Evaluation of water and sediment of the Graminha and Águas da Serra streams in the city of Limeira...

Spectrochimica Acta Part B 63 (2008) 1432–1442

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Spectrochimica Acta Part B

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Evaluation of water and sediment of the Graminha and Águas da Serra streams inthe city of Limeira (Sp-Brazil) by Synchrotron Radiation Total ReflectionX-ray Fluorescence☆

Silvana Moreira ⁎, Elizete Vieira FazzaUniversity of Campinas, School of Civil Engineering, Architecture and Urban Design, P. O. Box 602, Zip Code 13083-852, Campinas, SP, Brazil

☆ This paper was presented at the 12th ConferenFluorescence Analysis and Related Methods held in Trenispublished in the Special Issue of SpectrochimicaActa Par⁎ Corresponding author. Tel.: +55 19 3521 2377; fax:

E-mail addresses: [email protected] (S. Moreir(E.V. Fazza).

0584-8547/$ – see front matter © 2008 Elsevier B.V. Aldoi:10.1016/j.sab.2008.10.022

a b s t r a c t
a r t i c l e i n f o
Article history:
The city of Limeira is locat Received 10 October 2007Accepted 14 October 2008Available online 1 November 2008
Keywords:Heavy metalsWater qualitySedimentGalvanization industrySynchrotron Radiation Total Reflection X-RayFluorescence (SR-TXRF)

ed in the state of São Paulo, Brazil and has the second largest economy anddemographic growth of the state. It comprises an expressive economy with industries in several productivesectors. The source of the Graminha and Águas da Serra streams is located within the Limeira urban zone. Thestreams cross part of the rural zone and unite by draining into the Piracicaba River. It is possible that thesebasins suffer or have already suffered the impacts of environmental pollution caused by anthropogenic factors.Since the city has galvanization industries for the production of precious and semi-precious jewels as well asimitation jewelry, the concentration descriptions and interpretations of heavymetals inwaters and sedimentsindicate anthropogenic influence and the dumping of these compounds into the Piracicaba River. TheSynchrotron Radiation Total Reflection X-Ray Fluorescence (SR-TXRF) was used for determining the metals. Allmeasurementswere performed using awhite beam of synchrotron radiation for excitation and a Ge hyperpuredetector. Detection limits forwater sampleswere 0.04 μg L−1 and in sediment samples 0.03 μg g−1 for Cu and Znelements. In the water samples, concentrations higher than permissible as established by the Brazilianlegislation (CONAMA) for Al, Fe, Zn, Cr, Ni, Cu and Pb, were observed. For sediment samples, values higher thanquality reference values defined by the Brazilian legislation (CETESB) were verified for Cr, Zn, Cu, Ni and Pb.

© 2008 Elsevier B.V. All rights reserved.

1. Introduction

In Brazil, a large part of domestic and industrial waste is dumpeddirectly intowater bodies without treatment and this amount of wasteexceeds permissible standards for the water bodies. Therefore theevaluation of the real conditions of the water body and its watershedis an important part of an environmental management program thataims to recover or improve water quality of the basin. The region ofCampinas in São Paulo state is considered economically anddemographically developed and the city of Limeira is inserted in thisregion (Fig. 1).

Limeira has diverse industries with a large and varied productionof precious and semi-precious jewels, and imitation jewelry.

The evaluation of thewater and sediment qualities of the Graminhaand Águas da Serra streams in Limeira is a way to diagnose the impactgenerated by urban occupation. The aimof this study is to demonstratethe need for action to revert the current situation. The evaluation ofwater and sediment quality was carried out in six strategic points in

ce on Total Reflection X-rayto (Italy), 18–22 June 2007, andtB, dedicated to that conference.+55 19 3521 2411.a), [email protected]

l rights reserved.

each stream. The metal concentrations were determined by Synchro-tron Radiation Total Reflection X-Ray Fluorescence (SR-TXRF).

2. Theoretical analysis

Multielemental standard solutions, in different concentrationscontaining Al, Si, Ca, Ti, Cr, Fe, Ni, Zn, Ga and Sr for the K series (Table 1)and Mo, Ba, Sm, Lu, Pt and Pb for the L series (Table 2) were preparedby an adequate dilution of stock solutions. For Al, Si, Ti, Fe, Ni, Ga, Sr,Mo, Ba and Pt the solution elements used were Calibration Standardfor Environmental Analysis and for Cr, Zn, Sm, Lu and Pb elements,Atomic Absorption Standard Solution. Gallium was added as aninternal standard in all standard solutions and samples.

