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. 25, ETH Zentrum, CH-8092 Zurich, Switzerland (5) Laboratory of Inorganic Chemistry, ETH Hönggerberg, HCI, G113, CH-8093 Zurich, Switzerland INTRODUCTION Copper-bearing tourmalines (or “cuprian- detailed chemical study aimed for origin elbaites”) with neon-blue colors are considered determination using LA-ICP-MS has been highly valuable gemstones matching prices that published (Lit. Par11 and 33). Since it has been are normally only equaled by valuable rubies and proposed that the separation of tourmalines of sapphires. Part of the trade and some different origin using standard gemological laboratories have introduced the new variety testing is not possible, we acquired an extensive name “Paraíba” tourmalines for the “neon”-blue set of data using different analytical techniques. colored cuprian-elbaite. (www.gemresearch.ch/ In this study, we concentrate on the detailed news). Currently a large number of publications chemical profile analyses of color-zoned copper- were released on copper-bearing tourmalines bearing tourmalines from Brazil and Mozambique from various localities (see review Lit. Par11-44). using LA-ICP-MS spectroscopy and element Copper-bearing tourmalines were discovered in concentration mapping by electron microprobe. the Paraíba State, Brazil, in the late 1980’s (Lit. New insights on the chemical evolution during Par22 and 23), in the neighboring Rio Grande do growth of copper-bearing tourmalines were Norte State in Mulungu (Parelhas) and in Alto obtained with important consequences for origin dos Quintos (Lit. Par20 and 28). On the African determination and understanding of natural continent the tourmalines occured in Idaban chemical zoning in these tourmalines. A test State and Ofiki in Ilorin State, Nigeria (Lit. Par17, procedure is proposed that enables origin 18, 31, 32, 40 and 44) as well as in the Mavuco determination by the combination of ED-XRF and area in the Alto Lingonha pegmatite district of LIBS analyses in addition to LA-ICP-MS using Mozambique (Lit. Par41). matrix-matched calibration saples prior analyzed by EMPA and LA-ICP-MS. Historically, tourmalines from Paraíba were discovered first, followed by Rio Grande do Norte (both in Brazil), Nigeria and Mozambique. Cuprian-elbaite occurs in different colors, such as purple, violet, blue and green. Heat-treatment of purple and violet colors can be transformed to neon-blue colors (See e.g. Lit. Par11 and 33). Cu-bearing tourmalines from Mozambique have become commercially important gems with colors such as purple, violet, blue. The copper-bearing, unheated tourmalines occur in extremely large size, fine clarity and vibrant colors (Fig. Par05). Some of the magnificent tourmalines of Paraíba-type neon-colors reached extremely large sizes exceeding 100ct (Fig. Par05). These magnificent pieces were mostly heat-treated (Fig. Fig. Par01 Example of a pair of “neon-blue” copper- Par07). Large copper-bearing tourmalines of bearing tourmaline (or “Cuprian-elbaite”) from Brazil in such excellent clarity are less commonly known the mounting. This type of tourmaline is also known as from the Brazilian deposits. On the other hand, Paraiba tourmaline in the trade. The tourmalines are the color intensity of the “neon-blue” colors of the most valuable members of the tourmaline group. Paraíba tourmalines from Brazil is almost The two stones are total 15ct (7ct and 8ct). Photo unmatched (Fig. Par01, 09, 10 and 14d). A first courtesy P. Wild (Idar-Oberstein, Germany). 01 World-Wide Occurrence of Copper-Bearing Tourmalines

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 U.S.A. AUSTRIA MONGOLIA FRANCESWITZERLAND 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 D.R. CONGO INDONESIA BRAZIL TANZANIA Rio Grande do Norte ANGOLA PERU Paraiba ZAMBIA Alto Lingonha BOLIVIA ZIMBABWE Mavuco NAMIBIA MOZAMBIQUE PARAGUAY BOTSWANA MADAGASCAR o SOUTH o 30 AFRICA 30 CHILE URUGUAY ARGENTINA

60 o 60 o 60 o 30 o 0 o 30 o 60 o 90 o Fig. Par02 Geographic map shows the occurrence of copper-bearing tourmalines with commercial importance. The classical “Paraiba” tourmaline occurs in Brazil and new occurrences are found in Africa (Nigeria and Mozambique). The Brazilian occurrences are found in the state of Paraiba and Rio Grande do Norte (See Fig Par03).

