimentary record. Mar Pollut Bull 44:487–503

Chan LS, Ng SL, Davis AM, Yim WWS, Yeung CH (2001) Magnetic

properties and heavy-metal contents of contaminated seabed

sediments of Penny0s Bay, Hong Kong. Mar Pollut Bull

42:569–583

Che Y, He Q, Lin WQ (2003) The distributions of particulate heavy

metals and its indication to the transfer of sediments in the

Changjiang Estuary and Hangzhou Bay, China. Mar Pollut Bull

46:123–131

Corredeira C, Araujo MF, Jouanneau JM (2008) Copper, zinc and

lead impact in SW Iberian shelf sediments: an assessment of

recent historical changes in Guadiana river basin. Geochem J

42:319–329

Deely JM, Fergusson JE (1994) Heavy metal and organic matter

concentrations and distribution in dated sediments of a small

estuary adjacent to a small urban area. Sci Total Environ

153:97–111

Eysink GGJ (1988) Metais Pesados no Vale do Ribeira e em Iguape—

Cananeia. Ambiente 2:6–13

Figueira RCL, Tessler MG, Mahiques MM, Fukumoto MM (2007) Is

there a technique for the determination of sedimentation rates

based on calcium carbonate content? A comparative study on the

Southeastern Brazilian shelf. Soil Found 47:649–656

Freitas MC, Andrade C, Cruces A, Munha J, Sousa MJ, Moreira S,

Jouanneau JM, Martins L (2008) Anthropogenic influence in the

Sado estuary (Portugal): a geochemical approach. J Iber Geol

34:271–286

Geobras (1966) Complexo Valo Grande, Mar Pequeno, Rio Ribeira

de Iguape. Technical Report, Sao Paulo, DAEE

Grant A, Middleton R (1990) An assessment of metal contamination

of sediments in the Humber estuary, UK. Estuar Coast Shelf Sci

1:71–85

Hakanson L (1980) The quantitative impact of pH, bioproduction and

Hg-contamination on the Hg-content of fish (pike). Environ

Pollut Ser B Chem Phys 1:285–304

Hornberger MI, Luoma SN, van Geen A, Fuller C, Anima R (1999)

Historical trends of metals in the sediments of San Francisco

Bay, California. Mar Chem 64:39–55

Hosono T, Su C, Siringan F, Amano A, Onodera S (2010) Effects of

environmental regulations on heavy metal pollution decline in

core sediments from Manila Bay. Mar Pollut Bull 60:780–785

Jesus CC, de Stigter HC, Richter TO, Boer W, Mil-Homens M,

Oliveira A, Rocha F (2010) Trace metal enrichments in

Portuguese submarine canyons and open slope: anthropogenic

impact and links to sedimentary dynamics. Mar Geol 271:72–83

Johnson VG, Peterson RE, Olsen KB (2005) Heavy metal transport

and behavior in the lower Columbia River, USA. Environ Monit

Assess 110:271–289

Joshi SR, Shukla BS (1991) AB initio derivations of formulation for210Pb dating of sediments. J Radional Nucl Chem 148:73–79

Krumgalz BS, Fainshtein G, Cohen A (1992) Grain size effect on

anthropogenic trace metal and organic matter distribution in

marine sediments. Sci Total Environ 116:15–30

Lin C, He M, Zhou Y, Guo W, Yang Z (2008) Distribution and

contamination assessment of heavy metals in sediment of the

Scond Songhua River, China. Environ Monit Assess 137:329–

342

Lorenzo F, Alonso A, Pellicer MJ, Pages JL, Perez-Arlucea M (2007)

Historical analysis of heavy metal pollution in three estuaries on

the north coast of Galicia (NW Spain). Environ Geol 52:789–802

Mahiques MM, Burone L, Figueira RCL, Lavenere-Wanderley AAO,

Capellari B, Rogacheski CE, Barroso CP, Santos LAS, Cordero

LM, Cussioli MC (2009) Anthropogenic influences in a lagoonal

environment: a multiproxy approach at the Valo Grande mouth,

Cananeia–Iguape system (SE Brazil). Braz J Oceanogr

57:325–337

Martin L, Suguio K (1978) Le Quaternaire Marin du littoral bresilien

entre Cananeia et Barra de Guaratiba (RJ). In: Proceedings of

international symposium on coastal evolution in the quaternary.

Sao Paulo. Sao Paulo, IGCP, pp 296–331

Masson M, Blanc G, Schafer J (2006) Geochemical signals and

source contributions to heavy metal (Cd, Zn, Pb, Cu) fluxes into

the Gironde Estuary via its major tributaries. Sci Total Environ

370:133–146

Muller G (1969) Index of geoaccumulation in the sediments of the

Rhine River. Geo J 2:108–118

Osher LJ, Leclerc L, Wiersma GB, Hess CT, Guiseppe VE (2006)

Heavy metal contamination from historic mining in upland soil

and estuarine sediments of Egypt Bay, Maine, USA. Estuar

Coast Shelf Sci 70:169–179

Pereira E, Baptista Neto JA, Smith BJ, McAllister JJ (2007) The

contribution of heavy metal pollution derived from highway

Environ Earth Sci

123


runoff to Guanabara Bay sediments: Rio de Janeiro, Brazil. An

Acad Bras Cien 79:739–750

Petri S, Suguio K (1971) Some aspects on the neocenozoic

sedimentation in the Cananeia–Iguape lagoonal region, Sao

Paulo, Brazil. Estud Sedimentol 1:25–33

Petri S, Suguio K (1973) Stratigraphy of the Iguape–Cananeia

lagoonal region sedimentary deposits, Sao Paulo, Brazil. Part II:

heavy minerals studies, micro-organisms inventories and strati-

graphical interpretations. Bol IG-USP 4:7–85

Price GD, Winkle K, Gehrels WR (2005) A geochemical record of the

mining history of the Erme Estuary, South Devon, UK. Mar

Pollut Bull 50:1706–1712

Rubio B, Nombela MA, Vilas F (2000) Geochemistry of major and

trace elements in sediments of the Rıa de Vigo (NW Spain): an

assessment of metal pollution. Mar Pollut Bull 40:968–980

Singh M, Muller G, Singh IB (2002) Heavy metals in freshly

deposited stream sediments of rivers associated with urbaniza-

tion of the Ganga Plain, India. Water Air Soil Pollut 141:35–54

Suguio K, Martin L (1978) Formacoes quaternarias marinhas do

litoral paulista e sul-fluminense. In: Suguio K, Martin L (eds)

International symposium on coastal evolution in the quaternary,

IGCP, Sao Paulo, pp 1–5

UNEP (1995) Manual for the geochemical analyses of marine

sediments and suspended particulate matter. Ref Methods Mar

Pollut Stud 63:1–74

USEPA (United States Environmental Protection Agency) (1996)

Method 3050B. Acid digestion of sediments, sludges and soil.

Revision 2, December

USEPA (United States Environmental Protection Agency) (2007)

Method 6010C. Inductively coupled plasma-atomic emission

spectrometry. Revision 3, February

Zhang W, Yu L, Lu M, Hutchinson SM, Feng H (2001) Magnetic

approach to normalizing heavy metal concentrations for particle

size effects in intertidal sediments in the Yangtze Estuary, China.

Environ Pollut 147:238–244

Zourarah B, Maanan M, Carruesco C, Aajjane A, Mehdi K, Freitas

MC (2007) Fifty-year sedimentary record of heavy metal

pollution in the lagoon of Oualidia (Moroccan Atlantic coast).

Estuar Coast Shelf Sci 72:359–369

Environ Earth Sci

123

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