Caracterização de clorita portadora de Zn por espectroscopia Mössbauer (EM) e espectroscopia infravermelho (IV) - uma ocorrência associada ao depósito de Pb-Zn-Ag de Canoas, PR, Brasil

Imbernon, Rosely Aparecida Liguori; Blot, Alain; Pereira, Vitor Paulo; Franco, Daniel Ribeiro

doi:10.25249/0375-7536.2011412228236

Resumo:

Amostras de clorita associadas ao minério sulfetado de Pb-Zn-Ag do depósito de Canoas 1, Vale do Ribeira, Paraná, Brasil, foram analisadas por espectroscopia Mössbauer (EM) e infravermelho (IV). Os estudos empreendidos possibilitaram discutir questões relacionadas ao processo de cloritização associado à estrutura cristalina, e as formas pelas quais o Zn foi incorporado no mineral neoformado. Tais questões possibilitam retomar aspectos geoquímico/mineralógicos desse processo natural, onde a cristaloquímica e os mecanismos de formação de cloritas têm sido utilizados em vários campos das ciências aplicadas. Os resultados evidenciaram que se trata da ocorrência de clorita, que ao incorporar Zn na estrutura altera padrões estruturais que se refletiram nas análises por EM e IV. Os dados obtidos por EM evidenciaram que o Fe está localizado exclusivamente nos sítios octaédricos em arranjo trans, e a entrada de Zn durante o processo de cloritização ocorre, também, na camada brucítica.

Palavras-chave:
clorita zincífera; espectroscopia infravermelho; espectroscopia Mössbauer; depósito de Canoas-Brasil

Abstract:

In order to provide new insights on mineralogical aspects of geochemical mapping/natural processes related to the chlorite formation (e.g.crystallochemistry and mechanisms of formation of these materials, which has been applied in different studies of environmental profiles), we investigated chlorite samples associated to the Pb-Zn-Ag sulfide ore from Canoas 1 deposit (Vale do Ribeira, state of Paraná, Brazil). By means of Mössbauer (MS) and infrared (IV) spectroscopy, we addressed some issues as those related to the chloritization processes, as well as how Zn would be incorporated into its crystalline structure. Results carried out by ME and IV spectroscopy clearly pointed out for a chlorite occurrence, which in fact incorporates Zn into its structure and also alters the structural patterns for this mineral. Moreover, ME data sets indicated the presence of Fe which is located only in octahedral sites, in trans-configuration, and the Zn emplacement by the chloritization process also occurs in the brucite layer.

Keywords:
zinciferous chlorites; infrared spectroscopy; Mössbauer spectroscopy; Canoas deposit-Brazil

