DOI: 10.5935/0100-929X.20140002 Revista do Instituto Geológico, São Paulo, 35 (1), 19-29, 2014.

EVALUATION OF BIOLOGICAL ABSORPTION COEFFICIENT OF TRACE ELEMENTS IN PLANTS FROM THE PITINGA MINE DISTRICT, AMAZONIAN REGION

Maria do Carmo LIMA E CUNHA Lauro Valentim Stoll NARDI Vitor Paulo PEREIRA Artur Cezar BASTOS NETO Luiz Alberto VEDANA

ABSTRACT

Specimens of Ampelozizyphus amazonicus and Adiantum sp., together with adjacent soils, were sampled in the Pitinga Mine District, Amazonian region, in order to investigate the distribution of some trace elements in plants and soils, and their relation to the presence of mineral deposits. The Pitinga Mine contains large deposits of tin, with high concentrations of and zirconium, hosted by the Madeira , which is intrusive into a volcanic sequence named the Iricoumé group, all of them with Paleoproterozoic age. Our results point to the potential use, for both plants, of the Biological Absorption Coefficient (BAC) as an indicator of mineral deposits when the elements involved in this process have moderate to high mobility in the supergene environment. The high BAC for gold indicates that this element can be used as an indicator of gold deposits. The presence of sulfide deposits is indicated by high BAC for Cu, Zn and Pb, whereas tin deposits are indicated by increasing BAC for Y and Sn. This suggests that the BAC of some trace elements in both plants is a good indicator of geochemical enrichment associated with mineral deposits. The importance of biogeochemistry for mineral exploration is confirmed for areas with thick vegetal cover.

Keywords: Biologic Absorption Coefficient, biogeochemical prospecting, Pitinga Mine, tin deposits, Amazonian region.

RESUMO

AVALIAÇÃO DO COEFICIENTE DE ABSORÇÃO BIOLÓGICA DE ELEMENTOS- TRAÇO EM PLANTAS DA MINA PITINGA, REGIÃO AMAZÔNICA. Exemplares de Ampelozizyphus amazonicus and Adiantum sp. foram coletados juntamente com amostras de solo na Mina Pitinga, região amazônica, para averiguar a distribuição de alguns elementos-traço nas plantas e no solo e sua relação com a presença da mineralização na área. A Mina Pitinga caracteriza-se por extensos depósitos de estanho, com altas concentrações de nióbio e zircônio no Granito Madeira, que é intrusivo na sequência vulcânica do Grupo Iricoumé, ambas litologias de idade paleoproterozoica. O emprego do Coeficiente de Absorção Biológica (CAB) mostrou-se efetivo em ambas as plantas como indicador de depósitos minerais, quando os elementos envolvidos apresentam moderada a alta mobilidade no ambiente supergênico. Para o ouro o alto valor de CAB ressalta a possibilidade de usar este elemento como indicador de seus depósitos. Depósitos de sulfetos são indicados pelos altos valores de CAB para Cu, Zn e Pb, enquanto os de Sn, pelos significativos valores de CAB do Y e Sn. Sugere-se que o CAB de alguns elementos para ambos os vegetais estudados seja um bom indicador do enriquecimento geoquímico associado a depósitos minerais. Ainda, o emprego da biogeoquímica na exploração mineral é eficaz em áreas de espessa cobertura vegetal.

Palavras-chave: Coeficiente de Absorção Biológica, prospecção biogeoquímica, Mina Pitinga, depósitos de estanho, região amazônica.

