Environment International 32 (2006) 52 57 www.elsevier.

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Metal levels in sugar cane (Saccharum spp.) samples from an area under the influence of a municipal landfill and a medical waste treatment system in Brazil
S.I. Segura-Munoz a,*, A. da Silva Oliveira a, M. Nikaido a, T.M.B. Trevilato b, A. Bocio c, A.M.M. Takayanagui a, J.L. Domingo c
a

Environmental Health Laboratory, Department of Maternal Infant Nursing and Public Health, Ribeirao Preto College of Nursing, University of Sao Paulo, Av. Bandeirantes, 3900 Ribeirao Preto, Sao Paulo, Brazil b Metal Sector, General Hospital, Faculty of Medicine at Ribeirao Preto, Pediatric Department, University of Sao Paulo, Av. Bandeirantes, 3900 Ribeirao Preto, Sao Paulo, Brazil c Laboratory of Toxicology and Environmental Health, School of Medicine, Rovira i Virgili University, San Lorenzo 21, 43201 Reus, Spain Received 6 November 2004; accepted 19 April 2005 Available online 28 June 2005

Abstract In July 2003, duplicated samples of roots, stems and leaves of sugar cane (Saccharum spp.) were collected in 25 points of an area under direct influence of the municipal landfill site (MLS) and medical waste treatment system (MWTS) of Ribeirao Preto, Sao Paulo, Brazil. Cadmium (Cd), chromium (Cr), copper (Cu), mercury (Hg), manganese (Mn), lead (Pb) and zinc (Zn) were determined by atomic absorption spectrophotometry. The following concentrations (mg/kg) were found in roots: Cd, 0.22 T 0.12; Cr, 64.3 T 48.7; Cu, 140.6 T 27.7; Hg, 0.04 T 0.02; Mn, 561.6 T 283.3; Pb, 7.9 T 2.1 and Zn, 177.4 T 64.9. For some metals, these levels are higher than the concentrations previously reported for different plants, reaching, in some cases, values that might be considered toxic for vegetables. Metal levels in stems were 80 90% of those found in roots, while the concentrations detected in leaves were significantly lower than those in roots. The present results suggest that MLS and MWTS activities might have been increasing metal concentrations in edible tissues of sugar cane grown in the area under their influence. Moreover, the traditional agricultural practices in the production of sugar cane could be also another determinant factor to reach the current metal levels. The results of this study indicate that sugar cane is a crop that is able to grow in areas where metals in soils are accumulated. D 2005 Elsevier Ltd. All rights reserved.
Keywords: Metals; Sugar cane; Municipal landfill; Medical waste treatment system; Brazil

1. Introduction The presence of metals in soils is related with natural factors such as geographic location, type of soil, oxidation reduction potential, cation exchange capacity, clay content, nature of drainage waters and type of plants grown in those soils (Ramos et al., 1999; Blasser et al.,

* Corresponding author. Tel.: +55 16 602 3950; fax: +55 16 633 3271. E-mail address: susis@eerp.usp.br (S.I. Segura-Munoz). 0160-4120/$ - see front matter D 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.envint.2005.04.008

2000). However, anthropogenic inputs associated with agricultural practices, mineral exploration, industrial processes and solid waste management are important contributors to heavy metal contamination of natural ecosystems (Bilos et al., 2001; Keane et al., 2001; Alumaa et al., 2002). Most vegetable species growing in metal-polluted soils are unable to avoid the absorption of these elements (Baker, 1981). Accumulation of heavy metals and metalloids in agricultural soils is a subject of increasing concern due to food safety issues and potential health risks, as well as

