2007 International Nuclear Atlantic Conference - INAC 2007 Santos, SP, , September 30 to October 5, 2007 ASSOCIAÇÃO BRASILEIRA DE ENERGIA NUCLEAR - ABEN ISBN: 978-85-99141-02-1

ENVIRONMENTAL POLLUTION IN PIRACICABA BASIN, STATE, ‘STEEL VALLEY”, BRAZIL.

Marluce Teixeira Andrade Queiroz1, Maria Adelaide R. V. Veado1, Maria Ângela de B. C. Menezes2, Maria Ângela Amaral2

1 Centro Universitário do Leste de Minas Gerais (UNILESTE-MG - MG) Avenida Tancredo de Almeida Neves, 3500 35170-056 , MG Tel. 31 38425242 [email protected], [email protected]

2 Centro de Desenvolvimento da Tecnologia Nuclear Rua Professor Mário Werneck s/n - Pampulha 30123-970 , MG [email protected]

ABSTRACT

Total heavy metal and trace elements concentrations were evaluated in smelting waste areas, in Piracicaba River, Minas Gerais, Brazil. The studies samples were surface water, border sediment, and fish muscle (Acará - Geophagus Brasiliensis). Elevated concentrations were found in Acará muscle fish As (1.3 - 1.8 µg g-1), Hg (0.7 - 1.84 µg g-1), Cr (0.7 - 4.1 µg g-1), Zn ( 43 - 76 µg g-1); in sediment Fe (81996 - 461147 µg g-1), Cr (126 - 447 µg g-1), Co ( 540 - 1016 µg g-1), Th (7.9 - 50 µg g-1). For the water samples the similar high heavy metal concentrations of Al, As, Cr, Fe, and Zn in all sampling sites were above the maximum limits permitted by Brazilian Environmental Council. The high level of heavy metals can affect the aquatic and cattle animals and human health. To conclusion the region studied in Piracicaba River in Minas Gerais State, Brazil, is not in agreement with the environmental parameters for “water class 3” according to Resolution by Brazilian Environmental Standards (CONAMA). An urgent program of measures for assessment and monitoring is necessary in this River.

1. INTRODUCTION

Intense mining activities in Minas Gerais State – Brazil brings out tons of waste to the environment. Considerable concentrations of toxic elements penetrate the soil, ground waters and rivers. This endangers the environment quality not only in the surrounding areas but also in ichthyofauna and in more distant areas of cattle raising and agricultural activities. Metals smelting is considered as one of the most important anthropogenic sources of heavy metal pollution to the environment worldwide [1, 2]. Such pollutants have been attributed to emissions from both smelter stacks and fugitive sources such as stockpiles and waste heaps [3]. Smelting emitted metals are transferred to environmental compartments, such as river water, sediment, soil, forage, and fish can eventually enter the human bodies through food chains or direct ingestion, which will pose a threat to human health. Many studies have reported the high levels of Al, As, Fe, Cr, Co, Hg, Zn, Cu, Sb, Th and U in environmental samples in hydrographic basins and lakes in Brazil [4, 5, 6]

In this work the quality of surface water, border sediment and fish muscle (Acará - Geophagus Brasiliensis) were investigated in four different sites of the Piracicaba River - Minas Gerais State, Brazil [7]. Instrumental Neutron Activation Analysis – INAA was applied to determine heavy metals and trace elements. INAA is an analytical method with high precision, sensitivity for trace multi-elementar analysis.

2. MATERIALS AND METHODS 2.1. Study area

The Piracicaba River is located into the medium Doce River hydrographic basin which received intense waste of anthropogenic activities: - industries (steel, cellulose, Fe mining); - sludge without treatments and - agricultural discharges (agro toxics, fertilizers, organic materials). The sampling sites were localized in four different cities: P1 (Fonseca); P2 (Rio Piracicaba); P3 () and P4 (), see Figure 1.

Figure 1. Sampling sites in Piracicaba River, Minas Gerais State, Brazil

2.2. Experimental Procedures

The samples were collected in two different seasons, January and August of 2006. At each sample site, three samples of water, border sediment and twenty samples of fish (Acará - Geophagus Brasiliensis) were collected. Three replicates of all studied samples were analysed.

In addition, certified reference materials were analysed six times: Soil 7, Fish Tissue from the International Atomic Energy Agency – IAEA and Riverine Water SLRS-3 from National Research Council of Canada, to confirm the data obtained in this paper [8, 9, 10].

INAC 2007, Santos, SP, Brazil.

The measured of physical chemistry parameters: pH; Dissolved Oxygen; Electrical Conductibility; and Water Temperature were carried out in situ.

The water samples were collected along the river, near to the river bank at a depth of 15 cm, put into 125 ml bottles (Nalgene) and stored at 4 °C. The water samples were acidified at the site with 5 drops of high pure nitric acid (pH~2).