For the quantitative analysis, which shows the fluorescent intensityand the concentration relation, the following Eq. (1) was used:

Ii = SiCi ð1Þ

IiIGa

=SiSGa

Ci

CGaor

IiIGa

CGa =SiSGa

Ci ð2Þ

Assuming Ri =IiIGa

CGa and SR =SiSGa

ð3Þ

Results in Ri = SRd Ci ð4Þ

mailto:[email protected]

mailto:[email protected]

http://dx.doi.org/10.1016/j.sab.2008.10.022

http://www.sciencedirect.com/science/journal/05848547

Fig. 1. Location of the city of Limeira.

1433S. Moreira, E.V. Fazza / Spectrochimica Acta Part B 63 (2008) 1432–1442

Where: Ii and Ci=fluorescent intensity (cps) and concentration(μg mL−1) of the i element in the sample; IGa and CGa=fluorescentintensity (cps) and concentration (μg mL−1) of Ga (internal standard);Si and SGa=sensitivity of i element and Ga (cps. mL μg−1); SR=relativesensitivity for i element (non-dimensional), and Ri=product of relativeintensity (i element and Ga) by Ga concentration (μg mL−1).

The relative sensitivities of the system can be calculated by Eq. (4)using the standard solutions. Eq. (4)) is also used to determine theconcentration of the elements present in the samples [1].

The detection limits DLi for each element i is directly related to thebackground intensity Ii(BG), in agreement with Eq. (5) [2].

DL = 3

ffiffiffiffiffiffiffiffiffiffiffiffiffiIi BGð Þ

t

rCGa

IGadSRð5Þ

where t=measuring time in seconds.

Table 1Elemental concentrations in the standard solutions for K series calibration system

Concentration (mg L−1)

Element Code Dilution 1 Dilution 2 Dilution 3 Dilution 4 Dilution 5

Al 40,419-5 (Aldrich) 21.29 38.31 52.08 63.33 69.04Si 40,396-2 (Aldrich) 21.55 38.77 52.71 64.09 69.87Ti 40,388-1 (Aldrich) 6.03 9.05 10.85 14.59 18.09Cr C-5899 (Sigma) 6.03 9.05 10.85 14.59 18.09Fe 40,406-3 (Aldrich) 6.03 9.05 10.85 14.59 18.09Ni 40,399-7 (Aldrich) 6.06 9.09 10.91 14.66 18.18Zn Z-2750 (Sigma) 6.03 9.05 10.85 14.59 18.09Sr 40,393-8 (Aldrich) 6.09 9.14 10.96 14.74 18.27Ga 20,714-4 (Aldrich) 9.32 9.32 9.32 9.32 9.32

3. Experimental

3.1. Sampling site

The study area is characterized by heterogeneous conditions alongthe paths of the streams. There are regions with high populationdensity, urban regions with low demographic density and agriculturalregions. The areas near the streams are defined as PermanentPreservation Areas, but do not present the characteristics defined bythis legislation in relation to respecting the 30 m of protection for thestream bank and the 50 m of water head.

The hydrographic micro-basins in the urban area of Limeira weredivided into areas according to pluvial water and sewage contribu-tions, totalizing 12 areas in four major regions: Tatu, Águas da Serra,Graminha and Pinhal. The Tatu region is divided into sub-areas called:Margem Esquerda (1, 2, 3), Margem Direita (1, 2), Barroca Funda (1, 2),Lagoa Nova and Duas Barras. In Fig. 2 the micro-basins located in theurban area of Limeira can be observed.

The Águas da Serra and Graminha streams drain into the Coqueiroriver tributary of the Piracicaba River. The location and urban area ofthe Graminha and Águas da Serra streams can be visualized in Fig. 3.