OCEANO ATLANTICO Arela Branca Macau Touros

Joao Agu Angicos Camara Taipu Ceara Apodi Lajes Mirim Caraubus RIO GRANDE Natal Macalba Santana DO NORTE do matos Cerro Cora Sao Jose Pau dos Florania de Mipibu Ferros Curraia Santa Novos Cruz Luis Canguaratama Gornes Caco Nava Cruz Paralhas PARAIBA Quintos Mulungu

Batalha 0 50 100 km

Fig. Par03 Map shows the occurrence of copper-bearing tourmalines in Brazil in the State of Paraiba and Rio Grande do Norte. Although not all the tourmalines occur in the state of Paraiba, all copper-bearing tourmalines from Brazil are called “Paraiba” tourmalines, particularly if they possess so-called “Neon”-colors. 02 Jewelry Sets with High Valuable “Paraiba”-Type Copper-Bearing Tourmalines

Fig. Par04 Example of high valuable jewelry sets with “Paraiba”-type tourmalines as center stones. These copper- bearing tourmalines are of mixed origins, either from Brazil or Mozambique. Left: Stone in necklace is 72ct, in the ring is 32ct and in the ear clips of a total of 12ct. Jewelry set is of similar size but different design. Courtesy Hatta New World. Picture Anong Imaging and Hatta New World. Presentation Miriam Peretti. 03 Different Types of Faceted Copper-Bearing Tourmalines from Mozambique

140 ct

10 ct 11 ct

“Neon” -Greenish-Blue 31 ct

Violet 22ct Pastel Blue 38ct Vivid Violet 24ct

Purple-Pink 23ct Vivid Purple 41ct Vivid Green 16ct Vivid Yellowish-Green 9ct

Fig. Par05 Examples of gem-quality faceted copper-bearing tourmalines (cuprian-elbaites) from the origin of Mozambique. The faceted bluish-green tourmaline over 140ct is one of the largest example of “Paraiba”-type color so far tested by GRS. Copper-bearing tourmalines of different other vivid colors are also found. Copper- bearing tourmaline from Mozambique with “neon”-blue colors are most similar in appearance to counterparts from “Paraiba” (Brazil). 04 Materials and Statistic

MATERIALS

Copper-bearing tourmalines from Brazil were lines were acquired from Arnold Silverberg, Steve obtained at the Tucson show in 2005 from 3 differ- Jaquith in Bangkok and from Paul Wild. A total ent sources specialized in “Paraiba”- tourmaline number of 120 faceted or rough materials were from the Batalha mine (Van Wagoner, R.C. available for this study. From these stones 90% Gemmas, Bryan Pavlik). These materials were are unheated materials. All multicolored copper- partially from old inventories from the production bearing tourmalines used for LA-ICP-MS analysis year 1988 (Lit Par16). Photographs of the materi- are unheated. No multicolored samples were als see Fig. Par10, 17, 29, 58 and 61. Brazilian available from the origin of Nigeria. samples from Rio Grande do Norte were obtained In addition, over 100 gem-quality faceted from P. Wild (IdarOberstein, Germany) that origi- “Paraiba”-type tourmalines from Brazil and over nated from their own mining operation (Fig.Par64 600 faceted counterparts from Mozambique, both and 65). heated and unheated have been tested and certi- Copper-bearing tourmalines from Mozambique fied in the GRS laboratory between 2004 and were received from Gebr. Bank (Idar Oberstein) in 2008. These high-valued gemstones are consid- 2006 (produced in 2005, samples 2939, 2942, ered representative to the size and color of 2942.2, 2943, Tab. Par05) and further materials copper-bearing tourmalines available in the were acquired from African suppliers in Bangkok worlds gem market and have been used for a in the years 2006 and 2007 (Fig. Par06, 67a-b, 72, statistical study (Fig. Par07, 08, 11 and 12). 74, 75 and 77). Nigerian copper-bearing tourma-

Fig.Par06 Examples of rough 30 - 50 cts copper-bearing tourmalines from Mozambique of various colors including green, bluish green, pink, purple and violet as seen in Bangkok between 2006 and 2007. These samples were acquired from large lots from African dealers in Bangkok. Less than 1 percent of the samples were multicolored (See Fig. Par72, 74 and 77).

Statistics on Heated and Unheated Gem-Quality Copper-Bearing Tourmalines from Mozambique Sorted by Different Color-Categories Fig. Par07 Statistics on the 280 number of heated and unheated copper-bearing 260 tourmalines from Mozam- 240 bique in different color

220 categories. Note that the so-called “Paraiba”-type 200 colors (mixtures between 180 green and blue) are domi-

160 nantly heat-treated. Yellow- Heated green and purple colors are 140 Not heated mostly unheated but a 120 surprising percentage of

100 those tourmalines are heated as well. Due to the 80 limited success of heat- 60 treatment of this colors, they Number of Certified Copper-Bearing Tourmalines Tourmalines Number of Certified Copper-Bearing are expected to be mostly 40 unheated (See heating 20 experiments Lit. Par33). 0 Purple Purple-Pink Violet Blue Green-Blue Blue-Green Green Yellow-Green Heated and Unheated Tourmalines of Different Color-Categories