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1 INTRODUCTION Boa and the Madeira , both intruded in a volcanic sequence named Iricoumé Group, which is Some plant species can accumulate metallic mainly composed of acid pyroclastic and extrusive elements, which are toxic to plants in general, rocks (DAOUD 1988, PIEROSAN et al. 2011). even in small concentrations. This peculiarity This mine, which is one of the world’s largest makes certain species useful in mineral exploration producers of tin, contains important deposits of programs or in phytoremediation of contaminated cryolite and high concentrations of rare metals, soils. Although sometimes these plants do not such as Zr, Nb, Ta, Y, REE, Li-, Be-, Rb-, and Th- accumulate significant levels of metallic elements, enriched minerals, as well as sulfides, which have which is common in geochemically anomalous been reported by several authors (BORGES et al. soils, they are adapted to this environment giving 2003, HORBE & PEIXOTO 2006). them a character of indicator plants. Additional The Pitinga Mine is located approximately information on the use of biogeochemistry in 300 km north of the city of , in an area of mineral exploration in several areas of North rainforest with tropical climate, an annual average America, Australia, South America, Indonesia, temperature of 26° C, and an annual average Asia, Africa, and Europe was compiled by DUNN precipitation of 2000 mm (long rainy season (2007). between December and May). During intense The humid tropical climate of the Amazonian chemical weathering, the lateritic cover of the environment causes weathering of rocks and Pitinga Mine area formed sandy clay acid soils, intense soil leaching with significant loss of most which are poor in nutrients (COSTA 1991). chemical elements. In the supergene environment, Many petrological (DAOUD 1988, precipitation and remobilization of elements LENHARO 1998, COSTI 2000, PIEROSAN in thick sheets of regolith hinder the use of soil geochemistry since they make difficult the et al. 2011), mineralogical (BASTOS NETO et identification of the B horizon, which is usually al. 2005, 2010; PIRES et al. 2006; MINUZZI et covered by a dense layer of humus and laterite al. 2008; NARDI et al. 2012) and, geochemical crusts. An additional difficulty lies in sampling studies (HORBE et al. 1991, FERRON et al. 2010) along profiles or on regular grids, due to the lack have already investigated the granite bodies and of soil exposures in areas of dense vegetation. In associated volcanic rocks of the Pitinga Mine region. this case, biogeochemistry may be more effective However, studies on supergene geochemistry are to define geochemical anomalies, since plant roots still scarce (HORBE & COSTA 1999; HORBE & act as natural samplers, absorbing elements from PEIXOTO 2006; LIMA E CUNHA et al. 2008, substrate solutions, and accumulating them in their 2012), particularly with regard to the behavior of tissues (BROOKS 1983). minor and trace elements. The use of Biogeochemistry as an alternative This study aims to characterize the method of mineral prospecting in the Amazon biogeochemical signature of some trace elements region should be encouraged. Additionally, further (Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Y, Zr, Nb, Ta, studies on the distribution of trace elements in the Mo, Sn, Sb, Cs, Ba, W, Au, Pb, Bi, U and Th - Amazonian flora and soil are needed, since these Appendix 1), which can be used as indicative of studies will establish a database of the chemical geochemical patterns related to mineralization in composition of flora, and its relationship with soil the area of the Pitinga Mine. For this purpose, the and bedrock geochemistry. This research will lay Biological Absorption Coefficient (BAC), which is the foundation for future research on plant species the ratio of an element concentration in plants to tolerance to potentially toxic elements. Moreover, its concentration in soil, was used. Previous studies such studies will be useful for the implementation (KOVALEVSKY 1979, BROOKS 1983, BAKER of environmental monitoring programs to prevent 1981, ALLOWAY et al. 1988) have discussed this pollution from anthropogenic activities, and for parameter and indicated it can be used in mineral the identification of plant species, whose chemical exploration. According to EBONG et al. (2007), composition will be used in mineral prospecting this ratio is a convenient and reliable way to or as means of remediation of mined-out areas quantify the relative differences in bioavailability (DUNN & ANGELICA 2000). of metals to plants. As pointed out by Miao et The Pitinga Mine District, located in the al. (2011), the index of biological absorption Amazonas State, Brazil, contains large tin deposits coefficient can be used to predict the availability of genetically related to two granite bodies, the Agua each element in the soil-plant system.

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2 MATERIALS AND METHODS at the ActLabs Laboratory (Canada). The results are expressed in weight of ashes. Soil samples, Eighteen pairs of plant and soil samples weighing about 50 g each, were collected with a were collected on the alteration zone of the Biotite manual auger at a depth of approximately 20 cm Granite (BG) and Albite Granite (ABG), which at the same sampling location where plants were are both facies of the Madeira Granite, and in collected. They were dried at 80° C, disaggregated the areas of effusive volcanic rocks, pyroclastic in a porcelain grail, and the fraction of < 150 mesh and hypabyssal bodies, which make up the was used for chemical analysis by ICP-MS after Iricoumé Group (Figure 1). Plant species of the fusion with a flux composed of lithium borate at a family Rhamnaceae Ampelozizyphus amazonicus temperature of 1000 °C at the Acme Labs (Canada). (local name: saracura-mirá) and Pteridophytes of The fusion product was digested in a weak nitric the genus Adiantum sp. (maidenhair fern) were acid solution and then aspirated into the ICP-MS to selected due to their wide distribution and easy determine the elemental concentrations. identification in the area of the Pitinga Mine. It was necessary to choose two different types 3 RESULTS AND DISCUSSION of plants because the biogeochemical signature is a selective mixture of chemical components The composition of plant tissues reflects of the soil/water/rock system. Moreover, each the composition of the soil in which the plant soil horizon contains different concentrations of grows. Concentrations of trace elements in plants elements, and each plant species shows different depends on several factors, such as abundance abilities to absorb trace elements from the soil. In in the soil, bioavailability, plant age, speciation this study, leaves were chosen as samples because of elements, depth of root system and others. they are easy to collect; in perennial plants, Therefore, the variability is generally high. The analytical results are more uniform (less erratic Biological Absorption Coefficient (BAC) was regarding levels of branches). Roots were not used to determine the relationship between the sampled due to the difficulty in collecting and the concentration of chemical elements in the soil and easy contamination with soil elements. in the plants. Depending on the magnitude of the Plant samples (approximately 200 g of coefficient, the elements were classified into five leaves) were first dried at 80 oC and then, calcined groups: BAC > 10 – very strongly accumulated; at temperatures of 450-500 °C for 6 to 8 hours. from 1 to 10 – strongly accumulated; from 0.1 to The resulting ash (0.25 g) was digested with 1.0 – moderate absorption; from 0.01 to 0.1 – weak

HClO4-HNO3-HCl-HF and analyzed by ICP-MS absorption, and from 0.001 to 0.01 – very weak

FIGURE 1 – Geologic map of the Pitinga Mine area, showing the localization of sampling sites (modified from LENHARO et al. 2000).