Table 2Elemental concentrations in the standard solutions for L series calibration system


Element Code Dilution 1 Dilution 2 Dilution 3 Dilution 4 Dilution 5

Mo 40,400-4 (Aldrich) 17.15 32.47 46.22 58.65 69.93Ba 40,416-0 (Aldrich) 5.77 10.93 15.56 19.75 23.54Sm Acros-Organics 5.72 10.82 15.41 19.55 23.31Lu Acros-Organics 5.72 10.82 15.41 19.55 23.31Pt 20,736-5 (Aldrich) 5.55 10.50 14.95 18.96 22.61Pb L-4885 (Sigma) 5.77 10.93 15.56 19.75 23.54Ga 20,714-4 (Aldrich) 9.32 9.32 9.32 9.32 9.32

Fig. 2. Map showing the micro-basins of Limeira located in the urban area.

1434 S. Moreira, E.V. Fazza / Spectrochimica Acta Part B 63 (2008) 1432–1442

The Graminha and Águas da Serra streams present the followingproblems associated with urban and industrial pollution: (i) dumpingof domestic and industrial residues; (ii) deposits of constructionresidues; and (iii) irregular dumping of domestic and industrialsewage directly into the water source.

The location of the sampling points was established in function ofthe following criteria: (i) dumping or affluent located in the streams;(ii) location of previous studies; and (iii) ease of access. Six strategicpoints of study were determined in each stream, where the last twowith domestic sewage contribution. Two samplings were pro-grammed in order to cover a hydrologic year, one in the dry periodanother in the wet period.

The Águas da Serra and Graminha urban region and the locationswhere the samples were collected can be observed in Figs. 4 and 5,respectively.

3.2. Samples: preparation and measurement

The SR-TXRF analyses were carried out in the X-ray FluorescenceBeamline at the Brazilian Synchrotron Light Laboratory, located inthe city of Campinas, São Paulo, Brazil. All measurements wereperformed under normal conditions of pressure and temperatureand a geometry excitation standard was used. The standards andsamples were excited with a white beam, with energy from 2 to

24 keV, 2 mm width and 1 mm height, operating under totalreflection conditions [2]. The standards, water and sediment sampleswere measured for 100 s. The X-ray detection was performed by a Gedetector (165 eV, 5.9 keV).

For water sample preparation, 1 mL was transferred to anEppendorf® tube, and a 100 µL Ga solution (102.5 mg L−1) was thenadded. After this stage, the mixture was agitated for homogenizationand 5 µL was transferred to a Perspex support and dried under aninfrared lamp.

The sediment samples were dried in porcelain capsules in a stoveat 50 °C (±2 °C), in order to avoid loss by evaporation. The sampleswere then crushed (≤1.5 mm) and quartered in order to obtain arepresentative sub-sample for the digestion procedure.

The digestion of the sediment samples was performed using theUSEPA 3050B method [3]. After digestion, the procedure followed thesame steps as already described for water samples.

4. Results and discussion

4.1. System calibration and detection limits (DL)

The fluorescent intensities were obtained from fitting the spectrawith the Quantitative X-Ray Analysis System (QXAS) [4]. Experimentalrelative sensitivities were calculated for the K (Fig. 6) and L series

Fig. 3. Map showing the Graminha and Águas da Serra streams in Limeira.


(Fig. 7). Experimental data were fitted in order to determinethe sensitivity of the elements not presented in the standard solutions.

The detection limits for water and sediment samples werecalculated through Eq. (5) for 100 s measuring time (Table 3).

4.2. Data validation

In order to check the methodology, two standard referencematerials were analyzed. The concentrations measured by SR-TXRFwere compared with the certified values [5]. The results for TraceElements in Natural Water (NIST/SRM 1640) and San Joaquim Soil(NIST/SRM 2709) are presented in Tables 4 and 5. The samples wereprepared in triplicate and five measurements of each sub-samplewere performed resulting in fifteen determinations (n=15). Theaverage concentration was calculated based on the fifteen determi-nations. The confidence interval calculated at a 95% confidence level(α=0.05).

4.3. Water samples of the Graminha and Águas da Serra streams

The values for water samples were compared with the MaximumPermissive Values (MPV) established by the Brazilian legislation [6].The results for dry and wet periods and also the MPV can be observedin Tables 6 and 7 for the Águas da Serra stream and in the Tables 8

and 9 for the Graminha stream. Values higher than the maximumpermissive values are in italic and bold.