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detrimental effects on soil ecosystems (McLaughlin et al., 1999). Toxic effects of metals have been widely described. Elements such as arsenic, cadmium, lead, mercury, nickel, etc. have a wide spectrum of toxicity that includes neurotoxic, hepatotoxic, nephrotoxic, teratogenic and mutagenic effects among others (Domingo, 1994; Bucheim et al., 1998; Hudnell, 1999; Kelley, 1999; Lai et al., 1999). Moreover, elements such as cadmium, chromium and arsenic are also considered carcinogenic (Costa, 1998). In Ribeirao Preto (Sao Paulo State, Brazil), a municipal landfill site (MLS) for urban waste disposal has been operating since 1989. It was integrated with a medical waste incinerator plant (MWIP) and was deactivated in February 2002. One of the main reasons for deactivation of the facility was the lack of an adequate standard pollution control system to remove acids, organic compounds and heavy metals from the flue gas emissions (Segura-Munoz, 2002). Nowadays, a microwave system technology (MST) for treatment of medical waste of Ribeirao Preto and region is operating in the same zone. The soils under the MSL/MWTS (Medical Waste Treatment System) influence have been used to cultivate sugar cane (Saccharum spp.). Brazil is recognized as the most important sugar cane producer in the world. In 2001 2002, 296.25 million tons were produced. Among them, almost 70% were harvested in Sao Paulo State (Piacente and Piacente, 2004; UNICA, 2004). For the Brazilian financial system, Ribeirao Preto and its region are important areas of sugar cane production. Sugar cane production require wide use of pesticides (Duarte, 2003). Inputs of heavy metals to this vegetal species could also come from the use of some pesticides and fertilizers. Taking this into account, the purpose of the present study was to assess the concentrations of Cd, Cr, Cu, Hg, Mn, Pb and Zn in sugar cane plants collected within 2 km of distance from the MLS/MWTS.

2. Materials and methods 2.1. Sampling The MLS/MWTS is located in the south-western region of Ribeirao Preto, with an extension of approximately 225,000 m2 (Fig. 1). It is surrounded by agricultural areas, in which sugar cane (Saccharum spp.) has been the predominant crop. The soils in this area are classified as dusky latosol (Alvarenga et al., 1986). In July 2003 (corresponding with the dry season of the year), a total of 25 duplicated root, stem and leaf samples of sugar cane (Saccharum spp.) plants were collected along four transects established at the north (N), east (E), west (W) and south (S) directions from the facility, at 0, 50, 100, 200, 500, 1000 and 2000 m of distance from the MLS/MWTS, the sampling points were delimited using a GPS (Global Positioning System). All samples were kept in polyethylene bags. The materials used for sampling and storage were previously soaked overnight in 30% (v/v) HNO3 (65% Suprapur, E. Merck, Darmstadt, Germany). Duplicated samples of Saccharum spp. were collected in the vicinity of the Santa Teresa Preserved Forest, considered as a control area. Duplicated soil samples were also collected at the marked points for metal detection and pH determination. Results were recently reported (Segura-Munoz et al., 2004b). 2.2. Analytical methods Root, stem and leaf duplicated samples were dried in an oven at 60 -C for 48 h. Samples were homogenized and about 1.0 g of each sample was treated at 90 -C in Kjeldahl flasks with 65% nitric acid Suprapur (E. Merck). After cooling, solutions were filtered and made up to 25 ml with deionized water. Cadmium, Cr, Mn and Pb levels were determined by atomic absorption spectrophotometry with graphite furnace atomization (Varian 640 Zeeman). Mercury concentrations were measured by hydride generation atomic spectrophotometry (Varian VGA-77), while Zn and Cu levels were determined by atomic absorption spectrophotometry using acetylene flame (Varian 200) (Segura-Munoz et al., 2004a). Quantification limits were the following: 0.003 mg/kg for Cd, Mn and Pb; 0.0075 mg/kg for Hg; 0.03 mg/kg for Cr and Cu and 0.06 mg/kg for Zn.

Fig. 1. Localization of the municipal landfill site/medical waste treatment system of Ribeirao Preto, Brazil.