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absorption (KABATA-PENDIAS & PENDIAS The high BAC for Cu, Zn, and Ni obtained 1984). The increase in BAC in mineralized areas in samples collected from the granite and volcanic occurs when the elements are present in the soils suggests the presence of sulfide mineralization, form of soluble compounds or as fine-grained even though these elements are micronutrients and disseminations, which results in increasing their therefore, actively absorbed by plants. HORBE availability to plants (KOVALEVSKY 1979). & PEIXOTO (2006) reported the enrichment in The evaluation of BAC in pairs of samples of Cu, Pb and Zn in soils from volcanic rocks in the soil and plants collected in the areas of the albite Pitinga Mine area. BAC for Se and Pb is also high, granite and biotite granite facies of the Madeira but they are not micronutrients absorbed by most Granite and in the adjacent volcanic sequence of plants and can be toxic to many of them, which also the Iricoumé Group showed significant BAC values points to the presence of sulfide mineralization, for various elements, as shown in table 1. Two commonly enriched in these chalcophile elements. groups of elements stand out, the first consisting High concentrations of Se in plants are a good of those strongly concentrated in the studied plants indication of the presence of sulfide mineralization, (BAC > 10): Ni, Cu, Zn, Se, Rb, Sr and Au. In the as discussed by DUNN (2007). The high BAC for second group, elements have lower concentrations Au, particularly in the fern samples collected in in the plant than in the correspondent soil (BAC < the albite granite and volcanic areas, is probably 1): Ga, As, Zr, Nb, Ta, Mo, W, Bi, Th and U. A third related to mineralization of this element associated group with variable behavior was defined, which with sulfides. According to DUNN (1995) Au includes Y, Sb, Cs, Ba and Pb. plays no role in plant nutrition, and in areas with mineralization, Au can be accumulated in plants in amounts significantly greater than background levels (≤ 0.5 ppb). Biogeochemical studies on ultramafic TABLE 1 – Average values of Biological Absorption soils in southern Brazil reported high concentrations Coefficient (BAC) in the Pitinga Mine area. Ptdf. of Au (50ppb) associated with Pd, Pt, and Ag in fern Abg = maidenhair fern in the albite granite facies; Ptdf. Bg = maidenhair fern in the biotite granite; species (Adiantopsis cf. chlorophylla); additionally, Src Bg = saracura-mirá in the biotite granite; Ptdf. V precipitated metallic gold have been identified = maidenhair fern in the volcanic sequence; Src V = in plant tissues by scanning electron microscopy saracura-mirá in the volcanic sequence. (LIMA E CUNHA et al. 2004). High values of BAC were also observed for Sb in the BG area, and BAC Ptdf._Abg Ptdf._Bg Src_Bg Ptdf._V Src_V this rare element is usually associated with sulfides Ni 24.86 0.38 10 127.3 12.1 (BABULA et al. 2008). Although easily absorbed by Cu 7.5 82.5 168 138.2 157.41 plants when in a soluble form, Sb is not an essential Zn 55.95 28.6 55.65 35.18 35.65 element and occurs at very low concentrations. Ga 0.39 0.13 0.07 0.65 0.34 However, in areas with mineralization of Au-Sb-As, As 0.48 0.24 0.23 0.62 0.39 plants are generally enriched in Sb (DUNN 2007). Se 56.47 128 20 40 23.68 The BAC of elements such as Rb and Cs Rb 39.93 789 365.96 20.3 111.01 in the BG area reaches very high values (> 100), Sr 33.9 15.83 15.85 15.3 22.13 although concentrations in the soil are relatively Y 13.62 0.53 0.02 3 3.81 low (c.a. 1-20 ppm). The strong ability of plants Zr 0.003 0.001 0.0004 0.001 0.001 of accumulating Rb and Cs in impoverished soils Nb 0.004 0.005 0.02 0.01 0.02 is due to the high geochemical mobility of these Ta 0.01 0.003 0.17 0.02 0.1 elements. In areas of volcanic rocks, where the Mo 0.04 0.015 1.73 0.07 0.35 Sn 23.57 0.05 0.0009 2.4 3.72 concentrations of Cs in the soil are far higher than Sb 0.12 29.5 97.4 0.66 0.41 the background of this element (25 ppm according Cs 4.15 3.65 100.14 0.12 0.3 to WHITE & BROADLEY 2000), the BAC is very Ba 0.49 2.09 0.0013 97.9 26.87 low (< 0.4). This can be caused by the toxicity of W 0.047 0.01 0.02 0.07 0.08 this element triggering the activation of exclusion Au 32 8.25 15.47 37.5 27.05 mechanisms of the plant when its concentration in Pb 11.06 3.98 1.3 4.3 7.45 the soil is too high. Additionally, the adsorption of Bi 0.17 0.24 0.16 1.25 0.25 Cs by clay minerals can reduce its availability to Th 0.076 0.05 0.046 0.36 0.5 plants in enriched soils (KABATA-PENDIAS & U 0.047 0.038 0.042 0.15 0.08 PENDIAS 1984).