4.4. Sediment samples of the Graminha and Águas da Serra streams

The values determined for sediment samples were compared withthe Quality Reference Values for Soils (QRV) established by CETESB [7]because there are no reference values for sediments in the Brazilianlegislation.

The results for sediment samples were also compared with theCanadian Sediment Quality Guidelines for the Protection of AquaticLife (CSeQGs) established by the Canadian Council of Ministers of theEnvironment (CCME) [8]. The Threshold Effect Level (TEL) andProbable Effect Level (PEL) can be visualized in Table 10.

The results and the QRV can be observed in Tables 11 and 12 forGraminha (GR) and Tables 13 and 14 for Águas da Serra (AS). Thevalues higher than QRV (CETESB) are in italic and bold and thosehigher than PEL have an asterisk.

Sediment concentrations from Brazil and other countries ob-tained from the literature were compared to the results for theGraminha and Águas da Serra streams. This comparison can bevisualized on Table 15. For Cr, the average concentration was48 mg kg−1 for the Graminha Stream and 59 mg kg−1 for the Águasda Serra Stream. For the Tatu River, also located in Limeira the

Fig. 4. Map showing urban area and sediment and water sampling sites for the Águas da Serra stream.


values for sediment were 98 mg kg−1. The average concentrationfor Ni was 13 mg kg−1 for the Graminha Stream and for the TatuRiver, 45 mg kg−1. The same results were observed for Zn and Pbindicating, unexpectedly, that the Graminha and the Águas daSerra are as polluted as the Tatu River, which is the main River ofLimeira.

Fig. 8 presents a synopsis of the environmental pollution inwater and sediment samples of the Graminha and Águas da Serrastreams.

The results show that there are metals even in those samplingsites which do not receive city wastewater and that some samplingsites show higher concentrations of metals after the release ofwastewater.

The results indicated that the deterioration of the sediment qualityis lower in the dry period for the Graminha and the Águas da Serrastreams. In fact, in the dry season there is less interference of the raindragging material and the water resource volume is lower than in therainy season.

Fig. 5. Map showing urban area and sediment and water sampling sites for Graminha stream.


Fig. 6. Relative sensitivity, experimental and fitted, for K series using SR-TXRF.

Fig. 7. Relative sensitivity, experimental and fitted, for L series using SR-TXRF.

Table 4Measured, certified and reference values for trace elements in natural water (NIST/SRM1640)

Element Measured value (µg kg−1) Certified value (µg kg−1)

Caa 6.974±0.03a 7.045±0.089a,b

K 908±7 994±27b

V 12.96±2.07 12.99±0.37Cr 39.8±0.85 38.6±1.6Mn 109.6± 5.63 121.5±1.1Co 17.24±0.74 20.28±0.31Ni 20.8±1.5 27.4 1±0.8b

Cu 75.8±1.68 85.2±1.2b

Zn 54.8±0.96 53.2±1.1b

Rb 2.32±0.88 2.00±0.02b

Sr 112.99±5.51 124.2±0.7

a mg kg−1 n=15, α=0.05.b reference values.

Table 5Measured and certified values for San Joaquim soil (NIST/SRM 2709)

Element Measured value (mg kg−1) Certified value (mg kg−1)

Ca 17,916±1006 18,900±500V 113±8 112±5Cr 141±6 130±4Mn 549±6 538±17Fe 35,836±2000 35,000±1100Cu 36.4±3.0 34.6±0.7Zn 104±5 106±3

n=15 α=0.05.

Table 6Average concentration (n=4) and uncertainty of Al, Fe and Zn in water samples for dryand wet periods at Águas da Serra Stream


Al Fe Zn

Point Wet CV Dry CV Wet CV Dry CV Wet CV Dry CV

AS 01 2.3 3.6 5.5 7.1 5.0 0.4 13.4 2.0 0.18 7.8 1.01 0.6AS 02 4.0 2.3 4.2 6.0 1,.1 0.3 1.0 0.9 0.13 1.1 0.31 1.3AS 03 3.9 1.3 3.4 7.8 4.1 0.6 14.3 1.2 0.19 3.1 0.37 1.4AS 04 4.3 6.0 3.7 6.6 0.7 0.1 1.9 0.7 0.12 0.1 0.36 0.8AS 05 2.5 9.4 1.6 8.4 5.4 1.2 9.4 0.8 0.33 1.4 0.32 0.3AS 06 4.0 5.9 5.4 5.5 4.6 9.3 3.0 0.9 0.18 1.6 0.70 1.3MPV 0.1 mg L−1 0.3 mg L−1 0.18 mg L−1

CV=Coefficient of Variation (%).