05 heat-treated. Thelargest unheated violetandpurple colors are inthecategory of45-50 ct. in size.Larger sizesofalldifferentcolors areextremelyrare.Sizes ofover100ctexistbutthey aregenerally included, both heatedandunheatedrespectively (SeeFig.Par07). Themajorityofthesegems arebelow20cts sorted bycolor andsize,astestedinthe yearsbetween2006-2008. Onlygem-qualityfaceted stonesare Fig. Par08Statisticsofnumbercertified copper-bearing tourmalines(”cuprian-elbaites”)from Mozambique 140 Color and Size of Tested Gem Quality Copper-Bearing Tourmalines from Mozambique (Years 2006-2008)

120 Statistics ofSize,ColorandEnhancementCopper-Bearing Tourmaline Number ofCertifiedCopper-Bearing Tourmalines 100 Purple Purple-Pink

80 Violet Blue Green-Blue 60 Blue-Green Green Yellow-Green 40

20 from Mozambique

0 1-5 ct 5-10 ct 10-15 ct 15-20 ct 20-25 ct 25-30 ct 30-35 ct 35-40 ct 40-45 ct 45-50 ct 50-100 ct >100 ct 06 weight categories in carat (ct) Copper-Bearing Tourmalines from Brazil

Fig. Par09 Examples of faceted “Paraiba”- tourmalines from the Batalha mine (State of Paraiba, Brazil) are shown. The colors of valuable “Paraiba”-tourmalines are vibrant greenish-blue colors that are described as “neon”-blue colors in the trade. All shades of transition of from green to blue can be found. Largest sizes are 11-12ct. Picture P. Wild Archive, Idar-Oberstein (Germany).

Fig. Par10 Example of a large-sized “Paraiba”- tourmaline rough with typical "neon"-blue color (from the Quintos mine, Rio Grande do Norte). The tourmaline section has been cut perpendicu- lar to the c-axis and polished on both sides.

96 ct

07 Statistics of Size, Color and Enhancement of Copper-Bearing Tourmaline from Brazil

25

Color and Size of Tested Gem-Quality Copper-BearingTourmaline from Brazil (Tested in the Years 2004-2008)

20

15 Bluish-Green Blue-Green Green-Blue Greenish-Blue 10 Blue

Number of Certified Copper-Bearing Tourmalines Tourmalines Number of Certified Copper-Bearing 5

0 1-5 ct 5-10 ct 10-15 ct 15-20 ct 20-25 ct 50-100 ct Weight Categories in Carat (ct)

Fig. Par11 Statistics on certified copper-bearing tourmalines from Brazil, sorted according to color and size. They were tested and certified in the GRS laboratory in the years between 2004 and 2008. The stones listed are gem-quality faceted stones; both heated and unheated (see Fig. Par12). The majority of these gems are below 10 ct in size. Larger gem-quality Paraiba tourmalines over 10 ct are extremely rare and purple colors such as found in Mozambique in this size category did not appear in our laboratory (compare Fig. Par08).

Statistics on Heated and Unheated Gem-Quality Copper-Bearing Tourmalines from Brazil Fig. Par12 Statistics on the Sorted by Different Color-Categories number of heated and 30 unheated copper-bearing tourmalines from Brazil s

e (Paraiba or Rio Grande do n i l Norte) in different color a 25 m

r categories. The majority of u o

T “Paraiba”-tourmalines from 20 Brazil was found to be heated. Most of the unheated Paraiba tourma- Heated 15 lines are from the category Not heated of mixed green and blue colors. None of the pure 10 “neon”-blue colors that came to the GRS laboratory for testing were unheated. A 5 higher percentage of Brazil- ian tourmalines were Number of Certified Copper-Bearing unheated in comparison to 0 the Mozambique tourma- Bluish-Green Blue-Green Green-Blue Greenish-Blue Blue lines (See Fig. Par07). Heated and Unheated Tourmalines of Different Color-Categories

08 Type Locality of “Paraiba”-Tourmalines in Brazil: The Batalha Mine

Fig. Par13a Overlook on the classical Batalha tourmaline mine in the State of Paraiba (Brazil). View from the top of the "Heitor"-hill towards the direction of Sao Jose da Batalha village. Picture by Markus Paul Wild in 2006. P. Wild Archive.

Heitor Mine Parazul Border Shaft Joao Henrique

Parazul Valley

9 11 2005

Fig. Par13b A large number of claims and shafts cover the area of many different mine owners. Mining shafts are labeled according to the owner of the mines. Heitor mine see Fig. Par13d. Picture P. Wild Archive. 09 Underground Mining of “Paraiba”-Tourmalines

Fig. Par13c Fig. Par13d

Fig. Par13e Fig. Par13f Fig. Par13c-f A view into the underground mining of “Paraiba”-tourmalines in the Heitor shaft (Batalha mining area, Paraiba, Brazil). The vertical shafts are driven to a depth of 40m in soft "kaolinized" pegmatites (Fig. Par13e-f). Underground tunnels are partially collapsed (Fig. Par13d). Picture Markus Paul Wild. P. Wild Archive. 10 Archive Pictures from the “Paraiba”-Tourmaline Mining Operation at the Batalha Mine (Batalha, Paraiba, Brazil)

Batalha-Mine in August 1992

Fig. Par14a-b The original “Paraiba” tourmaline mine from Sao Jose da Batalha in August 1992 (Heitor mine). The whitish dumped material consists of kaolinized pegmatite materials and quartzite. Compare with the mining operation a decade later (See Fig. Par15a). Picture Bryan Pavlik.