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Table 1 Metal concentrations in samples (roots, stems, leaves) of sugar cane (Saccharum spp.) collected in the control area Metal Cd Sample Root Stem Leaf Root Stem Leaf Root Stem Leaf Root Stem Leaf Root Stem Leaf Root Stem Leaf Root Stem Leaf Mean T S.D. 0.055 T 0.001 0.034 T 0.02 0.012 T 0.001 17.6 T 1.8 22.9 T 7.6 17.6 T 1.4 37.5 T 1.9 31.3 T 10.4 <0.03 <0.0075 <0.0075 <0.0075 153.5 T 0.9 187.7 T 31.0 27.7 T 0.5 2.01 T 0.14 2.28 T 0.22 1.84 T 0.06 178.6 T 8.0 180.8 T 8.6 43.4 T 0.8 Range 0.051 0.058 0.018 0.067 0.009 0.016 16.4 19.2 15.0 32.1 16.5 18.9 36.5 39.1 22.2 45.7 150.7 155.5 148.8 232.5 27.3 28.6 1.93 2.35 1.76 2.28 1.77 2.01 174.2 185.9 166.7 188.1 41.3 46.5 Coefficient of variation (%) 1.8 59.2 8.3 10.2 33.3 7.9 5.1 33.2 0.5 16.5 1.8 6.9 10.4 3.2 4.5 4.8 1.8

Cr

Cu

Hg

Mn

Pb

Zn

Results are given in mg/kg (dry weight).

The quality control of the instrumental methods and analytical procedures was checked using certified samples (121-S, 127-S, PW-337, PW-341, NW-298, NW-340) from Quality Control Technologies Pty. Ltd. (Queensland, Australia). Soil pH was determined in a soil/water (1:25) suspension with a QUIMIS 200A Microprocessor pH meter. Transfer factors (TF) for Cd, Cr, Cu, Hg, Mn, Pb and Zn, defined as the ratio of the respective metal content in plant tissue ([M]v) to the total concentration of that metal in soil ([M]s), were calculated as follows: TF = [M]v/[M]s (Cui et al., 2004). 2.3. Data evaluation Statistical analyses of the data were performed using the Statistical Program GraphPad Prism (Version 3.02 for Windows, GraphPad Software, San Diego, CA, USA). The statistical significance of correlations was verified using the Spearman Correlation Nonparametric Test. A probability of 0.05 or less was considered to be significant.

their forms and associations in the soil. A number of geochemical factors operating at the soil root interface and differences in element selectivity and accumulation from soil solution are also involved (Sanita di Toppi and Gabrielli, 1999; Mohamed et al., 2003). Tables 1 and 2 summarize metal concentrations, ranges and variation coefficients for sugar cane root, stem and leaf samples collected in the control area and in the MLS area. Metal levels were found to vary notably depending on the different sampling points. According to Shaw (1989), varieties of the same vegetable species exposed to similar concentrations of metals may show differences in absorption and internal distribution of metals in the plant according to the differences in the retention capacity of the absorbed element in roots. The xylem can be reached through apoplastic and/or symplastic pathway, complexed by ligands such as organic acids or phytochelatins (Salt and Rauser, 1995). Other factors that must be also taken into account are the stage of development of the plant, the time of exposure to the metal and the chemical species of the element in each sampling point (Alloway, 1993). The concentrations of Cd, Cr, Mn and Pb in soils collected in the area under evaluation were recently reported (Segura-Munoz et al., 2004b), while Cu and Zn levels were 564.80 T 18.81 and 274.98 T 63.01 mg/kg, respectively. No significant correlation ( P > 0.05) between the pH of the soils in each sampling point and metal concentrations in roots, stems or leaves were found. Also, no direct relationship between the concentration in stems and leaves and those in roots was found by means of the Spearmans rank correlation coefficient test. The transfer factors showed that for most metals, the retention prevalence occurs in roots. However, it is important to note that the detected fraction in the edible parts (stem) of the sugar cane samples represented 80 90% of root concentrations (Table 3). These results are in agreement with those reported by Sereno
Table 2 Metal concentrations in samples (roots, stems, leaves) of sugar cane (Saccharum spp.) collected in the vicinity of the MSL/MWTS Metal Cd Sample Root Stem Leaf Root Stem Leaf Root Stem Leaf Root Stem Leaf Root Stem Leaf Root Stem Leaf Root Stem Leaf Mean T S.D. 0.23 T 0.07 0.20 T 0.06 0.13 T 0.06 64.3 T 48.7 59.7 T 45.9 2.65 T 1.58 140.6 T 75.1 127.3 T 68.3 67.7 T 12.7 0.030 T 0.017 0.024 T 0.010 0.024 T 0.013 561.6 T 317.5 466.2 T 234.1 283.3 T 174.8 7.95 T 4.21 6.71 T 2.40 2.09 T 1,18 177.4 T 64.9 170.3 T 61.7 81.4 T 34.6 Range 0.12 0.35 0.10 0.32 0.04 0.29 11.7 238.1 11.9 232.9 0.96 7.53 41.9 251.7 11.9 232.9 2.73 61.8 0.01 0.08 0.01 0.07 0.01 0.07 140.1 1253.1 144.4 944.0 79.3 754.6 2.92 22.27 3.5 13.8 0.45 5.51 96.3 347.0 101.2 306.5 42.5 205.7 Coefficient of variation (%) 32.5 30.0 51.2 75.7 76.9 59.6 53.4 53.6 45.8 56.7 41.7 54.2 56.5 50.2 61.7 52.9 35.8 56.5 36.6 36.2 42.5

