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PDF - Scientific Online Publishing
Sediment Geochemistry and Climatic
Influences in a River Influenced by Former
Mining Activities: the Case of Ribeira de
Iguape River, SP-PR, Brazil
Denis M. S. Abessa1 *, Lucas Gonçalves Morais1 , Fernando César Perina2 ,
Marcela Bergo Davanso3 , Valéria Guimarães S. Rodrigues4 , Letı́cia M. P.
Martins5 , Joel BarbujianiSı́golo6
UNESP, Pça Infante Dom Henrique, s/n, São Vicente, SP, Brazil, 11330-900.
IO-USP, Pça do Oceanográfico, 191, São Paulo, SP, Brazil, 05508-900.
3 Ministério do Meio Ambiente, Braslia, DF, Brazil. 70068-900.
EESC-USP, Av. Trabalhador São-carlense, 400, São Carlos, SP, Brazil, 13566-590.
PROCAM-USP, Av. Prof. Luciano Gualberto, 1289, São Paulo, SP, Brazil, 05508-010.
6 IGc-USP, Rua do Lago, 562, São Paulo, SP, Brazil, 05508-080.
*Corresponding author: [email protected]
The Ribeira de Iguape River (RIR) was historically contaminated by residues from mining
activities. These activities ceased in the late 1990’s, but the residues remained deposited
along the river banks. This study aimed to evaluate the sediment characteristics of the RIR
in different hydro-meteorological conditions and detect eventual changes in the geochemistry.
Three sampling surveys were conducted, in which sediments were collected in 6 sites, and
then analyzed for sediment textures and metals concentrations. Sediments were predominantly
sandy, and samples collected downstream to the mining areas tended to be enriched by metals,
especially Pb, Cr, Cu, Ni and Zn. Concentrations of metals in sediments tended to be higher
after rainstorm episodes, evidencing the pollution sources are not totally controlled and that the
stormwater runoff may carry metals to the RIR.
Environmental Recovery; Metals; Mining; Sediment; Toxicity
Climatic regime represents primarily the main factor to regulate hydrological balance of watersheds,
since it controls the amounts of water flowing towards the rivers both by surficial runoff, tributaries and
underground drainage [1, 2]. In special, extreme rainstorm episodes have potential to produce significant
landscape and geomorphology changes, since they may redistribute sediments along the drainage basin,
creating new or intensifying existing erosive and depositional areas, or even exporting material through
the fluvial system [3, 4].
The geomorphologic impacts of an extreme event are closely related to factors such as the parent
material erodibility, topography, vegetation cover and (historic) land use [5, 6]. Nevertheless, linkages
between hill slope and river channel processes might be expected to be important, especially those
concerning to removal of surficial sediments due to storm water runoff and eventual landslides [4]. Studies
reported increasing inputs of sediments to watersheds related to rainstorm precipitations [3, 4]. In addition,
the increase of water volumes and flow in watersheds are a secondary factor that may display sediment
transport through the basin, since settled particles can be ressuspended as a physical consequence to the
energy increase [7].
A further problem related to storm events is the contamination, as stormwater runoff may drag a series
of contaminants deposited on soils or associate to sediment particles, as pesticides and metals, among
others [8]. Such contaminants tend to be carried to low energy areas, as riverine lowlands, estuaries and
the sea, where contaminated particles set, producing environmental contamination [9].
In the Southeastern Brazil, the Ribeira de Iguape River (RIR) basin represented an important region for
mining activities, comprising nine major mines which mainly operated on lead extraction [10]. During
mines operation, tailing and metallurgical slags of blast furnace [11] were directly dumped into the
Ribeira de Iguape River till the early 1990’s decade, when the material started to be disposed directly on
the ground, on the river banks, exposed to the weathering [11] and consequently to lixiviation. Mining
activities have ceased in 1995, but about 89,000 m3 of metal rich residues were kept deposited on the
ground, close to the river [12], representing source of metals, especially Pb, to RIR and to the lower
portion of its basin, which is represented by the Cananéia-Iguape Estuarine Complex (CEIC), a sensitive
region that was recognized as a World Natural Heritage.