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In the volcanic and granite areas, BAC is were very strongly accumulated, (BAC > 10), as relatively high for Sr in both plants. In addition to illustrated in figure 2. In the granite areas (Figure its geochemical similarity to Rb, Sr is considered 3), the saracura-mirá shows BAC greater than an essential element for some plant species, with 10 for Ni, Cu, Zn, Se, Rb, Sr, Sb, Cs and Au. biochemical functions similar to those of Ca For the ferns, the BAC is greater than 10 for (KABATA-PENDIAS & PENDIAS 1984). Sn Zn, Se, Rb, Sb and Cu, and greater than 1 for has low mobility in the supergene environment, Cs, Ba, Au and Pb. Ferns collected in the albite and therefore low bioavailability, because it can granite facies show BAC greater than 1 for Co, be strongly absorbed by clay minerals or because Cu, Cs, and greater than 10 for Ni, Zn, Se, Rb, it occurs as , a detrital phase with low Sr, Y, Sn, Au and Pb (Figure 4). The elements solubility. According to GREGER (2004), Sn has with BAC exceeding 10 in areas covered by the low mobility in soil, but it can be easily absorbed three lithotypes are: Ni, Zn, Se, Rb, Sr and Au. from the solubilized fraction in enriched soil. The BAC for Sn, Y, and Pb is greater than 10 in The high BAC for Sn (> 23) observed in plants the albite granite facies area; in the biotite granite collected in the albite granite facies, which area, the BAC for Cu, Cs, and Sb is greater than contains high amounts of disseminated cassiterite, 10, and in the volcanic terrains, BAC for Cu and confirms that the increase in the BAC for Sn may be indicative of the presence of mineralization, as Ba is greater than 10. proposed by KOVALEVSKY (1979). The BAC for Y (c.a. 13) shows behavior similar to that of Sn. Moreover, Y concentration is very high in samples of soils and plants from the albite granite facies, which is consistent with the strong enrichment in Y in the Madeira granite mineralization, as reported by BASTOS NETO et al. (2012). According to WELCH (1984), the BAC for Y in terrestrial plants is 0.003. BAC for two characteristic elements of the Pitinga Mine mineralization, Nb and Ta, is low in the granitic facies and in areas of volcanic rocks, although the soils may show high concentrations of these elements. The low values of BAC are due to the low geochemical mobility of both FIGURE 2 – Biologic Absorption Coefficient (BAC > elements, since they are bound to minerals 1 and > 10) for plants in the volcanic terrains of the with low solubility, such as cassiterite, in soils, Pitinga Mine (▲ - maidenhair fern; ● - saracura-mirá). ores and host rocks, and consequently have low availability to plants. Nb has low mobility in natural environments (DUNN 2007), since most of the Nb compounds are slightly soluble in both acid and alkaline media. Weathering fluids have low dissolved Nb since it remains fixed within resistant minerals and therefore unavailable to plants (KABATA-PENDIAS & PENDIAS 1984). The low mobility of Nb in soils is supported by studies by SCHEIB et al. (2012), which estimate that 95% of niobium in Europe’s soils is not available to plants. In this case, as for other trace elements with low mobility, the BAC is not indicative of mineralization. In the volcanic rocks, for both species, Y, FIGURE 3 – Biologic Absorption Coefficient (BAC Sn, and Pb were strongly accumulated (BAC > > 1 and > 10) for plants in the granite terrains of the 1), whereas Ni, Cu, Zn, Se, Rb, Sr, Ba and Au Pitinga Mine (▲ - maidenhair fern; ● - saracura-mirá).