Cr

Cu

3. Results and discussion

Hg

It is known that metal concentrations in soil and vegetation samples collected in the vicinity of landfill sites and MWTS can be affected by factors such as the composition of the municipal solid waste, the nature of the landfill, the design of the incinerator and stack height, the combustion operating conditions, the emission control devices, the water solubility of deposited metal-containing particulates, the prevailing weather conditions, as well as root uptake of metals by plants (Bache et al., 1991; Schuhmacher et al., 1997; Prada et al., 1998; Llobet et al., 2002; Segura-Munoz et al., 2004b). It is generally accepted that the availability of metals, and uptake by plants, is related to both, their total concentrations and to

Mn

Pb

Zn

Results are given in mg/kg (dry weight).

S.I. Segura-Munoz et al. / Environment International 32 (2006) 52 57 Table 3 Metal transfer factors (TFs) from soila to various parts (roots, stems, leaves) of sugar cane (Saccharum officinarum) collected in MLS area Metal Cd Cr Cu Hg Mn Pb Zn
a

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Soil Root TF 1.01 T 0.33 2.06 T 1.24 0.25 T 0.14 0.70 T 0.62 1.28 T 1.11 0.93 T 0.57 0.67 T 0.25

Soil Stem TF 0.89 T 0.27 1.90 T 1.12 0.23 T 0.12 0.56 T 0.51 1.03 T 0.77 0.79 T 0.34 0.64 T 0.22

Soil Leaf TF 0.56 T 0.29 0.11 T 0.09 0.05 T 0.02 0.50 T 0.23 0.53 T 0.31 0.25 T 0.17 0.31 T 0.13

Soils values were reported at Segura-Munoz et al. (2004b).