During the 1980 and 1990 decades, high levels of metals, especially Pb, were reported to RIR waters
and sediments [10, 13–15]. On the other hand, there are indications that the Pb contents in waters and
sediments from RIR have been decreasing along time [16–19]; however, high concentrations of metals
have been found in bivalves [20, 21] and suspended sediments [11] from RIR indicating the persistence
of environmental problems in the river. Moreover, high concentrations of metals have been observed in
sediments collected in the CIEC [13, 22], indicating transport of contaminated material downstream.
This investigation aimed to evaluate the sediment characteristics of the RIR in different hydrometeorological conditions, as during a dry period, after an extreme rainstorm episode and after moderate
rain precipitations, detecting eventual differences in the geochemistry.
2.1 Study area
The study area is inserted into the Ribeira de Iguape River Basin, comprising the cities of Cerro Azul
and Adrianópolis, in the state of Paraná, and Iporanga, Ribeira, Eldorado, SeteBarras, Juquiá and Registro,
in the state of São Paulo. The region is known as Ribeira Valley, is situated between 24 00’S - 24 45’S
and 47 30’W - 49 30’W (Figure 1).
The Ribeira de Iguape River Basin is mainly situated in the Coastal Province, with a small portion
within Atlantic Uplands, presenting rugged topography and abrupt altitude variations [23]. Mostly,
topography hilly, with slopes higher than 15% and local amplitudes from 100 to 300m or >300m.
The local climate may be classified, according to Köppen, as following: 5% of basin are classified as
wet tropical without dry season, 50% belong to the wet subtropical type with warm summers and the
resting (45%) presents wet subtropical type with cool summers; however, these climatic limits are not
well defined and vary inter-annually [24]. The region is influenced by two main water masses; Tropical
Sediment Geochemistry and Climatic Influences in a River Influenced by Former Mining Activities: the Case of
Ribeira de Iguape River, SP-PR, Brazil
Figure 1. Map of the studied area (Ribeira de Iguape River basin) indicating the sampling sites.
Atlantic (which influences on rain distribution) and Polar Atlantic, responsible for lower temperatures.
However, the Tropical Atlantic is more influent. The mean precipitation is about 1,400 mm/year, but it
may reach up to 2,300 mm/year. The weather is characterized by a very rainy season, from October to
March, with mean precipitation rates above 120 mm/month, and a drier season, from April to September,
in which the monthly precipitation rates drop to about 70 mm.
The Ribeira de Iguape River Basin occupies about 28,000 km2, between the NE of Paraná and the
SW of São Paulo [17]. According to Theodorovicz & Theodorovicz (2007) [23], 61% from the basin
belongs to São Paulo, whereas 39% in at Paraná. The river length is 470km, between its spring head
(east from Paranapiacaba Ridge, at Paraná), and its mouth, in the Atlantic Ocean and close to the city of
Iguape. The main tributary of RIR is the Juquiá River. Close to the spring, the river is named Ribeirinha,
flowing eastward until receiving the contribution of Açunguı́ River, close to the city of Cerro Azul, at
380m altitude. From this point, the river starts to be named as Ribeira de Iguape, and flow through valleys,
presenting higher slopes and several waterfalls. After the city of Itaóca, the topography becomes a less
slope and the river exhibits a meandering pattern, producing depositional areas [14]. Close to the mouth,
the lowlands become wide, and the river forms flooding areas, close to the city of Iguape, and already
starts to be influenced by the tides and estuarine waters.
2.2 Sampling
The sampling sites comprised: (P1) or reference site, that was situated upper to mining activities and ore
processing; (P2) located just after Rocha mine; (P3) close to Ribeira City; (P4) after Plumbum processing
plant; (P5), after the confluence with Pardo River, and (P6), close to the city of Eldorado.
Sampling surveys were conducted in October 2010, August 2011 and April 2012. The 1st sediment
collection was made after a relatively dry period (e.g<35mm precipitation in the previous 20 days),
whereas the 2nd sampling occurred after a severe rainstorm (>220mm precipitation in 24h), which caused
extreme precipitation and destructive floods to cities and rural areas situated along the RIR. This rainstorm
caused the RIR level to rise up 14m in 24h. The 3rd sampling survey was conducted after weak to moderate
rains that did not cause flood in the region (approximately 65mm precipitation).