Fig. Par14b Fig. Par14c

Fig. Par14c “Paraiba” tourmaline crystal in quartz matrix from the first mining period at the Batalha mine (Paraiba, Brazil). Length of tourmaline in matrix is 10 cm. Additional display of rough and faceted gem- stones as shown at the Inhorgenta (Pavlik booth, Munich, 1993). Fig. Par14d Faceted “Paraiba” tourmaline from the Batalha mine in a weight range of 1 to 5ct. These archived gemstones were pictured more than 10 years before the mines in Africa were discovered. Picture (14a-d) are copyrighted by Bryan Pavlik and reproduced with permission of the “Pavlik Gem Fig. Par14d History Archive”, Vienna, Austria.

11 The Recent “Paraiba”-Tourmaline Mines at Batalha (Paraiba, Brazil)

Batalha-Mine in June 2005 “Heitor”-Wall

Fig. Par15a View into a mining landscape with many claims and shafts. Same view as in Fig. Par14a-b but 13 years later. Note extensive mining activities have created a deepened valley with numerous fences and walls between the claims in the decade since the mine was opened. Picture by Markus Paul Wild in 2005. P. Wild Archive.

“Heitor”-Wall

29 11 2003

Fig. Par15b shows the so-called “Heitor-wall” at the top of a hill for the purpose of protecting the “Heitor”-mine claim. P. Wild Archive. 12 Multicolored Tourmaline Rough Crystals from Paraiba (Brazil)

Fig. Par16a-b Examples of color zoned “Paraiba”-tourmalines from the Batalha mine, which were used for detailed chemical analyses in this report. The core of the rough crystal fragments is purple, followed by “neon”-blue and green colors in the outer rim. (LA-ICP-MS analysis profiles see Fig. Par59, 60 and 62).

Fig. Par16a

Fig. Par16b

Fig. Par17 A rare example of a perfect “Paraiba”-tourmaline crystal of intense “neon”-blue color. Such intensively unheated blue tourmaline crystals are exclusively found in Batalha (Paraiba, Brazil). Crystal length 4cm. These magnificent color varieties are named “Heitoritapura” and were typically found in the Heitor shaft (See Fig. Par15).

13 Paraiba Tourmalines in the Host Rock (Batalha Mine, “Heitor”-Shaft)

8 11 2005

Fig. Par18a A view into the underground rock formations containing pegmatite materials with copper-bearing tourmalines, albite (white) and quartz (grey) in the “Heitor”-mine (Purple = tourmaline and lepidolite). Picture P. Wild Archive.

Fig. Par18b A spectacular hand specimen with a color-zoned “Paraiba”-tourmaline from the Batalha mine (Heitor shaft). Note: Only very small portion of the tourmaline show the desired blue “neon”-color. Tourmaline on rock matrix with citrine and quartz. Picture P. Wild Archive.

14 The “Quintos” -Tourmaline Mine in the State of Rio Grande Do Norte (Brazil)

Fig. Par19 The Washing place at the P. Wild’s Quintos mine in the State of Rio Grande do Norte (Brazil). P. Wild Archive.

Fig. Par20 Underground mining tunnel at the Quintos tourmaline mine in Rio Grande do Norte State (Brazil) and view to the entrance tunnel (inserted). P. Wild Archive. 15 Underground Mining and Occurrence of Copper-Bearing Tourmalines in the Host Rock at the Quintos Mine in Brazil

Fig. Par21 Underground tunnel in the Quintos tourmaline mine that was driven into the hard quartzite rock. Only at certain positions can the gem-bearing pegmatites be found (See inserted pictures). P. Wild Archive.

18 6 2004 Fig. Par22 Occurrence of highly valuable copper-bearing tourmalines at the P. Wild’s Quintos mine. A quartz- feldspar pegmatite has intruded a quartzite host rock. In some zones the desired “neon-blue” colored copper- bearing tourmaline was formed. In the picture on the left the mining geologist and on the right the mining engineer. The Geological map (inserted) helped to find the gem-bearing layers. P. Wild Archive.

16 Multicolored Copper-Bearing Tourmaline in the Host Rock at the Quintos Mine (Rio Grande Do Norte, Brazil)

Fig. Par23 18 6 2004

Fig. Par24 30 4 2004

Fig. Par23, 24, 25, 26 A detailed view of the primary occurrence of copper-bearing tourmalines in the host rocks at the Quintos mine (Rio Grande do Northe, Brazil). Photo taken in the underground tunnel. The tourmaline crystals are growing in sizes larger than pencils. The multicolored tourmalines show a purple core and blue rim. The grey and white minerals of the matrix are quartz and feldspar respectively. P. Wild Archive.