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similar in both terrains, except for Sb and Cs, which show higher BAC in the granitic terrains, and for Ba, Sn and Y, which show higher BAC in the volcanic terrains. Therefore, the absorption capacity of most of the studied elements is greater in the fern samples of the volcanic soils. The variation of the BAC in the same species of plant, from one terrain to the other, is probably caused by the variation in abundance of the elements in soils and rocks, as well as by the way the elements are accumulated in soils and fixed in host rocks, either granites or volcanic rocks. Ni, Cu, Zn, Se, Rb, Sr, Pb, and Au show high BAC in most situations, i.e., in both terrains and FIGURE 4 – Biological absorption coefficient (BAC) for both plant species. A second group, formed by for maidenhair fern from the albite-granite-facies Ga, Zr, As, Nb, Ta, Mo, W, Bi, Th, and U, has, in terrain of the Pitinga Mine. general, BAC lower than 1, whereas some elements have a variable behavior. Y and Sn show BAC According to KOVALEVSKY (1979), BAC > 10 for plants collected in the terrain covering greater than 10 is indicative of the mineral phase the mineralization of the Pitinga Mine, which is in which the element is predominantly contained. enriched in these two elements, as well as in Zr, Nb, For example, in the case of Zn, a BAC over 10 and Ta. In the granitic terrain, the saracura-mirá is indicates the presence of sphalerite. According to extremely enriched in Cs, whereas the BAC for Ba that author, a BAC for Au greater than 10 indicates increases in the volcanic terrain. This increase is the occurrence of Au as grains scattered in clays, probably explained by the high concentrations of sulfides or iron oxides, and the high BAC for Pb this element in the volcanic rocks of the Pitinga indicates its presence as cerussite or anglesite, lead Mine area (PIEROSAN et al. 2011). carbonates and sulfates. Out of the main ore-forming elements in the 4 CONCLUSIONS Pitinga Mine (Sn, Nb, Ta, Zr, Y and Rb), only Sn The Biological Absorption Coefficient (BAC) and Y show high values of BAC, particularly for the can be indicative of the presence of mineralization maidenhair fern, which can indicate the presence of when the elements involved have moderate to mineralization. The reason for this is that the BAC high mobility; whereas the BAC for elements with behavior depends on the toxicity of the elements low mobility, such as Zr, Nb, Ta, does not show a to the plants, and on the availability of the element consistent variation. Particularly for the maidenhair in the soil. Additionally, soil samples are usually fern samples from granitic and volcanic terrains, representative of a relatively small volume of the high BAC for Au, ranging from 8 to 40, material; on the other hand, the plant, through its reinforces the possibility of using this element root system, covers several cubic meters of all soil as an indicator of its deposits in biogeochemical horizons, sometimes reaching up to the underlying exploration. Regarding sulfide mineralization, the rock. In this sense, from an exploration point of same conclusion can be applied to Cu, Zn, and view, high concentrations of Y, Zr, Nb, Pb, Sn and Pb. BAC for Y and Sn increased significantly in Th in the maidenhair fern (Table 2) collected in the tin mineralized areas and therefore it was proposed area of the pegmatoid cryolite deposits, are quite that this parameter could be used as an additional significant. tool in mineral exploration. The comparison between the BAC of the Moreover, the results of this work suggest elements in fern and saracura-mirá in both types of that A. amazonicus (saracura-mirá) is useful as terrains (granitic and volcanic) shows that the fern an indicator in mineral exploration programs in has the highest BAC in the volcanic terrain, which the Amazonian region, as previously suggested is usually around ten times the BAC in the granitic by other authors (LIMA e CUNHA et al. 2008). terrain. The comparison is the opposite for Rb, Se, Therefore, despite the difficulties faced in the Sb and Cs, which show higher BAC in the granitic Amazonian environment, such as the selection areas. For the saracura-mirá, the BAC values are of the most representative plants, the precise

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identification of the B horizon, which is usually BORGES, R.M.K.; DALL’AGNOL, R.; COSTI, covered by thick layers of humus and lateritic crust, H.T. 2003. Geologia, Petrografia e Química and the lack of exposed soils, the results obtained Mineral das Micas dos Greisens Estaníferos in this study support the use of biogeochemistry as Associados ao Pluton Agua Boa, Pitinga a valuable tool in mineral exploration. (AM). Revista Brasileira de Geociências, 33(1): 51-62 5 ACKNOWLEDGEMENTS BROOKS, R.R. 1983. Biological methods of This work was supported by the project CT- prospecting for minerals. Wiley, New York, Mineral/MCT/CNPq nº 027/2004. 322 p.