(2004), who concluded that Saccharum spp. plants were capable to accumulate high amounts of some metals in roots, verified by experimental analysis. In 2000, a survey was conducted in the same area. Cadmium concentrations were analyzed in 16 samples of Saccharum spp. collected in a ratio up to 200 m away from the limits of the MLS. The current Cd concentrations in roots decreased when compared with those found in 2000 (0.51 vs. 2.94 mg/kg), considering only the samples collected in that ratio (Segura-Mun oz, 2002). Cadmium levels detected in roots, stems and leaves of sugar cane samples were compared with Cd concentrations reported for other vegetation samples collected near a municipal waste incinerator in Spain, which were found to be lower than 0.11 mg/kg (Meneses et al., 1999). However, some authors found that Saccharum spp. is a specimen with potential tolerance to high Cd concentrations in experimental conditions (Fornazier et al., 2002; Sereno, 2004). The concentrations of Cr in roots and stems may be considered rather high taking into account that most vegetable species showed mean levels of Cr between 2.7 and 3.0 mg/kg in their tissues (CETESB, 2001). Although there is no sufficient scientific evidence to demonstrate that Cr is an essential nutrient for plants, it is recognized that not all plants tolerate high Cr concentrations in the available form (WHO, 1988). Cary et al. (1977) reported that when absorbed by plants, Cr is mainly retained in roots, while normally, only a small quantity is transferred to other parts of the plant. However, the current TF shows that Cr content in stems was close to the content found in roots. Bioaccumulation of Cu in environmental compartments occurs when this element is biologically available (Bettiol and Camargo, 2000). In general terms, vegetation grown in soils with high contents of Cu reflects the Cu levels in tissues, varying according to the physiological requirements of each species (WHO, 2001). It is estimated that in unpolluted soils, Cu concentration in vegetable tissues ranges between 6 and 25 mg/kg. However, in Cu-polluted soils the concentration of this element in vegetable tissues may reach 80 mg/kg (WHO, 2001). The current Cu concentrations in roots and stems of sugar cane were above 120 mg/kg (Table 2). When Cu levels are higher than 150 mg/kg, some agricultural species may show adverse effects. An experimental study, where young sugar cane plants grew in solutions containing levels of Cu between 50 and 500 AM, concluded that solutions with concentrations over 100 AM of Cu inhibited the development rate in 48% (Sereno, 2004). In the present study, the concentration of Cu in soils (564.80 mg/kg) could be affecting the sugar cane production in the area, considering that soils with concentrations between 500 and 1000 mg/kg of Cu act as a strong selective process, allowing only Cu-tolerant vegetable species and families to survive (WHO, 2001; Sereno, 2004).

Mercury did not present quantifiable levels in sugar cane samples collected in the control areas (Table 1). The detected levels of Hg in sugar cane plants collected in the area under influence of the MLS and MWTS in Ribeirao Preto indicate that it may be considered as non-contaminated by Hg (HMSO, 1991). This is an important finding taking into account the toxicity of Hg and its bioaccumulation capacity (Garcia and Dorronsoro, 2002). The levels of Mn in sugar cane tissues showed also elevated concentrations. The analyzed soil samples showed pH variations from 5.3 to 6.5, values that may promote the reduction to Mn2+ form, increasing the solubility and being bioavailable for plants. It was demonstrated that vegetable Mn absorption capacity varies according to the respective species (WHO, 1981). The present results show that Saccharum spp. has a high capacity to retain Mn in its tissues. The presence of Mn in stem of this vegetable suggests the necessity of additional research, taking into account that this part of the plant is commercially used for sugar production. Lead showed normal levels in Saccharum spp. samples analyzed in 2000 and 2003. Typical Pb levels vary between 1 and 12 mg/kg in plants (Fleming and Parle, 1977; Turkan et al., 1995). In turn, the current Zn levels in Sacharum spp. samples indicate that such concentrations can be considered as normal for vegetables (25 200 mg/kg) (Fleming and Parle, 1977; Turkan et al., 1995). The results of the present study suggest that in addition to disposition and treatment of solid waste, the possibility that fertiirrigation have increased metal levels in soils, and consequently in sugar cane grown in the zone, cannot be discarded. Fertiirrigation is defined as the application of sugar cane industrial residues (such as vinasse and filter cake) in soils. Nowadays, this is a general Brazilian custom, becoming an alternative for residues approach as mineral compost in agricultural areas (Polo et al., 1988; Piacente and Piacente, 2004). The utilization of vinasse in soils cultured with sugar cane emerged due to excessive production, more than 115 million m3 per year during harvest time. It represents approximately 1000 l of liquid effluents for each ton of grounded sugar cane (Cortez et al., 1992). In relation to filter cake, the production is about 30 kg/ton of grounded sugar cane (Orlando Filho and Leme, 1984). During a long period, sugar cane sub-products flowed into rivers and lakes in the vicinities of sugar mills, polluting them (Ludovice, 1996). Since 1976, the National Law CONAMA 20/86 banned their release in superficial watercourses (CONAMA, 1986). It is considered that the incorporation of those sub-products in soils may increase the natural composition of macro- and micronutrients in soil, including some metals (Ludovice, 1996; Ramalho and Amaral Sobrinho, 2001). Metals were being incorporated to the vinasse and filter cake during the productive process, probably by plumbing, piping and vintage tubes abrasion (Ramalho, 1996). A number of studies have shown that vinasse contains high levels of organic matter and elements such as Cu, Mn and Zn, while the filter cake has notable concentrations of Cd, Co, Cr, Cu, Ni and Pb (Vasconcellos and Oliveira, 1983; Cerri et al., 1988; Ramalho and Amaral Sobrinho, 2001). Recent studies have demonstrated that among metals, Mn, Cu and Zn show higher hydrosoluble and biotransferable fractions, being more available to plants (Ramalho and Amaral Sobrinho, 2001). In the 1980s, it was considered that the agricultural use of sugar cane sub-products did not represent a critical risk factor as modifiers of soil composition, being a potential alternative to avoid superficial water resources pollution (Bolsanello and Vieira,