Instrumental Neutron Activation Analysis: INAA was used for determine heavy metals in this work. Due to the effect of radiolysis, water samples had to be prepared in a solid form prior to irradiation for INAA, and 30 ml samples were evaporated in polyethylene tubes (evaporation of 1ml for a day).

The border sediment samples were collected in 20 ml polyethylene tubes, which represent a quantity of approximately 150 g and stored at a temperature of 4 °C. They were dried for a day at 40 °C prior to analysis. According to Dobbs and Grant (1978) there is no problem for As volatization at 60 °C. They also state that 13–27, 22–44, and 70–77% of arsenic is volatilized at temperatures of 400, 800, and 1000 °C, respectively [11].

The sediment sample was poured into a cone shaped heap, divided into four equal parts. Two opposite quarters were combined and re-coned. The process was repeated until the amount of sample had been reduced to 0.30 g that required for analysis.

The fish muscle samples, Acará- Geophagus Brasiliensis were frozen at -70 °C in an external freezer for 12 h, and lyophilized in freeze dried (Labconco® Benchtop Freeze Dry System). Aliquots of around 0.30 g were analysed.

2.3. Analytical Method: INAA

Instrumental Neutron Activation Analysis, INAA, is based on a simultaneous irradiation comparison between standard and studied samples in a nuclear reactor.

The irradiation characteristics are chosen to determine the isotopes under the best conditions. In this work the INAA was applied using the TRIGA MARK I IPR – R1 reactor at the Nuclear Technology Development Center of the National Committee of Nuclear Energy (CDTN/CNEN), in Belo Horizonte city, Minas Gerais State, Brazil. At 100kW of potency the flux of neutrons is 6.6 × 1011 n.cm−2.s−1.

After the necessary decay time for the interfering radioisotopes, the gamma spectrometry was applied in the high-purity germanium (HPGe) detector “Canberra”, coupled to a 4096 high pulse analyser. The “Canberra” Gennie 2000 software was used to analyse the spectra.

The isotopes nuclear characteristics in INAA, half-time, type of emission and gamma ray energies are well known and the “k0 parametric neutron activation analysis” (k0PNA) was a complementary method used to determine multi-elements in a given sample [12, 13].

INAA is an analytical method with high precision, sensitivity for trace multi elementary analysis. The elements obtained by INAA in this work were Al, Mn, V, As, Br, K, La, Na, Ce, Co, Cr, Cs, Fe, Hg, Rb, Sc, Sm, Th and Zn. . INAC 2007, Santos, SP, Brazil.

3. RESULTS AND DISCUSSION

The measurement obtained of physical chemistry parameters: pH; Dissolved Oxygen; Electrical Conductibility; and Water Temperature are indicated in Table 1. The obtained results for the international reference material to validate the achieved results were in quite a good agreement with the certified values as shown in Tables 2 to 4.

The average results (σ = 5%) obtained in surface water and border sediment analyzed is shown in Table 5. The average values (σ = 10%) for muscle fish are shown in Table 6. For the water, and muscle fish samples the results were compared with the maximum limits permitted (MLP) by Brazilian Environmental Council (CONAMA) [14]. For the water samples the concentrations of Al, As, Cr, Fe, Mn, V and Zn in all sampling sites were higher than the limit values for “water class 3”, according to Resolution CONAMA n. 357 of 17/03/2005.

-1 The much more important result was the level of Hg in Acará fish in P1: 1.8 µg g (MLP: 0.50 -1 -1 µg g ). In sediment samples the values for Cr concentration were between 126 µg g in P3 -1 -1 and 447 µg g in P4 MLP: 50 µg g in non contaminated sediments according Bryan & Langston [15]. The levels of heavy metals were above the limits which can affect the animals and human health. Mercury cause damage to the brain and chromium hexavalent is carcinogenic. In this work, the results obtained for the heavy metals were above the limits in all samples.

Table 1. Physical chemistry parameters measured.

January 2006 Sample pH Dissolved Electrical Water sites Oxygen Conductibility Temp. (mg L-1) (µS cm-1) (ºC) P1 6.42 4.15 41.7 25.4

P2 6.46 4.28 40.6 25.9

P3 6.38 4.33 43.7 26.5

P4 6.40 4.17 37.6 26.8 August 2006 Sample pH Dissolved Electrical Water sites Oxygen Conductibility Temp. (mg L-1) (µS cm-1) (ºC) P1 6.48 4.35 42.4 18.1

P2 6.48 4.47 41.8 18.6

P3 6.44 4.82 44.6 19.2

P4 6.42 4.25 38.7 19.3

INAC 2007, Santos, SP, Brazil.