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Paleoproterozoic Volcanic and Granitic Rocks 2004. Diagnose de Microbiólitos Metálicos (1.89 to 1.88 Ga) of the Pitinga Province, em Espécies Vegetais Endêmicas em Solos Amazonian Craton, Brazil. Journal of South de Rochas Ultramáficas por Microscopia America Earth Science, 53(8): 946-979. Eletrônica de Varredura. Pesquisas em Geociências, 31(1): 17-28. GREGER, M. 2004. Metal availability, uptake, transport and accumulation in plants. In: LIMA E CUNHA, M.C.; PEREIRA, V.P.; M.N.V. Prasad (ed.) Heavy metal stress in MENEGOTTO, E.; BASTOS NETO, nd plants: From biomolecules to ecosystems. 2 A.C.; OLIVEIRA, E.L.O.; FORMOSO, ed., Berlin, Springer, p. 1-27. M.L.L. 2008. Biogeochemical behavior of HORBE, A.M.C.; COSTA, M.L. 1999. Ampelozizyphus amazonicus Ducke in the Geochemical evolution of a lateritic Sn-Zr- Pitinga mining district, Amazon, Brazil. Th-Nb-Y-REE bearing ore body derived from Environmental Geology, 55: 1355-1362. apogranite: the case of Pitinga, Amazonas - LIMA E CUNHA, M.C.; PEREIRA, V.P.; NARDI, Brazil. Journal of Geochemical Exploration, 66: 339-351. L.V.S.; BASTOS NETO, A.C.; VEDANA, L.A.; FORMOSO, M.L.L. 2012. REE HORBE, A.M.C; PEIXOTO S.F. 2006. Distribution Pattern in Plants and Soils from Geochemistry of Pitinga Bauxite Deposit Pitinga Mine -Amazon, Brazil. Open Journal - Amazonian Region - Brazil. In: R.W. of Geology, 2: 253-259. Fitzpatrick & P. Shand (ed.) Regolith - Consolidation and Dispersion of Ideas. The MIAO, L.; MA, Y.; XU, R.; YAN, W. CRC Leme Regolith Symposium, Hahndorf 2011. Environmental biogeochemical Resort, Proceedings, p. 144-146. characteristics of rare earth elements in soil and soil-grown plants of the Hetai goldfield, HORBE, M.A.; HORBE, A.C.; COSTI, H.T.; Guangdong Province, China. Environmental TEIXEIRA, J.T. 1991. Geochemical Earth Science, 63: 501-511. characteristics of cryolite – tin-bearing granites from the Pitinga Mine, Northwestern MINUZZI, O.R.R.; BASTOS NETO, A.C.; Brazil - a review. Journal of Geochemical FORMOSO, M.L.L.; ANDRADE, S.; JANASI Exploration, 40: 227-249. V.A.; FLORES, J.A.A. 2008. Rare earth element and yttrium geochemistry applied to KABATA-PENDIAS, A.; PENDIAS H. 1984. Trace elements in soils and plants. CRC, the genetic study of cryolite ore at the Pitinga Boca Raton, 315 p. mine (Amazon, Brazil). Anais da Academia Brasileira de Ciências, 80: 719-733. KOVALEVSKY, L.A. 1979. Biogeochemical Exploration for Mineral Deposits. Oxonian NARDI, L.V.S.; FORMOSO, M.L.L.; JARVIS, Press PVT, Nova Delhi, 136 p. K.; OLIVEIRA, L.; BASTOS NETO, A.C.; FONTANA, E. 2012. REE, Y, Nb, U, and LENHARO, S.L.R. 1998. Evolução magmática Th contents and tetrad effect in zircon from a e modelo metalogenético dos granitos magmatic-hydrothermal F-rich system of Sn- mineralizados da região de Pitinga, rare metal–cryolite mineralized granites from Amazonas, Brasil. Departamento de the Pitinga Mine, Amazonia, Brazil. Journal of Engenharia de Minas, Escola Politécnica, South American Earth Sciences, 33(1): 34-42. Universidade de São Paulo, São Paulo, Tese de Doutorado, 290 p. PIEROSAN, R.; LIMA, E.F.; NARDI, L.V.S.; CAMPOS, C.P.; BASTOS NETO, A.C.; LENHARO S.L.R.; POLLARD, P.J.; BORN, JARVIS, K.; FERRON, J.M.; PRADO, M., H. 2000. Matrix rock texture in the Pitinga 2011. Geochemistry of Palaeoproterozoic Topaz Granite, Amazonas, Brazil. Revista volcanic rocks of the Iricoumé Group, Brasileira de Geociências, 30(2): 238-241. Pitinga Mining District, Amazonian craton, LIMA E CUNHA, M.C.; MARIATH, J.E.A.; Brazil. International Geology Review, 53(8): MENEGOTTO, E.; FORMOSO, M.L.L. 946-979.

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PIRES, A.C.; BASTOS NETO, A.C.; PEREIRA, Geochemistry: Exploration, Environment, V.P.; BOTELHO, N.F. 2006. A gagarinita- Analysis, 12: 293-302. (Y) do granito Madeira (Pitinga, Amazonas): exsolução de ETRL a partir de fluoreto WELCH, G.R. 1984. Biochemical dynamics in metaestável e formação de um possível novo organized states: A holistic approach. In: J. mineral semelhante à fluocerita. Revista Ricard & A. Cornish-Bowen (ed.). Dynamics Brasileira de Geociências, 36 (1): 155-164. of Biochemical Systems. New York, Plenum Press, p. 85-101. SCHEIB, A.J.; FLIGHT, D.M.A.; BIRKE, M.; TARVAINEN, T.; LOCUTURA, J.; GEMAS WHITE, P.J.; BROADLEY, M.R. 2000. Project Team. 2012. The geochemistry of Mechanisms of caesium uptake by plants. niobium and its distribution and relative New Phytology, 147: 241-256 (Tansley mobility in agricultural soils of Europe. Review Nº 113).