The results indicate anthropogenic pollution coming from pluvialwaters, residues in general and clandestine emissions in the watersource since metal concentrations in water and sediment samples

Table 3Detection limits for water and sediment samples for 100 s measuring time by SR-TXRF

Element Water (μg L−1) Sediment (mg kg−1)

Al 14.03 4.54Si 7.86 2.38S 4.45 1.32Cl 2.48 0.73K 1.35 0.44Ca 0.36 0.11Ti 0.18 0.06Cr 0.10 0.03Mn 0.07 0.03Fe 0.06 0.02Ni 0.05 0.03Cu 0.05 0.03Zn 0.06 0.03Sr 0.44 0.09Pb 0.24 0.11

were higher than legal standards even in the sampling sites wherethere are no effluent contributions.

The presence of metals such as Fe, Cr, Ni, Cu, Zn and Pb, mainlybefore points 5 and 6, can indicate the interference of the precious,semi-precious and imitation jewelry industries in the environmentalfractions of water and sediment of the springs in study, since thosemetals are widely used in this sect.

5. Conclusions

In the water samples, concentrations higher than permissivevalues established by the Brazilian legislation (CONAMA) forAl, Fe, Zn, Cr, Ni, Cu and Pb were observed. For sediment sam-ples, values higher than the reference quality value, defined byBrazilian legislation (CETESB), were verified for Cr, Zn, Cu, Ni andPb. The results point to the need for adequate management of

Table 9Average concentration (n=4) and uncertainty of Cr, Mn, Ni, Cu and Pb in water samples for dry and wet periods at Graminha Stream

Concentration (μg L−1)

Cr Mn Ni Cu Pb

Point Wet CV Dry CV Wet CV Dry CV Wet CV Dry CV Wet CV Dry CV Wet CV Dry CV

GR 01 27 4.5 8 6.4 23 5.6 37 7.8 9 9.0 5 4.8 62 2.4 15 7.7 6 9.1 b0.25 –

GR 02 33 4.0 187 2.5 29 9.6 22 2.5 13 5.8 19 4.6 17 7.9 21 9.7 15 9.3 b0.25 –

GR 03 188 2.2 8 6.2 87 5.4 32 4.2 52 6.7 3 8.9 21 6.9 50 1.4 94 8.8 b0.25 –

GR 04 1223 2.9 11 9.7 126 7.7 44 2.4 11 5.1 2 9.3 212 3.6 16 9.3 173 2.0 b0.25 –

GR 05 41 6.8 143 6.5 130 2.8 69 9.1 16 7.5 39 9.4 46 3.1 163 7.3 8 9.8 b0.25 –

GR 06 20 4.7 12 5.8 90 3.9 73 5.3 35 5.9 11 6.2 130 2.0 73 2.6 43 6.2 b0.25 –

MPV 50 μg L−1 100 μg L−1 25 μg L−1 9 μg L−1 10 μg L−1


Table 7Average concentration (n=4) and uncertainty of Cr, Mn, Ni, Cu and Pb in water samples for dry and wet periods at Águas da Serra Stream

Concentration (μg L−1)

Cr Mn Ni Cu Pb

Point Wet CV Dry CV Wet CV Dry CV Wet CV Dry CV Wet CV Dry CV Wet CV Dry CV

AS 01 1085 0.6 30 5.9 91 10.3 12 1.3 207 3.1 8 5.5 52 2.8 77 3.8 68 7.2 95 5.1AS 02 18 4.6 10 8.3 64 2.2 75 4.1 45 4.0 10 9.3 46 1.7 29 4.8 876 1.2 8 4.2AS 03 125 2.8 54 1.7 134 5.5 18 8.7 29 5.6 b0.05 – 12 8.3 8 4.1 b0.25 – 50 3.1AS 04 11 2.3 30 9.4 32 8.5 71 7.2 5 4.5 12 6.8 16 8.9 23 5.2 29 2.4 18 8.7AS 05 788 2.3 599 1.6 104 7.2 73 7.7 159 1.4 158 2.1 25 9.1 16 6.1 20 9.1 36 8.0AS 06 18 8.3 b0.10 – 207 5.0 104 3.5 49 0.1 18 7.9 194 3.1 38 8.5 23 8.3 b0.25 –