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Referências

Bailey S.W. 1988. Structures of layer silicates. In: Brindle G.W., and Brown G. (eds.) Crystal Structures of Clay Minerals and their X-ray Identification Londres, Mineralogical Society, p. 1-124.
Bettencourt J.S., Daitx E.C., Moreira M.Z., Matsui E. 1992. Estudo isotópico pelos métodos ¹³C/¹²C, ¹⁸O/^16o, dD e ³⁴S/³²S dos depósitos de chumbo-zinco-prata do vale do Ribeira, Estados de São Paulo e Paraná. São Paulo, FAPESP. (relatório de Pesquisa Processo 90/2139-2).
Blot A., Imbernon R.A.L. 2000. Caractérization par analyse thermique de la constitution cristallochimique de diverses chlorites zinciféres. C. R. Acad. Sci. Paris, Sciences de la Terre e des Planètes: 330(7):469-472.
Blot A., Oliveira S.M.B., Magat P. 1995. La chloritisation supergène zincifère des phlogopites de Canoas (PR, Brésil). C. R. Acad. Sci. Paris, Sciences de la Terre e des Planètes, 321(II a):651-658.
Brindley G.W., Brown G. (eds.) 1984. Crystal structures of Clay Minerals and their X-ray identification Londres, Min. Soc., 504 p.
Coey J.M.D. 1975. Clay minerals and their transformations studied with nuclear techniques: the contribution of Mössbauer spectroscopy: At. Energy Rev 18:1-124.
Daitx E.C. 1996. Origem e evolução dos depósitos sulfetados tipo-Perau (Pb-Zn-Ag), com base nas jazidas Canoas e Perau (Vale do Ribeira, PR) Tese de Doutorado, Instituto de Geociências e Ciências Exatas, Universidade Estadual Paulista Júlio de Mesquita Filho, Rio Claro, 453 p.
Dyar M.D. 1990. Mössbauer spectra of biotite from metapelites. American Mineralogist, 75:656-666.
De Grave E., Vandenbruwaene J., Van Bockstael M. 1987. ⁵⁷Fe Mössbauer spectroscopic analysis of chlorite. Phys. Chem. Minerals, 15:173-180.
Dunn P.J., Peacor D.R., Ramik R.A., Su S.C., Rouse R.C. 1987. Franklinfurnaceite, a Ca-Fe³⁺-Mn³⁺-Mn²⁺ a zincosilicate isotopic with chlorite, from Franklin, New Jersey. American Mineralogist, 72:812-815.
Hawthorne F.C. 1988. Mössbauer spectroscopy. Reviews in Mineralogy, 18:255-340.
Fleischer R. 1976. A pesquisa de chumbo no Brasil. In: SBG, Congresso Brasileiro de Geologia, 29, Anais, p. 19-32.
Foster M.D. 1962. Interpretation of the composition and a classification of the chlorites. U.S. Geol. Surv. Prof. Paper, 414-A:1-33.
Franco D.R., Berquó T.S., Imbernon R.A.L., Partiti C.S.M., Enzweiler J. 2007. Environmental monitoring of magnetic iron phases of urban water reservoir lake sediments (Taiaçupeba Lake, metropolitan region of São Paulo, Brazil) by using Mössbauer spectroscopy. Environmental Geology, 52:831-842.
Gadsden J.A. 1975. Infrared spectra of minerals and related inorganic compounds London, Butterworth & Co., 277 p.
Goodman B.A., Bain D.C. 1978. Mössbauer spectra of chlorites and their decomposition products In: Elsevier Scientific Pub. Co. Amsterdan, International Clay Conference, 6, Anais, p. 65-74.
Hayashi H., Oinuma K. 1967 Si-O absorption band near 1000 cm^-1 and OH absorption bands of chlorite. American Mineralogist, 52:1206-1210.
Imbernon R.A.L. 1998. Os chapéus de ferro associados aos depóstios de Canoas (Pb-Zn-Ag), Adrianópolis (PR) e O’Toole (Cu-Ni-EGP), Fortaleza de Minas (MG) Tese de Doutorado, Instituto de Geociências, Universidade de São Paulo, São Paulo, 120 p.
Imbernon R.A.L., Blot A., Oliveira S.M.B., Magat P. 1999. Os chapéus de ferro associados ao depósito de Pb-ZnAg na região de Canoas, Adrianópolis, PR - Evolução geoquímica e mineralógica. Geochim. Brasil, 13(2):145-161.
Joswig W., Fuess H., Rothbauer R., Takéuchi Y., Mason S.A. 1980. A neutron diffraction study of a one-layer triclinic chlorite (pennite). American Mineralogist, 65:349-352.
Murad E. 1998. Clays and clay minerals: what can Mössbauer spectroscopy do to help understand them? Hyperfine Interaction, 117:39-70.
Newman A.C.D., Brown G. 1987. The chemical constitution of clay. In: Newman, A.C.D. (ed.) Chemistry of Clays and Clays Minerals Essex, Longman Scientific and Technical, p. 1-128.
Parseval P., Fournes L., Fortune J.P., Moine B., Ferret J. 1991. Distribution du fer dans les chlorites par spectrométrie Mössbauer (⁵⁷Fe): Fe³⁺ dans les chlorites du gisement de talc-chlorite de Trimouns (Pyrénées, France). C. R. Acad. Sci. Paris, Sciences de la Terre e des Planètes, 312(2):1321-1326.
Phillips T.L., Loveless J.K., Bailey S.W. 1980. Cr³⁺coordination in chlorites: a structural study of ten chromian chlorites. American Mineralogist, 54:112-122.
Rule A., Radke F. 1988. Baileychlore, the Zn end member of the trioctahedral chlorite series. American Mineralogist, 73:135-139.
Shirozu H. 1980. Cation distribution, sheet thickness, and O-OH space in trioctahedral chlorites-an X-ray an infrared study. Miner. Journal, 10:14-34.
Shirozu H. 1985. Infrared spectra of trioctahedral chlorites in relation to chemical composition. Clay Sci 6:167-176.
Tuddenham W.M., Lyon R.J.P. 1958. Relation of infra-red spectra and chemical analysis for some chlorite and related minerals. Anal.Chem 3l:377-380.
Zazzi Å., Hirsch T.K., Leonova E., Kaikkonen A., Grins J., Annersten H., Edén M. 2006. Structural investigations of natural and synthetic chlorite minerals by X-ray diffraction, Mössbauer spectroscopy and solid-state nuclear magnetic resonance. Clays and Clay Minerals, 54(2):252-265.