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S.I. Segura-Munoz et al. / Environment International 32 (2006) 52 57 Bache CA, Gutenmann WH, Rutzke M, Chu G, Elfving DC, Lisk DJ. Concentrations of metals in grasses in the vicinity of a municipal refuse incinerator. Arch Environ Contam Toxicol 1991;20:538 42. Baker AJM. Accumulators and excludersstrategies in the response of plants to heavy metals. J Plant Nutr 1981;3:643 54. Bettiol W, Camargo OA. Impacto ambiental do uso agrcola do lodo de esgoto. Jagauriuna EMBRAPA; 2000. Bilos C, Colombo JC, Skorupka CN, Rodrigues PMJ. Sources, distribution and variability of airbone trace metal in La Plata City area, Argentina. Environ Pollut 2001;111:149 58. Blasser P, Zimmermann Luster J, Shotyk W. Critical examination of trace element enrichments and depletion in soils: As, Cr, Cu, Ni, Pb and Zn in Swiss forest soils. Sci Total Environ 2000;249:257 80. Bolsanello J, Vieira JR. Caracterizacao da composicao qumica dos diferentes tipos de vinhaca da regiao da regiao de Campos-RJ. Bras Acucar 1980;96:45 59. Bucheim K, Stoltenburg-Didinger G, Lilienthal H, Winnike G. Miopathy: a possible effect of chronic low level lead exposure. Neurotoxicology 1998;19:539 46. Cary FE, Allway WH, Olson OE. Control of chromium concentrations in food plants. J Agric Food Chem 1977;25:300 9. Cerri CC, Polo A, Andreux F, Lobo MC, Eduardo BP. Resduos organicos da agroindustria canavieira: 1R Caractersticas fsicas e qumicas. STAB, Acucar, Alcool e Subprodutos 1988;6:34 7. CETESB. Companhia de Tecnologia de Saneamento Ambiental. Relatorio de Estabelecimento de Valores Orientadores para Solos e Aguas Subterraneas no Estado de Sao Paulo. Sao Paulo Centro de Editoracao da Secretaria de estado do Meio Ambiente; 2001. p. 245. CONAMA. Instituto Brasileiro do Meio Ambiente dos Recursos Naturais Renovaveis. Resolucao No. 20 de 18 de junho de 1986. http::// www.ibamarpr.hpg.ig.com.br/02086.htm; 1986. accessed 10 March 2004. Cortez L, Magalhaes P, Happi J. Principais subproductos da agroindustria canavieira e sua valorizacao. Rev Bras Energ 1992;2:85 9. Costa M. Carcinogenic metals. Sci Prog 1998;81:329 39. Cui YJ, Zhu YG, Zhai RH, Chen DY, Huang YZ, Qiu Y, et al. Transfer of metals from soil to vegetables in an area near a smelter in Nanjing, China. Environ Int 2004;30:785 91. Domingo JL. Metal-induced developmental toxicity in mammals: a review. J Toxicol Environ Health 1994;42:123 41. Duarte NF. Potenciais Impactos Ambientais da Monocultura de Cana-de Acucar. In: Valadao RC, Landau EC, editors. Analise Integrada do Meio Ambiente-Lagoa da Prata, MG, Brasil Publicado em CD-ROM. Belo Horizonte Universidade Federal de Minas Gerais; 2003. Fleming G, Parle P. Heavy metals in soil, herbage and vegetables from an industrialized area west of Dublin City. Ir J Agric Res 1977; 16:35 48. Fornazier RF, Ferreira RR, Vitoria AP, Molina SMG, Lea PJ, Azevedo RA. Effects of cadmium on antioxidant enzyme activities in sugar cane. Biol Plant 2002;45:91 7. Garcia I, Dorronsoro C. Contaminacion del suelo Curso: Tecnologia de Suelos. Tema 2002;15 http://edafologia.ugr.es/conta/Tema15 (accessed January 4, 2002). HMSO London. Protection of workers and the general public during the development of contaminated land. Health and safety executive guidelines for the classification of contaminated soils; 1991. p. 20. Hudnell H. Effects from environmental Mn exposure: a review of the evidence from non-occupational exposure studies. Neurotoxicology 1999;20:379 98. Keane B, Collier MH, Shann JR, Rogstad SH. Metal content of dandelion (Taraxacum officinale) leaves in relation to soil contamination and airborne particulate matter. Sci Total Environ 2001;281:63 78. Kelley C. Cadmium therapeutic agents. Curr Pharm Des 1999;5:229 40. Lai JC, Minski MJ, Chan AW, Leung TK, Lim L. Manganese mineral interactions in brain. Neurotoxicology 1999;20:433 44. Llobet JM, Schuhmacher M, Domingo JL. Spatial distribution and temporal variation of metals in the vicinity of a municipal solid waste incinerator