The techniques used to collect, transport and store the sediments followed the procedures established
by National Guidelines [25]. Surficial sediment samples (2-cm surface layer) were collected with small
plastic shovels from the river banks, at the water level, and conditioned in sealed plastic bags. Immediately
after collection, samples were transferred to thermic containers with ice, and transported to the laboratory.
In laboratory, sediment samples to chemistry analyses were frozen at -20 C. In August 2011, a sample of
the metallurgical wastes disposed on the ground, produced during the smelting process of ore by Plumbum
Company, was collected and analyzed aiming to compare concentrations of metals to those obtained
previously by [15].
2.3 Sedimentological analyses
The grain size distribution was obtained by dry sieving method [26]. Initially, 150g aliquots from each
sediment sample and the slag were previously dried at 60 C for at least 72h. Then, the material was sieved
for 10 minutes in a set of different mesh sizes (2mm, 1.7mm, 1.18mm, 600µm, 150µm, 75µm and <
75µm) installed on a shaker. The fractions retained in each mesh were weighted in analytical balance
and recorded. The analysis of organic matter was made by the method of loss by ignition in a muffle and
gravimetry [27].
2.4 Chemical analyses
Sediment samples were analyzed by inductively coupled plasma optical emission spectrometry (ICPOES) [28, 29], after acid extraction by acquaregia. Concentrations of aluminum (Al), arsenic (As),
cadmium (Cd), lead (Pb), copper (Cu), chromium (Cr), iron (Fe), manganese (Mn), nickel (Ni) and zinc
(Zn) were measured. For sediments, QA/QC consisted of analyzing a standard sample fortified with
metals (Standard Soil – RTC – CRM023) and blanks; QL were 0.5 mg/kg for most of elements and 0.05
mg/kg for Cd. Recoveries were within the acceptable ranges, and ranged between 90 and 110% for most
elements and 82% for Cd. The laboratory is accredited by ISO17025 standard. The same procedure
was used to evaluate chemical composition of the sample of the metallurgical wastes from Plumbum.
The metals concentrations in sediments were compared to Canadian Sediment Quality Guidelines (SQG)
for freshwater [30], considering TEL (threshold effect level) and PEL (probable effect level), and to the
background values proposed tor RIR basin [31, 32].
Sediment Geochemistry and Climatic Influences in a River Influenced by Former Mining Activities: the Case of
Ribeira de Iguape River, SP-PR, Brazil
Table 1. Mean Concentrations of Metals (mg/kg) in Residues from Mining Activities in the Upper Portion ofRIR
Residue type
Tailings from Rocha Mine
Tailings from Panelas (Plumbum) Mine
Slags from Plumbum Plant
Slags from Plumbum Plant
6366.70 8817.00 110.90
34018.00 118004.33 2730.33
26615.00 100087.00 1357.00
42.10 111624.20
214.17 3656.00
This study
3.1 Characterization of Primary Sources of Metals
The primary contamination sources to RIR consists of residues from mining activities (tailings from ore
processing) and metallurgical wastes (slags), which were better studied and described previously [11, 15].
Although mining has ceased, residues from such activities are still deposited close to the former mines
and to the metallurgical plants.
Two main old mines still presented tailings deposited directly on the ground (Rocha and Panelas mines,
respectively located on Adrianópolis and Ribeira municipalities) [15]. Tailings from Rocha Plant were
deposited close to the Rocha creek, and present an approximately volume of 3,000m3 . In their turn, the
residues from Plumbum (Panelas mine) were deposited on the RIR riverbank, with a volume of about
89,000m3 [12].
The residues of metallurgical activities (from Plumbum Plant) were formerly discharged into the RIR
(along 40 years), but during the 1990’s decade these slags were deposited directly on the RIR riverbanks,
totalizing 200,000m3 [12] of residues with As, Cd, Pb, Cu, Cr and Zn.
Guimarães [15] evaluated the chemical composition of slags from Rocha and Panelas mines, and
observed high concentrations of Pb and other elements (Table 1). Guimarães&Sı́golo [11] analyzed the
slags from the Plumbum Plant and detected much higher concentrations. Results obtained in the present
study for these slags also showed very high concentrations of some metals, which were similar to those
previously observed [11]. Considering their higher volume and higher contamination, the slags from
Plumbum may be considered the more relevant source of metals to RIR.
