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Type Tourmalines from Brazil and Mozambique: Implications for Origin and Authenticity Determination

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Type Tourmalines from Brazil and Mozambique: Implications for Origin and Authenticity Determination No.9 May 2009 Chemical Variations in Multicolored “Paraíba”-Type Tourmalines from Brazil and Mozambique: Implications for Origin and Authenticity Determination “Cuprian-Elbaite”-Tourmaline from Mozambique “Paraiba”- Tourmaline from Brazil Manganese Mn Inner core Mn Bi Cu Bi Copper Chemical Variation in “Paraiba”-Tourmaline Chemical Distribution Mapping Editor Message from the Editors Desk: When Dr. A. Peretti, FGG, FGA, EurGeol trace element research matters most GRS Gemresearch Swisslab AG, P.O.Box 4028, 6002 Lucerne, Switzerland When copper bearing tourmalines were found 20 [email protected] years ago in the state of Paraíba in Brazil, they intrigued by their “neon”-blue color and soon became known as “Paraíba” tourmalines in the trade. In the Previous Journal and Movie years before and into the new Millennium, these tourmalines have emerged to become one of the most valuable and demanded gems, comparable to prestigious rubies and sapphires. In the last couple of years an unprecedented tourmaline boom has occurred due to the discovery of new copper-bearing tourmaline deposits. The name “Paraíba” tourmaline was originally associated only with those copper-bearing tourmalines (or “cuprian-elbaites”), which were found in the state of Paraíba (Brazil). New mines were subsequently encountered in Rio Grande do Norte in Brazil, as well as in Nigeria and in Mozambique. The market and the laboratories were split on the issue whether to call the newly discovered neon-blue colored tourmalines “cuprian-elbaites” or “Paraíba tourmaline” regardless of origin. While this controversy initiated the first high-profile law suite in the USA (currently dropped), the debate on Paraíba tourmalines progressed into a new direction. A first theory emerged on the Internet and in a seminar at the Tucson show in 2009, arguing that Paraíba tourmaline may have been diffusion-treated. In 2006, GRS has announced on its website, that it had achieved to apply a chemical testing procedure which enables to distinguish “Cuprian-Elbaites” from different origins, based on an extensive research program. In the light of the new controversy, GRS and the laboratory of Inorganic Chemistry and Applied Biochemistry from the ETH Zurich decided to publish this specialized research report in full length. Although some chemical data on the origin of Paraíba tourmalines have been published elsewhere, we have chosen a different approach in our research and combined the capabilities of different analytical This journal follows the rules of the Commission on techniques. We concentrated on the analysis of New Minerals and Mineral Names of the IMA in all matters concerning mineral names and nomenclature. element variations within single crystals of copper-bearing tourmalines, which contain Distributor pronounced color zoning and extensive chemical variability. Fortunately, it was possible to solve two GRS (Thailand) Co., LTD different issues at the same time: Establish criteria 257/919 Silom Rd., JTC Building for