Endereço dos autores:

Maria do Carmo Lima e Cunha, Lauro Valentim Stoll Nardi, Vitor Paulo Pereira e Artur Cezar Bastos Neto – Centro de Estudos em Geoquímica e Petrologia, Instituto de Geociências, Universidade Federal do Rio Grande do Sul, Caixa Postal 15001, Porto Alegre, RS, Brasil. E-mails: [email protected]; lauro. [email protected]; [email protected]; [email protected]

Luiz Alberto Vedana – Curso de Pós Graduação em Geociências, Instituto de Geociências, Universidade Fe- deral do Rio Grande do Sul, Caixa Postal 15001, Porto Alegre, RS, Brasil. E-mail: [email protected]

Artigo submetido em 21 de maio de 2014, aceito em 12 de agosto de 2014.

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13426 miolo.indd 27 1/21/15 4:49 PM Lima e Cunha et al. 5 V 8 30 34 1.5 0.7 113 1.6 240 404 121 228 861 133 3.51 33.2 12.1 4.25 35.6 0.58 16.7 3530 Src18 0.191 8 5 V 4 74 14 43 31 1.1 7.1 0.5 210 267 412 48.3 0.49 39.8 25.2 53.1 1.05 49.6 4.17 1410 Src17 0.009 9 5 V 3 64 39 8.4 1.5 0.7 1.4 0.6 238 294 80.1 18.5 1.11 0.32 16.3 2.58 1.04 1.91 20.5 1660 Src16 0.013 9 5 V 2 30 2.1 1.5 0.9 1.2 112 207 616 101 12.2 0.13 7.49 1.25 1.42 0.57 19.1 0.25 1360 Src15 0.566 0.102 6 5 V 1 28 7.9 8.8 2.8 1.5 2.7 243 290 212 76.5 0.17 0.25 0.14 45.7 0.25 2650 Src14 0.255 0.719 0.665 0.067 8 4 5 V 3 39 1.5 0.6 1.4 0.6 0.6 249 437 162 82.1 26.6 0.59 20.3 1.65 3.25 1.45 7.14 1130 Src13 0.016 6 V 2 10 1.5 0.9 106 404 656 179 396 101 66.4 0.25 14.2 7.55 1.08 0.25 0.59 3.76 0.25 1400 0.532 0.022 Ptdf12 8 V 5 20 10 45 2.7 2.9 0.7 195 270 447 47.4 93.4 0.76 48.3 36.4 1.62 55.7 6.79 39.1 1200 0.236 0.009 Ptdf11 7 5 3 Bg 33 31 1.8 8.9 1.5 1.1 2.7 0.9 104 242 176 12.2 0.41 0.57 1.37 0.11 2.68 0.16 69.9 3880 Src10 6 5 1 Bg 43 20 1.1 4.2 1.5 0.6 5.9 293 126 11.6 97.7 0.21 Src9 0.56 1.37 1.64 0.14 0.05 61.2 0.25 4550 5 5 10 Bg 76 7.1 1.5 0.6 3.3 0.9 131 292 236 140 15.5 0.54 13.1 Src8 0.98 2.38 1.26 0.02 0.18 52.9 2710 7 5 5 Bg 39 1.5 1.2 2.7 125 266 175 217 132 17.3 0.65 10.3 12.6 Src7 1.74 0.32 40.9 0.25 2100 0.588 0.012 5 5 9 Bg 8.1 1.7 1.5 2.1 1.7 0.5 188 222 383 80.7 0.25 0.92 Src6 0.28 0.48 0.85 0.02 0.12 18.6 0.25 2350 3 Bg 28 2,5 1.5 4.2 1.9 138 110 335 239 37.6 53.9 0.58 13.7 10.6 52.2 0.01 0.34 17.4 0.25 5370 Ptdf5 0.652 0.254 5 5 2 Bg 56 21 1.8 1.5 273 140 94.6 13.8 0.22 5.02 1.46 0.25 1.43 0.07 58.7 0.25 4250 Ptdf4 0.551 0.098 0.098 8 8 50 Ab 2,5 1.5 1.9 311 502 130 149 204 53.3 3.89 57.2 15.8 11.6 12.7 0.11 53.1 12.9 8860 1700 Ptdf3 0.267 5 10 Ab 20 12 92 1.5 4.2 2.5 110 152 33.4 2.76 38.1 6.19 79.8 17.4 0.22 86.4 1180 1370 5370 3900 Ptdf2 0.673 5 35 30 21 Ab 14 14 1.5 2.3 112 388 112 101 199 10.2 70.8 6.48 15.4 0.11 58.8 9.07 1190 2940 Ptdf1 0.235