17 Multicolored Copper-Bearing Tourmaline in the Host Rock at the Quintos Mine (Rio Grande Do Norte, Brazil)

Fig. Par25 28 4 2004

28 4 2004 18 6 2004

Fig. Par26 Fig. Par27 Spectacular example of a large sized “neon”-blue “Paraiba” tourmaline in a matrix of quartz (grey) and feldspar (white). These large tourmalines are heavily fractured and with numerous nontransparent areas. Only very small transparent areas are present in the large tourmalines that are suitable for faceting. P. Wild Archive.

18 Zn-concentrations SeeFig.Par31hand Tab. Par03. the F-concentrations iscorrelatedwiththe increaseinCu-concentrations inpoint5(Fig.Par28c). For of the traceelements inthetourmalinecrystal (compareFig.Par28b with Fig.Par36a).Notethat theincrease Both methods,EMPA and LA-ICP-MS-analysesrespectively, of producedexactlythesamedistribution pattern (Bi). focussed onthemeasurement ofsomeadditionalelementssuchasFluor(F),Chlorine (Cl)andBismuth and was of thetourmalinecrystal.Fig. Par28cisfromasecondmeasuringsessionwith less measuringpoints part Par36a. LowestMnO-concentrations andhighestCuO-concentrationsarefound inthe”neon”-bluecolored ofFig. c-axis. (SeeFig.Par29).Fig.Par28a-b isfromthesamerunandcorrespondsto theLA-ICP-MSanalyses tothe Fig. Par28a-cElectronmicroprobeprofileanalysisacrossazoned “Paraiba”-tourmaline perpendicular dispersive with 5wavelength ment equipped on aJEOLwas performed JXAinstru- 8200 The electron probemicroanalysis(EMPA) MICROPROBE ANALYSISELECTRON Electron MicroprobeProfile Analysis ofParaibaTourmalines: MethodsandResults 19 wt.-% wt.-% 0 0 0 0 1 1 1 1 3 4 4 ...... 5 0 5 0 2 4 6 8 1 2 4 6 8 2 1 21 Green Rim

wt.-% 41 0 0 0 0 1 1 1 1 ...... 0 2 4 6 8 1 2 4 6 8 61 1 2 81 3 4 number ofmeasuredpointsinprofile 101 5 Neon blue outer core 6 7 121 8 Purple Core Purple Core 9 141 10 11 161 12 13 were coated with a 20 nm layer of carbon. nm layer with a20 coated were The dispersive spectrometer(EDS). All samples x-ray spectrometers(WDS)andanenergy 181 14 15 16 Neon blue 201 17 outer core 18 221 Neon blue outer core 241 Fig. Par28c Green Rim MnO Cl CuO Bi F 261 2 O 3 281 301 Fig. Par28a Fig. Par28b SiO FeO TiO CaO MnO CuO Al 2 O 2 2 3 per imageelement. s 1 was time dwell The applied. were μm current of40nA andabeamdiameter<1 of 15kV,voltage acceleration abeam distribution mapsan For theelemental for Fluorwas0.1wt.-%. inter elementcorrection. The detectionlimit 11 wt-%ofB of a fixedamount achieved B isnoteasily of was applied.Becausethequantification the CITZAF fluorescence) code(Lit.Par02) element effects (i.e.excitation,absorption, For thecorrectionofinter background. dead time, instrumental drift and x-ray were correctedfordetector measurements synthetic silicateandoxideminerals. All tions. and natural were used The standards the peakand40sposi- on background selected, s on was 40 time oranyelement counting were The lines used. was line Mα the Bi Kα for whereas the Bi except for F.layer crystal(LDE1) Forallelements Bi, TAP for Si, Al, Mg and Naa multi- Zn, Cu, FeandMn,PET forCa,K, Ti and monochromator of were LIFfortheanalysis crystals used The 10μm. of diameter 15kV,current of20nA abeam a beam and voltage of were anacceleration analysis electron beamconditionsfor quantitative 2 O 3 was added to improve the to improve wasadded Electron Microprobe Profile Analysis: Methods and Results

ELECTRON MICROPROBE ANALYSIS

The electron probe microanalysis (EMPA) x-ray spectrometers (WDS) and an energy was performed on a JEOL JXA 8200 instru- dispersive spectrometer (EDS). All samples ment equipped with 5 wavelength dispersive were coated with a 20 nm layer of carbon. The

“Neon”- blue outer core

Fig. Par29 “Paraiba”-tourmaline cross sections cut perpendicular to the c-axis. Note the pronounced color zoning in these copper-bearing tourmalines with a purple inner core, a “neon”-blue outer core and a green rim. (Batalha mine, Brazil, R.C. Gemmas Co.). Sizes approx. 6-8 mm.