MPV 50 μg L−1 100 μg L−1 25 μg L−1 9 μg L−1 10 μg L−1


Table 8Average concentration (n=4) and uncertainty of Al, Fe and Zn in water samples for dry and wet periods at Graminha Stream


Al Fe Zn

Point Wet CV Dry CV Wet CV Dry CV Wet CV Dry CV

GR 01 2.4 6.6 1.4 7.5 1.2 1.4 0.6 0.4 0.23 1.7 0.21 0.5GR 02 2.2 7.6 2.5 5.7 2.1 0.6 1.8 1.6 0.25 0.7 0.22 1.7GR 03 5.1 9.4 1.6 6.0 5.1 1.3 0.8 0.8 1.94 0.4 0.12 1.4GR 04 5.7 7.9 1.5 2.9 11.2 0.9 1.4 0.5 1.24 1.7 0.13 1.3GR 05 1.4 4.9 9.2 8.7 2.9 0.1 1.4 3.3 0.37 0.4 0.23 3.3GR 06 2.9 8.8 0.8 2.7 2.6 0.4 1.9 0.7 0.83 0.5 0.17 1.8MPV 0.1 mg L−1 0.3 mg L−1 0.18 mg L−1


Table 10Canadian Sediment Quality Guidelines for the Protection of Aquatic Life

Element Cd Cu Cr Ni Pb Zn

TEL (mg kg−1) 0.6 35.7 37.3 18 35 123PEL (mg kg−1) 3.5 197 90 35.9 91.3 315

Table 11Average concentration (n=4) and uncertainty of Al, Fe, Zn and Cr in sediment samples for d

Concentration (mg kg−1)

Al Fe

Point Wet CV Dry CV Wet CV Dry

AS 01 2118 5.8 965 9.4 16834 0.8 14162AS 02 947 8.6 982 6.3 11195 0.3 11424AS 03 1534 8.1 1017 0.5 17090 0.4 8141AS 04 723 7.5 1195 3.4 16069 0.7 37038AS 05 826 5.7 2479 5.8 8087 0.6 8056AS 06 483 9.8 1020 3.0 10376 0.2 8556QRV Not established Not established

1) CV=Coefficient of Variation (%) 2) in italic and bold values higher than QRV (Quality Refea Values higher than PEL (Probable Effect Level).


the basins and the presence of negative impacts in the studiedregion.

Acknowledgments

This study had technical support from the Brazilian SynchrotronLight Laboratory (under research proposal D09B-XRF5702) and

ry and wet periods at Águas da Serra Stream

Zn Cr

CV Wet CV Dry CV Wet CV Dry CV

0.4 65 2.8 210 1.0 48 6.1 158 1.90.8 61 1.0 65 2.2 28 5.3 22 6.10.2 206 2.2 48 1.8 184a 1.5 14 5.60.9 30 4.9 132 1.8 58 3.8 113a 1.60.7 25 2.8 486a 0.4 21 5.7 18 9.70.4 32 2.4 48 2.2 29 4.9 18 1.9

60 mg kg−1 40 mg kg−1

rence Values for Soils).

Table 12Average concentration (n=4) and uncertainty of Mn, Ni, Cu and Pb in sediment samples for dry and wet periods at Águas da Serra Stream


Mn Ni Cu Pb

Point Wet CV Dry CV Wet CV Dry CV Wet CV Dry CV Wet CV Dry CV

AS 01 70 5.6 62 5.8 b0.03 – 8 9.4 26 6.5 13 10.6 74 6.6 54 8.5AS 02 30 6.6 38 8.7 b0.03 – b0.03 – 25 5.2 17 4.4 58 6.0 44 4.9AS 03 66 4.3 184 0.5 b0.03 – b0.03 – 25 6.4 13 6.0 72 4.0 40 4.6AS 04 22 6.6 42 8.2 b0.03 – b0.03 – 15 3.7 34 5.6 57 5.4 107* 3.9AS 05 17 8.7 81 5.1 b0.03 – 13 5.8 12 5.4 266* 0.9 34 1.1 54 3.2AS 06 27 3.1 30 5.6 b0.03 – b0.03 – 8 7.1 15 5.8 34 3.5 34 6.3QRV Not established 13 mg kg−1 35 mg kg−1 17 mg kg−1

1) CV=Coefficient of Variation (%) 2) in italic and bold values higher than QRV (Quality Reference Values for Soils)⁎Values higher than PEL (Probable Effect Level).