Table 2. Results obtained (µg g-1) by INAA, soil reference, soil 7 by International Atomic Energy Agency, Vienna, Austria

Concentration ± Certified values Concentration ± Certified values Analyst standard (signif. level: 0.05) Analyst standard (signif. level: 0.05) deviation deviation 47000* Al 52000±800 La 28±3 28 (27-29) (44000-51000) As 13.3±1.3 13.4 (12.5-14.2) Mn 680±60 (631-660) Ba 141±20 159* (131-196) Na 2300±20 - Ce 58±6 61 (50-63) Rb 61±6 51 (47-56) Co 8.6±0.8 8.9 (8.4-10.1) Sb 1.9±0.2 1.7 (1.4-1.8) Cr 63±6 60 (49-74) Sc 9.4±0.9 8.3 (6.9-9.0) Cs 5.5±0.5 5.4 (4.9-6.4) Zn 108±10 104 (101-113) Cu 10 ±2 11 (9-13) Th 8.1±0.8 8.2(6.5-8.7) 25700* Fe 25700±2000 (25200-26300) *Non-certified value

Table 3. Results obtained (µg g-1) by INAA, riverine water reference, SLRS-3 by National Research Council of Canada

Concentration ± Certified values Analyst standard deviation ± confidence limits

Al 29±1 29±1

As 0.67±0.07 0.72±0.05 Ba 14±2 13.4±0.6 Co 0.042±0.008 0.027±0.003 Cr 0.38±0.03 0.30±0.04 Cu 1.5 ±0.1 1.35 ±0.07 Fe 110±10 100±10 Na 2450±250 2300±200 Zn 2.7±0.3 1.04±0.09

Table 4. Results obtained (µg g-1) by INAA, fish reference, Fish Tissue - 407 by IAEA. Concentration measured Certified values Analyst ± standard deviation ± confidence limits Al 12.0 ± 1.0 13.8 (12.4–15.2) As 12.5 ± 0.4 12.6 (12.3–12.9) Co 0.08 ± 0.01 0.10 (0.09–0.11) Cr 0.75 ± 0.04 0.73 (0.67–0.79) Cu 3.26 ± 0.10 3.28 (3.20–3.36) Fe 142 ± 10 146 (143–149)

Hg 0.20 ± 0.02 0.222 (0.216–0.228)

K 12.0 ± 1.4 13.1 (12.2–14.0)

Mg 2.60 ± 0.20 2.72 (2.58–2.86) Na 13.2 ± 0.1 13.1 (12.4–13.8) Zn 67.4 ± 0.6 67.1 (66.3–67.9)

. INAC 2007, Santos, SP, Brazil.

Table 5. Average results obtained (µg g-1 , σ~5%) by INAA, in sediment and water samples, Piracicaba River, Minas Gerais State, Brazil

Cr Fe Co Ce La Zn Th As Na Al Sc Mn V Sm

P1 (Fonseca) Sediment 447 552984 1016 79 16 - 7.9 35 264 * - * * -

Water 0.8 478 - - 0.1 24 - 4.9 3114 98 0.06 102 4.0 0.02

P2 (Rio Piracicaba) Sediment 202 461147 588 57 20 - 11 10 599 * - * * -

Water 0.4 1609 0.8 - 0.4 34 - 0.6 2108 189 0.04 180 5.0 -

P3 (Nova Era) Sediment 126 81966 789 75 18 128 11 6.5 1760 * - * * -

Water 0.2 577 0.3 - 0.2 17 - 0.3 2764 102 0.02 46 4.52 0.03

P4 (Ipatinga) Sediment 173 194987 540 181 96 80 50 3.6 1868 * - * * -

Water 1.7 705 0.4 - 1.0 14 39 1.5 2433 269 0.04 32 4.2 0.2

MLF: Maximum Limits Water 0.05 5.0 0.2 - - 5.0 - 0.03 - 0.2 - 0.5 0.1 - Permitted * Analyst not determined

INAC 2007, Santos, SP, Brazil.

Table 6. Average results obtained (µg g-1 σ~10%) by INAA, in fish muscle, Acará, Geophagus Brasiliensis, Piracicaba River, Minas Gerais State, Brazil

As Cr Hg Zn As P1 (Fonseca) 2.8 1.8 1.8 76 2.8

P2 (Rio Piracicaba) 1.3 1.0 1.0 55 1.3

P3 (Nova Era) 1.8 0.7 0.7 50 1.8

P4 (Ipatinga) 1.9 4.1 0.8 43 1.9 *Non contaminated sediment 1.00 0.10 0.50 50 1.00

*Non contaminated sediments according Bryan & Langston [15].