1.2 electron beam conditions for quantitative analysis were an acceleration voltage of 1.0 15kV, a beam current of 20 nA and a beam diameter of 10μm. The monochromator 0.8 crystals used were LIF for the analysis of 0.6 Zn, Cu, Fe and Mn, PET for Ca, K, Ti and Bi, TAP for Si, Al, Mg and Na and a multi- F (wt.-%) 0.4

layer crystal (LDE1) for F. For all elements 0.2 except Bi the Kα lines were selected, Fig. Par30a whereas for Bi the Mα line was used. The 0 0 0.5 1 1.5 2 2.5 3 counting time or any element was 40 s on MnO+CuO+Bi2O3 (wt.-%) the peak and 40 s on background posi- 1.4 tions. The standards used were natural and Fig. Par30b synthetic silicate and oxide minerals. All 1.2 measurements were corrected for detector 1.0 dead time, instrumental drift and x-ray background. For the correction of the inter 0.8 element effects (i.e. excitation, absorption, fluorescence) the CITZAF code (Lit. Par02) 0.6 was applied. Because the quantification of Bi2O3 F (wt.-%) 0.4 CuO B is not easily achieved a fixed amount of MnO Linear (Bi2O3) 11 wt-% of B2O3 was added to improve the 0.2 Linear (CuO) inter element correction. The detection limit Linear (MnO) 0 for Fluor was 0.1 wt.-%. 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 For the elemental distribution maps an wt.-% acceleration voltage of 15 kV, a beam Fig. Par30a-b Regression plot of concentrations of minor current of 40 nA and a beam diameter < 1 elements against Fluorine (F). Increase in these minor μm were applied. The dwell time was 1 s elements is correlated with increase in F-concentrations per image element. in the tourmaline. Details on variations in F-concentrations, see Fig. Par28. 20 Backscattered Electron Images and Element Distribution Mapping of Paraiba Tourmaline EMPA

Back Scattered Electron Microscope Fig. Par31e Fig. Par31a Sodium (Na) Na LvArea% 0.0 890 0.0 835 0.0 779 0.0 723 0.0 668 0.0 612 0.0 556 0.0 501 0.0 445 0.0 389 0.0 334 0.2 278 4.0 222 69.5 167 2.7 111 1.1 55 22.4 0 1 mm 0.0 153 Fig. Par31b Aluminium (Al) Fig. Par31f Magnesium (Mg)

Al LvArea% Mg LvArea% 0.0 0.1 1789 257 0.0 0.0 1711 240 0.0 0.0 1633 224 0.0 0.1 1555 208 0.5 0.1 1478 192 9.1 0.1 1400 176 37.7 0.1 1322 2.4 160 25.3 0.2 1244 144 2.7 0.2 1167 128 0.9 0.3 1089 3.6 112 0.5 0.4 1011 96 0.3 1.9 933 80 0.2 27.4 856 64 0.2 45.0 778 48 0.2 5.4 700 32 0.1 259 8.7 622 16 0.1 9.9 545 0 22.0 0.0 1037 54 Fig. Par31c Silicon (Si) Fig. Par31g Titanium (Ti)

Si LvArea% Ti LvArea% 0.0 0.0 1180 838 0.0 0.0 1131 786 0.9 0.0 1082 733 15.0 0.0 1032 681 32.1 0.0 983 629 20.8 0.0 934 576 5.0 2.9 0.0 884 524 1.0 0.0 835 471 0.6 0.1 786 419 0.4 0.1 737 9.6 366 0.3 0.2 687 314 0.2 0.5 638 262 0.2 14.7 589 209 0.1 59.7 539 157 0.1 11.4 490 441 104 0.1 3.0 441 52 0.1 10.3 391 0 22.0 0.0 773 166 Fig. Par31d Calcium (Ca) Fig. Par31h Zinc (Zn)

Ca LvArea% Zn LvArea% 0.1 0.0 833 468 0.0 0.0 781 439 0.0 0.0 729 409 0.0 0.0 677 380 0.0 0.0 625 351 0.0 0.0 573 322 436 0.0 14 0.0 520 292 0.0 0.0 468 263 0.0 0.0 416 234 0.0 0.1 364 26 204 0.1 0.1 395 312 175 0.2 0.2 260 146 11.4 0.4 208 117 45.5 1.0 156 87 12.7 32.5 104 58 1113 9.5 1564 44.2 52 29 20.5 21.3 0 0 0.0 0.0 139 46