origin determination of “Paraíba tourmalines” as Bangkok 10500, Thailand. well as to characterize natural chemical zoning patterns within these tourmalines. We are confident Journal and Website Copyrighted by GRS (Thailand) that our research will prevent further confusion Co. LTD, Bangkok, Thailand and GRS Gemresearch between “chemical fingerprints” induced by nature Swisslab AG, Lucerne, Switzerland and those claimed to be potentially inflicted by treatment techniques. This report is available online at www.gemresearch.ch ISBN 978-3-9523359-9-4 Adolf Peretti Contents of Contributions to Gemology No.9 Introduction 1 The “Quintos” -Tourmaline Mine in 15 o o o o o o o 60 30 0 30 60 90 o 60 UNITED 60 KINGDOM DENMARK RUSSIAN FEDERATION NETHERLANDS BELARUS GERMANY POLAND BELGIUM CZECH. REP UKRAINE AUSTRIA U.S.A. FRANCE MONGOLIA the State of Rio Grande Do Norte SWITZERLAND ROMANIA ITALY BULGARIA KYRGYZSTAN PORTUGAL SPAIN GREECE TURKEY TAJIKISTAN SYRIAN TUNISIA CYPRUS Jammu and ARAB REP IRAN AFGHANISTANKashmir CHINA MOROCCO LEBANON IRAQ o ISRAEL JORDAN o KUWAIT PAKISTAN 30 ALGERIA LIBYAN ARAB NEPAL 30 Western BAHRAIN BHUTAN JAMAHIRIYA EGYPT QATAR Sahara SAUDI CUBA ARABIA UNITED ARAB INDIA EMIRATES MYANMAR MAURITANIA OMAN LAO MALI NIGER THAILAND SENEGAL CHAD YEMEN BURKINA SUDAN VIETNAM GAMBIA FASO CAMBODIA GUINEA BENIN NIGERIA VENEZUELA SIERRA LEONE GHANA CENTRAL ETHIOPIA AFRICAN REP LIBERIA . SRI LANKA COLOMBIA CAMEROON MALAYSIA UGANDA SOMALIA o CÔTE CONGO SINGAPORE o 0 D'IVOIRE GABON KENYA 0 World-Wide Occurrence of (Brazil) D.R. CONGO INDONESIA BRAZIL TANZANIA Rio Grande do Norte 2 ANGOLA PERU Paraiba ZAMBIA Alto Lingonha BOLIVIA ZIMBABWE Mavuco NAMIBIA MOZAMBIQUE PARAGUAY BOTSWANA MADAGASCAR o SOUTH o 30 AFRICA 30 CHILE URUGUAY ARGENTINA Copper-Bearing Tourmalines 60 o 60 o 60 o 30 o 0 o 30 o 60 o 90 o Underground Mining and 16 Jewelry Sets with High Valuable 3 Occurrence of Copper-Bearing “Paraiba”-Type Copper-Bearing Tourmalines in the Host Rock Tourmalines at the Quintos Mine in Brazil Different Types of Faceted 4 Multicolored Copper-Bearing 17-18 Copper-Bearing Tourmalines from Tourmaline in the Host Rock Mozambique at the Quintos Mine (Rio Grande Do Norte, Brazil) Number of heated and unheated gem quality cuprian-elbaites from Mozambique sorted in different color categories Materials and Statistic 5 Electron Microprobe Profile Heated 19-20 Not heated Statistics of Size, Color and 6 Analysis of Paraiba Tourmalines Enhancement of Cuprian-Elbaite (-Tourmaline) from Mozambique Backscattered Electron Images 21 and Element Distribution Mapping Copper-Bearing Tourmalines From 7 of Paraiba Tourmaline EMPA Brazil Electron Microprobe Analysis: 22 Statistics of Size, Color and 8 Element Distribution Mapping Enhancement of Copper-Bearing Tourmaline from Brazil Electron Microprobe (EMPA) 23 and LA-ICP-MS Analysis Type Locality of 9 “Paraiba”-Tourmalines in Brazil: LA-ICP-MS, LIBS and ED-XRF 24 The Batalha Mine Analysis (Methods) Mn Underground Mining of 10 Mn max Cu Mn max LA-ICP-MS Chemical Analysis 25-32 Bi Neon blue “Paraiba”-Tourmalines outer core Profiles of Paraiba Tourmaline, Bi max Bi max Cu>>Mn Batalha Mine Archive Pictures from the 11 Sample No. GRS-Ref2976 “Paraiba”-Tourmaline Mining Operation at the Batalha Mine LA-ICP-MS Chemical Analysis 33-34 (Batalha, Paraiba, Brazil) Profiles