1980). However, with the present intensification of sugar cane production and fetiirrigation patterns, there is concern with underground watercourses contamination, and the intensive use of in natura vinasse and filter cake residues. It can be increasing the metal content in different environmental matrices (Piacente and Piacente, 2004). In sugar cane production, the use of fertilizers (N, K, P and Ca compounds) are necessary to improve the plant growth rate and the use of phosphate fertilizers input heavy metals to soils. Also, soil fertilization with compounds that content chlorides, nitrates and sulfates may also be factors that enhance metals solubility and bioavailability (Duarte, 2003). In Brazil, sugar cane plantations suffer the attack of different kinds of plagues, such as Amaranthus viridis, Amaranthus hybridus, Brachiaria plantaginea, Bidens pilosa, Sida rhombifolia, Richardia brasiliensis and Emilia sanchifolia, among others. To fight against these plagues, chemicals such as triazines (atrazines), phenoxiacetics, urea derivates, organic arsenic products, glyphosates, etc. are commonly used (Duarte, 2003). The interaction of environmental toxicants with organic substances affects the speciation and dynamics and subsequent toxicity, mobility and fate of toxicants in the environment (Tarn Lin et al., 2004). The application of P fertilizers is favorable to the metals entrance in the soil plant system (Mei Zhou et al., 2004). The results of this study suggest a possible interest in monitoring the zones under direct influence of MLS/MWTS activities in Ribeirao Preto, controlling the environmental con ditions of the surrounding agricultural areas. In order to avoid a potential future increase of toxic levels of metals, it would also be important to perform an exhaustive evaluation of the application of sugar cane industrial residues, vinasse and filter cake. The results of this study also indicate that sugar cane is a crop that is able to grow in areas where some metals in soils are accumulated. The interactions between metals, fertilizers and herbicides could be also a subject of further studies on Saccharum spp. not only in areas of risk, but also in other zones.

Acknowledgements This study was financially supported by FAPESPFundacao de Amparo a Pesquisa do Estado de Sao Paulo, ` Brazil (Grant N. 02/11831-6) and by the CAPES-Coordenacao de Aperfeicoamento de Pessoal de Nvel Superior, Brazil, through the ProDoc/CAPES Program. The authors thank the authorities of the Municipal Solid Waste Management Department of Ribeirao Preto (DAERP), Sao Paulo, for collaboration. The collaboration of the Sugar Refinery in authorizing the sample collection in their properties is also appreciated.

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