21 Electron Microprobe Analysis (EMPA): Element Distribution Mapping

ELECTRON MICROPROBE ELEMENT Bi-concentrations are highest at border of the coupled to a DRCII + ICP-MS (Perkin Elmer, CHEMICAL COMPOSITION LIBS ANALYSIS Fig. Par31i Fluorine (F) 3 DISTRIBUTION MAPPING Cu-rich outer core towards the inner rim of the Norwalk, USA). A 20 cm ablation cell and a 1.5 The major, minor and trace elements of tourma- Laser induced breakdown spectroscopy (LIBS) F LvArea% Fig. Par31 Elemental distribution maps were crystal. The Bi distribution resembles an intense m tube were used as transport system for the 0.0 lines from Paraiba and Mozambique were ana- was used for direct analysis of the tourmalines. 14 0.0 produced by electron microprobe analysis of impact at the latest stage of the “neon”-blue laser-generated aerosols. Helium was used as 13 lyzed and sorted accordingly to the color of the Therefore, a 30 mJ frequency double 266 nm 0.0 12 important elements. The analyzed sample is a 0.0 growth phase that gradually faded away during carrier gas and merged with argon in front of the individual growth zones. The most pronounced Nd:YAG (Continuum, USA) with a pulse width of 6 11 0.0 “Paraiba” tourmaline from the Batalha mine. The 10 further crystal growth (Fig. Par31a). ICP-MS torch to provide optimum excitation changes in color representative for the chemical ns was coupled to an in-house built ICCD/Echelle 0.0 9 tourmaline has been cut perpendicular to the 0.0 F-concentrations are lowest in the core of the conditions within the ICP. The calibration was 5000 8 evolution of the tourmalines are accompanied by spectrometer with a working range of 190-900 nm. 0.1 7 c-axis (compare Fig. Par28-29). The trail of the 0.3 crystal and increase gradually to the mantle of the carried out using the NIST 610 glass. The element a significant change of the minor element concen- The ICCD detector works in a wavelength range 7 0.0 craters are form LA-ICP-MS analysis (Compare 6 crystal (Fig. Par31i). They are well correlated with concentrations of NIST 610 were taken from Lit. trations of Cu, Mn, Bi (See Fig. Par36a, 46a-b, between 180-800 nm. The crater ablated on the 1.0 5 Fig. Par32-39). The picture of the tourmaline is 2.8 the backscattered image. Darker parts in the Par03. The acquisition protocol included always 2 55a-b, 59a, 62a, 66a, 75a-b, 78a-b, 90a-b and sample and every element was acquired using 20 4 6.9 shown in Fig. Par31 for comparison of the visual 3 91c-d). This chemical transition can also be spectra (single pulse). Single element spectra 14.1 BSE-image match with low F-concentrations. NIST 610 analyses at the beginning and the end 2 and the electron microprobe electron concentra- 22.1 were acquired for Cu (324.754 nm), Be (313.042 10000 1 Higher F-concentrations correlate with higher of each run and allowed to analyze 16 sample extracted from the Pb-Zn-Mg correlation (Fig. 24.3 0 tion mappings. The colors of the pictures shown in 28.5 concentrations of Mn, Cu and Bi (See Fig. positions in-between. Since tourmaline are Par34, 59b, 62b, 66b-c, 76b and 91b). These nm) and Mn (403.076 nm). Ablation crater were 0 Fig. Par31a-l are artificial and arbitrary chosen to 1 mm 0.0 trends can further be supported by the elements generated closely matched to the position of 1 achieve maximum contrast to show the differ- Par28c). Mg, Ti and Zn show a similar distribution heterogeneous systems and consist of a large Fig. Par31j like those observed for Mn. They increase number of major elements, the normalization such as Be, and Fe and Ti (Fig. Par33b, 41a, LA-ICP-MS analysis. The concentrations were Maganese (Mn) ences in element concentrations. To calibrate the 43a-b, 49b, 59c,e, 62b,f, 66b,d, 76a, 78f, 84, 85, correlated using the LA-ICP-MS data. Crater chemical concentrations, average chemical analy- towards the mantle of the crystal with very distinct procedures for metallic samples (Lit. Par06) and Mn LvArea% 86 and 87). In addition to the major and minor diameters using LIBS were selected in the same 0.0 ses by LA-ICP-MS (Tab. Par02) are projected into oscillations at certain positions (compare Fig. oxides (Lit. Par04) were applied. The analysis and 1156 0.0 elements, 1-5 μg/g concentrations were deter- order of magnitude as applied for LA-ICP-MS to 1083 Par31f, Par31g, Par31h and Par31j). A similar data reduction were carried out following an 0.0 the picture (μg/g). 1011 mined for Sr, Nb, U, Th, La, Ce, Pr, V and Ta. Con- ensure similar destruction of the sample. The 0.0 939 element concentration pattern was measured by acquisition, data reduction and quantification 0.0 Fig. Par31a Back scattered electron image centrations between 0.01 and 1 μg/g were deter- results on the LIBS-measurement in comparison 867 0.0 LA-ICP-MS. However, the detection capabilities of protocol (Lit. Par07). 