3.2 Sediment Geochemistry
Grain size distribution analyses showed that sediments presented a preponderantly sandy composition,
with variable percentages of gravel and fines, and predominance of fine and very fine sands (Table 2). The
organic matter (OM) contents were generally low, ranging between 0.39% (P6) and 4.96% (P3). There
were no clear spatial or temporal patterns concerning to OM distribution and variations or to grain size.
The data obtained in this investigation are compatible to that available in the literature.The monitoring
program made by State Environmental Agency has systematically registered values lower than the
background for the majority of analyzed elements; however, at same time, Pb concentrations exceeding
the TEL values have been frequently observed by such monitoring [18, 33–40] in RIR sediments. On the
other hand, low concentrations of Pb in sediments from RIR were found by Melo et al. [41], whereas
Guimarães&Sı́golo [11] detected high concentrations of Pb and other elements in sediments from RIR,
which were lower than those observed in a recent past [13].
Figure 2. Concentration of metals (mg/kg) in sediments from RIR (2010, 2011 and 2012). Yellow and red-brownish
lines show respectively TEL and PEL values [30], whereas black lines show background values [31, 32].
Sediment Geochemistry and Climatic Influences in a River Influenced by Former Mining Activities: the Case of
Ribeira de Iguape River, SP-PR, Brazil
Table 2. Grain Size Distribution and Organic Matter in Sediments from Ribeira de Iguape River in the 2010, 2011
and 2012 sampling surveys.
Grain Size Distribution (%) and Organic Matter
October 2010
VFS Fines OM (%)
3.19 2.82 2.35 27.03 27.10
2.67 9.86 17.12 32.10 23.67
5.03 10.79 31.16 31.62
4.48 8.72 7.02 41.70 15.44
1.43 2.02 5.97 24.73 30.39
August 2011
P1 0.34 5.15
P2 0
P3 4.58 4.44
P5 0
P6 23.8 33.56
16.29 41.20
32.00 32.09
5.35 34.35
28.50 52.69
12.88 6.03
April 2012
VFS Fines OM (%)
VFS Fines OM (%)
P1 1.84 10.71 18.35 19.79 37.05 11.69 5.60
P2 0
0.65 10.12 28.08 46.95 13.83 3.75
P3 0
0.10 0.18 3.81 51.69 43.65 10.69 2.82
P4 0.58 0.26 0.65 10.73 58.91 28.41 11.18 1.53
P5 3.45 1.25 1.50 11.80 59.05 22.45 11.87 0.70
P6 0.17 0.18 0.78 42.76 49.01 6.88 4.15
G = gravel; VCS = very coarse sand; CS = coarse sand; MS = medium sand; FS = fine sand; VFS = very fine sand; and OM =
organic matter.
Previous studies [42–46] have shown that areas under influence of mining activities present environmental fragilities or contamination. In this study, positive correlation between sandy fractions and metals
may be related to the nature of the mining residues, which are thick and are comminuted when residues
are transported downstream [15].
On the other hand, the grain size distribution analyzes showed that the samples were predominantly
composed by fine and very fine sands, indicating the sampling sites did not constitute depositional areas.
The upper RIR region is hilly, being characterized by steeper slopes, which attribute more energy to the
system and make the river channel to be seated in the relief, hindering the formation of the depositional
areas. The low concentrations of the majority of metals in sediments possibly could be explained by
the sandy nature of sediments and the high energy in the system. Some enrichment by metals could be
observed in the sites located downstream, suggesting the influence of former mining activities, especially
at P4, P5 and P6. The sediment from P4 exhibited enrichment trends for other elements present in
mining residues, as Cu and Zn. The worse conditions observed at P4 for Pb probably were related to the
concentrate residues of Plumbum plant.
In the second sampling campaign, concentrations of metals in sediments tended to be slightly higher
than those observed in the first campaign, but generally levels were below TEL and close to background
values [31, 32]. Pb concentrations exceeded the PEL in P5, and Cr levels exceeded the TEL in samples
from P2 and P6. The sediment from reference area exhibited concentrations of Cu, Zn and Cr slightly
above the background values, in the sampling survey conducted in 2011, after an extreme rainstorm
In the third sampling campaign, levels were again generally low and close to background levels. The
TEL values were exceeded for Pb in P5 and for Cr in P2, whereas background values were exceeded for
Pb (P5), Ni (P4 and P5), Cr (P2), Cu (P1, P2, P3, P4 and P5) and Zn (P4 and P5).