Datas de Publicação

Publicação nesta coleção
Apr-Jun 2011

Histórico

Recebido
03 Dez 2010
Aceito
04 Out 2011

Este é um artigo publicado em acesso aberto sob uma licença Creative Commons

[1] Bailey S.W. 1988. Structures of layer silicates. In: Brindle G.W., and Brown G. (eds.) Crystal Structures of Clay Minerals and their X-ray Identification Londres, Mineralogical Society, p. 1-124.

[2] Bettencourt J.S., Daitx E.C., Moreira M.Z., Matsui E. 1992. Estudo isotópico pelos métodos ¹³C/¹²C, ¹⁸O/^16o, dD e ³⁴S/³²S dos depósitos de chumbo-zinco-prata do vale do Ribeira, Estados de São Paulo e Paraná. São Paulo, FAPESP. (relatório de Pesquisa Processo 90/2139-2).

[3] Blot A., Imbernon R.A.L. 2000. Caractérization par analyse thermique de la constitution cristallochimique de diverses chlorites zinciféres. C. R. Acad. Sci. Paris, Sciences de la Terre e des Planètes: 330(7):469-472.

[4] Blot A., Oliveira S.M.B., Magat P. 1995. La chloritisation supergène zincifère des phlogopites de Canoas (PR, Brésil). C. R. Acad. Sci. Paris, Sciences de la Terre e des Planètes, 321(II a):651-658.

[5] Brindley G.W., Brown G. (eds.) 1984. Crystal structures of Clay Minerals and their X-ray identification Londres, Min. Soc., 504 p.

[6] Coey J.M.D. 1975. Clay minerals and their transformations studied with nuclear techniques: the contribution of Mössbauer spectroscopy: At. Energy Rev 18:1-124.

[7] Daitx E.C. 1996. Origem e evolução dos depósitos sulfetados tipo-Perau (Pb-Zn-Ag), com base nas jazidas Canoas e Perau (Vale do Ribeira, PR) Tese de Doutorado, Instituto de Geociências e Ciências Exatas, Universidade Estadual Paulista Júlio de Mesquita Filho, Rio Claro, 453 p.

[8] Dyar M.D. 1990. Mössbauer spectra of biotite from metapelites. American Mineralogist, 75:656-666.

[9] De Grave E., Vandenbruwaene J., Van Bockstael M. 1987. ⁵⁷Fe Mössbauer spectroscopic analysis of chlorite. Phys. Chem. Minerals, 15:173-180.

[10] Dunn P.J., Peacor D.R., Ramik R.A., Su S.C., Rouse R.C. 1987. Franklinfurnaceite, a Ca-Fe³⁺-Mn³⁺-Mn²⁺ a zincosilicate isotopic with chlorite, from Franklin, New Jersey. American Mineralogist, 72:812-815.

[11] Hawthorne F.C. 1988. Mössbauer spectroscopy. Reviews in Mineralogy, 18:255-340.