4. CONCLUSION

To conclusion the region studied, Piracicaba River – Minas Gerais State, is not in agreement with the environmental parameters for “water class 3” according to Resolution by Brazilian Environmental Council (CONAMA). The pollution is credited to the tons of waste poured without treatment into the river from several mining companies and other clandestine human activities. Part of the waste has been accumulated in the water, sediment of the river and spread and caused serious environmental problems. During the period of floods, contamination is found in fish, reaching and harming both people and animals that live in the marginal region. A program of measures for assessment and monitoring is necessary in this River. The multi elementary analysis technique INAA was applied to determine heavy metals as well as the major elements concentrations. The elements obtained were Al, As, Br, Ce, Co, Cr, Cs, Eu, Fe, K, La, Mn, Na, Rb, Sc, Sm, Th, V and Zn.

ACKNOWLEDGEMENTS

This work was supported by CNPq – National Council for Scientific Research – Brazil, Profix-540861/01-4. The analyses were carried out at the Center of Nuclear Technology Development – National Committee of Nuclear Energy, in Belo Horizonte city, Minas Gerais State of Brazil.

REFERENCES

1. J. S. RIEUWERTS, M. FARAGO, “Heavy metal pollution in the vicinity of a secondary lead smelter in the Czech Republic” Appl. Geochem., 23, pp. 11-17 (1996).

2. T. STERCKEMAN, F. DOUAY, N. PROIX, H. FOURRIER, Environ. Pollut., “Vertical distribution of Cd, Pb and Zn in soils near smelters in the North of France”, 107 pp. 377-389 (2000).

3. J. S. RIEUWERTS, M. FARAGO, Rieuwerts, J.S., and Farago, M.E. “Lead Contamination in Smelting and Mining Environments and Variations in Chemical Forms and Bioavailability, Chemical Speciation and Bioavailability”, 7(4), pp. 113-123 (1995).

INAC 2007, Santos, SP, Brazil.

4. M. A. R. V. VEADO, I. A. ARANTES, A. H. OLIVEIRA, M. R. M. G. ALMEIDA, R. A. MIGUEL, M. I. SEVERO, H. L. CABALEIRO, Metal Pollution in the Environment of Minas Gerais, Environmental Monitoring and Assessment, 117, pp. 157-172 (2006).

5. M. A. R. V. VEADO, A. H. OLIVEIRA, G. REVEL, G. PINTE, S. AYRAULT, P. TOULHOAT, Study of water and sediment interactions in the Das Velhas River, Brazil – Major and trace elements, Water S. A., 26, pp. 255-261 (2000).

6. C. P. JORDÃO, M. G. PEREIRA, A. T. MATOSB, J. L. PEREIRA, J. Influence of Domestic and Industrial Waste Discharges on Water Quality at Minas Gerais State, Brazil, Braz. Chem. Soc., 16, pp. 241-250 (2005).

7. M. A. T. QUEIROZ, Bioacumulação de Metais Pesados no Rio Piracicaba, Minas Gerais, Aplicando a Análise por Ativação Neutrônica Instrumental. Master Science Thesis, Curso de Mestrado em Engenharia Industrial, University Center of Eastern Minas Gerais, UnilesteMG, Brazil, Coronel Fabriciano, 105p. (2006), (in Portuguese).

8. International Atomic Energy Agency, Reference Material IAEA- SOIL 7 Trace Elements in Soil, Reference Sheet (2000).

9. International Atomic Energy Agency, Reference Material IAEA-407 Trace Elements And Methylmercury In Fish Tissue, Reference Sheet (2003).

10. National Research Council Canada, Standard Reference Material for Trace Elements in River Water (SRLS-3) (1996).

11. A. J. DOBBS, D. PHIL, C. GRANT, The volatilization of arsenic on burning copper- chromium-arsenic (CCA) treated wood, Holzforschung, 32, pp. 32-35 (1978).

12. De Corte, F. “The traceability of the nêutron activation analysis (NAA) K0 standardization method” Trace and Microprobe Techniques, 5:2-3, pp. 115 – 134 (1987).

13. R. A. MIGUEL, Otimização da Técnica de Análise por Ativação Neutrônica Instrumental e Adequação do Software K0Labsue, Método Paramétrico do K0. Master Science Thesis, Curso de Ciências e Técnicas Nucleares, Federal University of Minas Gerais State, Brazil, Belo Horizonte, 145p., (2003) (in Portuguese).

14. CONAMA: Conselho Nacional do Meio Ambiente. Ministério do Meio Ambiente. Resolução 357 de 17/03/2007.

15. G. W. BRYAN & W. J. LANGSTON, “Bioavailability, accumulation and effects of heavy metals in sediments with special reference to United Kingdom estuaries: a review” Environ. Pollut., 76, pp. 89-131 (1992).

INAC 2007, Santos, SP, Brazil.