Y U Bi Ni Sr Se As W Zr Zn Th Ta Sn Cu Sb Rb Cs Ga Nb Ba Au Pb Mo APPENDIX 1 – Chemical composition of plant samples. Values in ppm of ashes, except for Au (ppb). Ptdf.: maidenhair fern; Src: saracura: Ab: Albite Granite (3); Bg: Au Ab: in (ppb). ppm Ptdf.: of maidenhair ashes, fern; except Src: for saracura: APPENDIX 1 – Chemical composition of Values plant samples. (8). Volcanics V: Biotite Granite (7);

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13426 miolo.indd 28 1/21/15 4:49 PM Revista do Instituto Geológico, São Paulo, 35 (1), 19-29, 2014. 7 5 V 14 10 0.8 0.6 0.3 0.9 0.7 1.6 6.6 2.7 5.6 160 36.8 15.3 40.5 39.8 21.2 30.6 40.2 0.25 1063 SL18 V 10 14 95 0.5 0.5 0.6 8.6 0.5 1.5 2.6 5.1 7.2 1.2 13.2 50.3 18.6 63.5 0.25 16.2 15.7 42.8 69.4 1677 SL17 6 1 V 50 23 73 0.7 0.6 6.5 0.6 5.9 9.3 0.4 3.3 6.3 6.8 0.5 64.2 0.25 17.8 15.8 47.8 80.8 2102 SL16 4 V 40 52 0.9 0.6 3.6 0.4 2.5 0.9 8.2 0.6 0.3 0.3 6.8 7.5 3.9 61.1 79.9 0.25 18.5 23.2 92.4 2943 SL15 4 5 9 V 13 34 0.2 0.4 3.6 2.3 0.7 0.3 3.4 9.8 135 40.4 74.1 0.25 13.4 56.5 14.7 0.25 2607 SL14 102.9 6 6 V 27 54 13 48 0.5 0.6 0.2 5.3 9.8 0.7 0.6 3.6 3.7 4.8 0.8 48.9 50.6 0.25 10.4 32.1 2027 SL13 7 9 V 38 0.6 1.4 0.2 0.7 1.4 8.5 3.5 5.6 263 23.6 44.8 13.9 52.2 0.25 37.8 35.3 44.4 0.25 1052 SL12 112.1 V 10 14 95 0.5 0.5 0.6 8.6 0.5 1.5 2.6 5.1 7.2 1.2 13.2 50.3 18.6 63.5 0.25 16.2 15.7 42.8 69.4 SL11 1677 5 1 11 38 Bg 0.6 0.8 4.9 2.8 6.4 6.6 2.8 3.3 1.1 198 80.8 0.25 20.9 14.5 64.4 27.7 2477 SL10 267.7 235.8 4 68 19 Bg 0.7 0.6 7.2 2.3 4.7 5.2 9.3 2.2 0.5 0.9 5.7 239 SL9 260 77.5 0.25 22.1 26.7 33.6 3235 225.1 4 26 Bg 0.6 0.4 6.7 3.3 4.3 6.7 1.2 0.1 1.1 SL8 188 67.5 0.25 21.1 10.2 83.4 24.2 26.1 <0.5 2698 197.6 199.4 5 1 64 Bg 0.5 0.8 3.1 7.9 1.4 0.6 120 130 SL7 11.9 18.5 11.7 52.5 0.25 20.5 16.3 53.1 15.5 0.25 2486 106.2 5 5 1 2 63 72 Bg 1.1 0.6 1.4 8.3 7.6 0.8 0.3 100 SL6 12.3 44.1 0.25 12.6 16.6 40.7 92.5 12.7 2461 1 6 1 8 7 6 1 1 1 10 10 46 57 10 21 33 77 62 87 12 Bg 0.6 SL5 0.25 2182 4 1 10 68 19 Bg 0.6 7.2 2.3 4.7 0.3 5.2 9.3 0.5 5.7 239 260 SL4 77.5 22.1 26.7 26.7 33.6 225.1 3234.7 2 20 12 Ab 0.3 2.1 2.9 0.4 1.9 161 621 SL3 13.1 34.9 49.9 95.5 0.25 2450 2451 4791 111.7 372.5 196.1 148.8 545.6 8 10 Ab 0.3 1.2 8.3 5.8 5.6 0.7 0.6 107 516 SL2 101 21.2 0.25 23.3 28.2 14.4 33.9 0.25 1331 2335 219.3 875.4 7 6 54 Ab 0.1 1.7 1.5 2.4 0.3 1.1 155 SL1 54.4 0.25 48.2 0.25 36.9 1397 4748 1791 213.2 205.8 130.2 571.7 14921

Y U Bi W Sr Ni Se Zr Ta As Sn Sb Zn Th Cs Rb Cu Ba Au Pb Nb Ga Mo APPENDIX 1– (cont.) Chemical composition of the soils samples. in Values ppm, except for Au (ppb). (8). SL: soil; Volcanics Ab: Albite Granite (3); Bg: Biotite Granite (7); V:

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