[12] Fleischer R. 1976. A pesquisa de chumbo no Brasil. In: SBG, Congresso Brasileiro de Geologia, 29, Anais, p. 19-32.

[13] Foster M.D. 1962. Interpretation of the composition and a classification of the chlorites. U.S. Geol. Surv. Prof. Paper, 414-A:1-33.

[14] Franco D.R., Berquó T.S., Imbernon R.A.L., Partiti C.S.M., Enzweiler J. 2007. Environmental monitoring of magnetic iron phases of urban water reservoir lake sediments (Taiaçupeba Lake, metropolitan region of São Paulo, Brazil) by using Mössbauer spectroscopy. Environmental Geology, 52:831-842.

[15] Gadsden J.A. 1975. Infrared spectra of minerals and related inorganic compounds London, Butterworth & Co., 277 p.

[16] Goodman B.A., Bain D.C. 1978. Mössbauer spectra of chlorites and their decomposition products In: Elsevier Scientific Pub. Co. Amsterdan, International Clay Conference, 6, Anais, p. 65-74.

[17] Hayashi H., Oinuma K. 1967 Si-O absorption band near 1000 cm^-1 and OH absorption bands of chlorite. American Mineralogist, 52:1206-1210.

[18] Imbernon R.A.L. 1998. Os chapéus de ferro associados aos depóstios de Canoas (Pb-Zn-Ag), Adrianópolis (PR) e O’Toole (Cu-Ni-EGP), Fortaleza de Minas (MG) Tese de Doutorado, Instituto de Geociências, Universidade de São Paulo, São Paulo, 120 p.

[19] Imbernon R.A.L., Blot A., Oliveira S.M.B., Magat P. 1999. Os chapéus de ferro associados ao depósito de Pb-ZnAg na região de Canoas, Adrianópolis, PR - Evolução geoquímica e mineralógica. Geochim. Brasil, 13(2):145-161.

[20] Joswig W., Fuess H., Rothbauer R., Takéuchi Y., Mason S.A. 1980. A neutron diffraction study of a one-layer triclinic chlorite (pennite). American Mineralogist, 65:349-352.

[21] Murad E. 1998. Clays and clay minerals: what can Mössbauer spectroscopy do to help understand them? Hyperfine Interaction, 117:39-70.

[22] Newman A.C.D., Brown G. 1987. The chemical constitution of clay. In: Newman, A.C.D. (ed.) Chemistry of Clays and Clays Minerals Essex, Longman Scientific and Technical, p. 1-128.

[23] Parseval P., Fournes L., Fortune J.P., Moine B., Ferret J. 1991. Distribution du fer dans les chlorites par spectrométrie Mössbauer (⁵⁷Fe): Fe³⁺ dans les chlorites du gisement de talc-chlorite de Trimouns (Pyrénées, France). C. R. Acad. Sci. Paris, Sciences de la Terre e des Planètes, 312(2):1321-1326.

[24] Phillips T.L., Loveless J.K., Bailey S.W. 1980. Cr³⁺coordination in chlorites: a structural study of ten chromian chlorites. American Mineralogist, 54:112-122.

[25] Rule A., Radke F. 1988. Baileychlore, the Zn end member of the trioctahedral chlorite series. American Mineralogist, 73:135-139.

[26] Shirozu H. 1980. Cation distribution, sheet thickness, and O-OH space in trioctahedral chlorites-an X-ray an infrared study. Miner. Journal, 10:14-34.

[27] Shirozu H. 1985. Infrared spectra of trioctahedral chlorites in relation to chemical composition. Clay Sci 6:167-176.

[28] Tuddenham W.M., Lyon R.J.P. 1958. Relation of infra-red spectra and chemical analysis for some chlorite and related minerals. Anal.Chem 3l:377-380.

[29] Zazzi Å., Hirsch T.K., Leonova E., Kaikkonen A., Grins J., Annersten H., Edén M. 2006. Structural investigations of natural and synthetic chlorite minerals by X-ray diffraction, Mössbauer spectroscopy and solid-state nuclear magnetic resonance. Clays and Clay Minerals, 54(2):252-265.

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