of Paraiba Tourmaline, Batalha Mine The Recent “Paraiba”-Tourmaline 12 Sample No. GRS-Ref 2976.2 Mines at Batalha (Paraiba, Brazil) LA-ICP-MS Chemical Analysis 35-36 Profiles of Paraiba Tourmaline, Multicolored Tourmaline Rough 13 Batalha Mine Crystals from Paraiba (Brazil) Sample No. GRS-Ref2965 Paraiba Tourmalines in the Host 14 REE LA-ICP-MS Chemical Analysis 37-38 Rock (Batalha Mine, “Heitor”-Shaft) Profiles of Paraiba Tourmaline, Batalha Mine 1988, MN/10,000 Cu/10,000 Pavlik Collection Sample No. GRS-Ref3111 Contents of Contributions to Gemology No.9 LA-ICP-MS Chemical Analysis 39-40 Comparison of Variation of Pb- and 58 Profiles of “Paraiba”-Tourmaline, Be-Concentrations in Multicolored Rio Grande Do Norte, Pb, Be Copper-Bearing Tourmalines from Quintos Mine (P. Wild), Brazil and Mozambique Sample No. GRS-Ref2079 Be-(Mn+Cu) Diagram for Origin 59-60 Inclusion Research Case Study Determination of Copper-Bearing 41 Be-Mn-Cu of a Copper-Bearing Tourmaline Tourmalines from Mozambique: Materials Cu+Mn Diagram for Origin 61-62 Inclusion Research Case Study Determination of Copper-Bearing 42-45 Pb/Be of a Copper-Bearing Tourmaline Tourmalines from Mozambique Diagram:fier Origin 63-64 Inclusion Research Case Study 46 Cu+Mn Determination of Copper-Bearing of a Copper-Bearing Tourmaline Pb/Be Tourmalines: from Mozambique: Summary and Different Color Groups Interpretation Classification of Copper-Bearing 65 Color-Zoning in Copper-Bearing 47 Tourmalines Using Mn- and Tourmalines from Mozambique Bi-Concentrations (LA-ICP-MS and ED-XRF Analysis ) LA-ICP-MS Analysis Profiles of 48-50 Multicolored Tourmaline from Conclusions 66 Pb A-C Mozambique A-C C B 2976 Sample No. GRS-Ref3134. D Chemical Evolution Trends in 2976 67-68 2976 A D 7782 3134 Copper-Bearing Tourmalines E 2079 Bi, Mn max Mn Mg Zn Cu LA-ICP-MS Analysis Profiles 51-52 D-H Bi Cu>Mn Cu max of Multicolor Tourmaline from About the Authors, 71-72 Mozambique Acknownledment and Literature Sample No. GRS-Ref7782 Chemical Compositions from 73 Comparison of Chemical Analysis 53 Analyses Brazil. Sample No. GRS-Ref3111, Profiles: 2079, 2965 Ga-Pb Ga- and Pb-Concentrations LA-ICP-MS Analysis Chemical Compositions from 74 Brazil. Sample No. GRS-Ref2976 Ga-Pb Diagram for Origin 54-55 and Determination of Tourmalines Chemical Compositions from 75 Cu-Ga LA-ICP-MS Analysis Mozambique. Sample No. GRS-Ref7782, 3134 Diagram for Origin 56 Cu/Ga Determination of Tourmalines Chemical Compositions from 76 Comparison of ED-XRF with Mozambique. LA-ICP-MS Analysis Sample No. GRS-Ref2939, 2942, 2943, 3138, 3143 Origin Determination of 57 Copper-Bearing Tourmalines: Chemical Compositions from 77 Flow Chart of Methods Nigeria Introduction CHEMICAL VARIATIONS IN MULTICOLORED “PARAIBA”-TYPE TOURMALINES FROM BRAZIL AND MOZAMBIQUE: IMPLICATIONS FOR ORIGIN AND AUTHENTICITY DETERMINATION Adolf Peretti (1,2,3), Willy Peter Bieri (2,3), Eric Reusser (4), Kathrin Hametner (5) and Detlef Günther (5) (1) GRS Gemresearch Swisslab AG, Sempacherstr. 1, CH-6003 Lucerne, Switzerland (2) GRS Gemresearch Swisslab AG, Rue du Marché 12, CH-1204 Geneva, Switzerland (3) GRS (Thailand) CO LTD, Bangkok, Silom 919/257, 10500 Bangkok, Thailand (4) Institute of Mineralogy and Petrography, Clausiusstr.
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