The results of each campaign were observed separately. In 2010, the concentrations of metals in
sediments were relatively low (Figure 2). The lowest Pb concentration was observed in the reference
sample (3.5 mg/kg), which was also lower than the proposed background for RIR basin, that is 12-16 mg/kg
[31, 32]. The sediment sample from P4 presented the highest concentrations of all analyzed elements;
in this sample, the concentration of Pb was above the local background and about 7x greater than the
concentration measured in the reference sediment (P1). The Cd levels were below the quantification limits
for all samples. Comparing the obtained concentrations to the Canadian SQGs [30], the concentrations of
all analyzed metals were below TEL.
Regarding to the contents of metals, concentrations were generally low (i.e., below the TEL and/or
the background values) and tended to increase downstream (Figure 2), especially Pb, Ni, Cu, Zn and
Mn. For Pb, lowest concentrations were observed in the reference sample, which was lower than the
proposed background for RIR basin [31, 32]. On the other hand, the sediment sample from P5 presented
the highest concentrations of Pb, exceeding TEL (2010 and 2011) and PEL (2011). The Cd levels were
below the quantification limits for all samples. For Cr, concentrations above TEL were detected in P2 and
P6.Concentrations of Cu, Zn and Ni eventually were found above the background values.
The results of this investigation are also coherent to the published data, as literature suggests that
metals levels in RIR sediments are decreasing along time [16–18, 38, 39]. Thus, the results corroborate,
at least partially, the official reports from the State Environmental Agency on natural attenuation in RIR
catchment [18]. Natural restoration has been observed worldwide in rivers contaminated by metals from
mining activities [47–49]; but this process may be slow and depends on several factors [50].
On the other hand, literature indicates that the restoration process is not complete, as suspended
sediments seem to be still enriched by Pb [11], and bioaccumulation of metals in burrowing bivalves has
been reported [20, 21]. This is corroborated by the remaining enriched levels of metals in sediments from
RIR, especially Pb, which suggests a residual influence of mining contamination. Mahiques et al. [22]
detected a continuous enrichment of Pb and Cr in the sediments from the Estuarine Complex of Iguape
and Cananéia, at the mouth of RIR, which was, in its turn, directly related to the former mining activities,
situated upper RIR. Moraes et al. [14] estimated that about 840,000 tons of Pb are transported downstream
RIR each year, mostly associated to fines. Such transport of metals may explain the enrichment in
sediments along RIR, especially in its lower portion and in the downstream estuarine areas [13, 22].
In addition, our data showed that the concentrations tended to be higher in the 2nd and 3rd sampling
surveys, which were conducted after rainstorms. According to Costa et al. [51] the rainstorms have
major role in removing surface soils and contaminants along the RIR basin. In a study conducted in the
Yellow River, Xu (2002) [52] demonstrated that strong rainstorms may cause hyper concentrated flows of
suspended sediment concentrations of more than 300 kg/m3. If such suspended solids are contaminated,
they would be the carriers of contaminants to the watercourse. The increase of concentrations of metals
and nutrients in the sediments of a RIR tributary during the rainy season was observed by Cunha et al.
[53]; these authors stated that rainstorms were related to an increase in the adsorption and complexation
reactions between fines, organic matter, metals and nutrients. Corsi& Landim [10] have indicated that the
lixiviation process is related to the increase of metals inputs from mining areas to some RIR tributaries,
which could explain the data obtained in the present investigation.
In summary, in spite of the natural restoration process which is in progress along RIR, there is still
enrichment by Pb and other elements in its sediments, especially downstream of the former mining
activities, and the rainstorms still have a role in carrying metals to the RIR catchment.
Sediment Geochemistry and Climatic Influences in a River Influenced by Former Mining Activities: the Case of
Ribeira de Iguape River, SP-PR, Brazil
The authors thank São Paulo Research Foundation (FAPESP) (grants2009/52762-6 and 2008/54607-5)
and CNPq for the financial support. We also acknowledge the NEPEA staff for the assistance, and the
local inhabitants from Ribeira de Iguape Valley for the help during field activities.
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