Table 13Average concentration (n=4) and uncertainty of Al, Fe, Zn and Cr in sediment samples for dry and wet periods at Graminha Stream


Al Fe Zn Cr


GR 01 716 9.0 252 5.4 8864 0.4 1868 0.2 78 2.6 64 0.8 31 2.2 5 9.6GR 02 443 2.7 531 0.1 2830 0.2 7563 0.2 38 0.7 34 4.2 9 3.1 52 3.1GR 03 199 5.3 197 8.3 721 0.9 2496 0.3 33 0.6 37 0.8 6 4.0 7 5.5GR 04 263 8.2 188 8.9 1939 0.4 1601 0.2 14 3.9 17 1.2 6 2.0 4 6.2GR 05 b4.5 – 149 9.2 460 0.5 1365 0.3 7 2.0 40 0.9 2 3.9 18 3.3GR 06 353 6.7 619 3.5 810 0.6 1989 0.8 14 1.0 5276* 0.4 4 9.2 431* 1.6QRV Not established Not established 60 mg kg−1 40 mg kg−1

1) CV=Coefficient of Variation (%) 2) in italic and bold values higher than QRV (Quality Reference Values for Soils) ⁎ Values higher than PEL (Probable Effect Level).

Table 14Average concentration (n=4) and uncertainty of Mn, Ni, Cu and Pb in sediment samples for dry and wet periods at Graminha Stream


Mn Ni Cu Pb


GR 01 37 5.5 99 1.1 b0.03 – b0,03 – 34 3.6 6 5.2 40 3.4 10 3.8GR 02 16 1.1 21 5.0 b0.03 – b0.03 – 8 5.7 11 3.7 13 8.3 27 7.3GR 03 1 2.9 10 6.7 3 2.1 b0.03 – 4 3.8 6 4.8 6 3.1 17 1.2GR 04 4 5.8 9 6.1 b0.03 – 1 3.4 4 8.9 3 5.2 8 8.2 8 5.1GR 05 b0.03 – 2 9.4 b0.03 – 5 2.1 2 4.9 38 1.0 b0.10 – 7 7.8GR 06 7 4.1 14 8.5 b0.03 – 43* 2.4 3 5.0 17 7.8 6 9.6 4 5.4QRV Not established 13 mg kg−1 35 mg kg−1 17 mg kg−1

1) CV=Coefficient of Variation (%) 2) in italic and bold values higher than QRV (Quality Reference Values for Soils) ⁎Values higher than PEL (Probable Effect Level).

Table 15Metal concentrations in sediments according to the literature

Sediments (lakes, rivers) Concentration (mg kg−1)

Cr Cu Ni Zn Pb

Paranoá Lake [9] 81 40 17 49 –

Arroio do Salso [10] 35 5 3 47 –

Piracicaba River Basin [11] 0,4 41 – 111 –

Jaguari Mirim River [12] 1 8 1 10 –

Canoas River [12] 2 7 2 6 –

Barra Bonita River [13] 2 5 6 11 –

Pirapora River [13] 44 121 105 147 –

Billings Dam [14] 137 35 21 1952 22Billings Dam [15] 47 142 10 192 57Billings Dam [15] 54 895 25 408 110Billings Dam [15] 219 204 74 481 100Billings (Grande River) [16] 55 1849 71 114 764Tatu River [17] 98 181 45 217 –

Tisza River [18] – 229 – 836 964Graminha Stream 48 39 13 471 13Águas da Serra Stream 59 11 – 117 55


Fig. 8. Synopsis of the environmental pollution in water and sediment samples for Águas da Serra and Graminha streams.


financial support from CAPES (scholarship) and CNPq (Process308432/2007-0).

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Evaluation of water and sediment of the Graminha and Águas da Serra streams in the city of Limeira...

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