794 (BSE) mined for Sn, Cr, Co, Rb, Zr, Mo, Ag, Cs, Ba, Nd, to the LA-ICP-MS of same samples are shown in 0.0 1420 722 LA-ICP-MS allowed to expand the analysis of the 427 individual LA-ICP-MS analysis were carried 0.0 Sm, Eu, Gd, Tb, Er, Ho, Tm, Yb and Lu, whereas Fig. Par85 and 86. 650 0.0 The BSE-image provides different grey tones that 578 elemental distribution in “Paraiba”-tourmalines by out on 6 Paraiba tourmalines (Samples 2079*, 0.0 0.01 represents the lowest limits of detection 296 505 are produced by the different atoms present. 0.6 focusing into other elements at μg/g concentra- 2965*, 2972*, 2976.2*, 2976*, 3111-a*) and 260 433 determined throughout this study (See table 2.7 Higher total number of heavy atoms result in 361 tions that are below the limits of detection of elec- individual analyses were acquired from 8 Mozam- 6.0 Par02-05 and corresponding figures on pages 289 brighter grey tones. Fig. Par31a shows a dark 30.6 216 tron microprobe analysis. bique samples (Samples 2939, 2942, 2942.2, 25-40 and pages 48-53). 17.8 5610 144 core and lighter rim. This can be explained by the 2.5 2943, 3134*, 3138, 3143, 7782* (*traverse). The 72 LA-ICP-MS ANALYSIS 39.7 increase of heavy elements from the core to the ACCURACY ED-XRF ANALYSIS 0 0.0 samples were surface polished prior to the 154 rim of the crystal. Lighter grey tones can be corre- Laser Ablation-Inductively Coupled Plasma Mass Testing of the accuracy was carried out using ED-XRF analysis are carried with a Fischer Instru- lated with increase in Mn, Cu and Bi (Fig. Par31k). LA-ICP-MS analysis. On each sample, 60 μm Fig. Par31k Copper (Cu) Spectrometry analysis were carried out using a craters were place next to each other to provide EPMA concentration and LA-ICPMS concentra- ment (XAN-DP) using a 50kV acceleration The dark-grey core can be correlated with low 193 nm ArF Excimer laser ablation system tion profiles across the Paraiba Tourmaline voltage, a 1000micron Al-Filter, using different Cu LvArea% concentrations of Mn and Cu (Fig. Par31j). The spatial resolution across different growth zones of 0.0 (GeoLasM, Lambda Physik, Göttingen, Germany) sample 2976 (compare Fig. Par28b with Fig. beam collimators (0.2mm-2mm, smaller collima- 798 the tourmalines. 0.0 outer core is dominated by elevated copper- (Cu) 748 Par36a-b). The accuracy of the quantification tors with longer measuring time) and a drift correc- 0.0 698 and low Mn-concentrations in the BSE image (Fig. 0.0 approach using NIST 610 for calibration applied tion mode. The measurement was carried out for 648 0.0 Par31k) correlates well with the visual color 598 for LA-ICP-MS was carried out using different minimum of 50-100 seconds. A standard-less 0.0 548 zoning (Fig. Par32). “Neon”-blue colors are found 0.0 spatial resolution for the two independent, but element calculation procedure provided by the 3487 498 0.0 in the areas of the crystal at these elevated Cu 448 0.0 complementary techniques (EPMA approx. 10 μm manufacturer was used to obtain element concen- 399 0.0 and depleted Mn-concentrations. Elemental distri- 349 and LA-ICP-MS approx. 60 μm). Based on the trations of Al, Cu, Mn, Bi, Fe, Zn and Ga. For 7879 0.0 299 bution of other elements such Si, Al, Ca, Na Mg, 0.4 difference in the spatial resolution, 65 data points validation purpose, we measured 12 LA-ICP-MS 249 4.7 Zn, F and Bi may not be directly correlated with 199 (LA-ICP-MS) and 306 data points (EPMA) were standards with ED-XRF analyses. The sampling 15.3 149 the visible color zoning as they are not the cause 42.4 acquired on the same traverse shown in Fig. volume of the LA-ICP-MS and ED-XRF are differ- 3920 99 17.7 of blue color in the tourmaline (e.g. Lit Par10, 11, 49 19.4 Par28b-c and 36a. It can be seen that the concen- ent and the number of measured points by 0 0.0 33). 106 tration profiles (Na, Ca, Ti, Fe, Cu, Bi and Mn) are LA-ICP-MS had to be averaged (Tab. Par02-05), Fig. Par31l Fig. Par 31b-l Element distribution mapping of in very good agreement between the two indepen- before they could be compared to ED-XRF analy- Bismuth (Bi) various elements dently calibrated techniques. For example, the ses. A linear regression was made for each Bi LvArea% profile of Mn starts for both methods at very simi- element measured by 2 different methods (LA- 0.0 The element distribution mapping shows that 39 lar concentrations (EPMA 12000 mg/kg, LA-ICP- ICP-MS versus ED-XRF) on the basis of 12 stan- 0.0 37 Al-concentrations are slightly higher in the core 0.0 34 MS 11500 mg/kg). For further comparison, the dards. A consistent difference between ED-XRF 0.0 than in the rim of the tourmaline (Fig. Par28a, 31b) 32 0.0 average concentrations of the most homoge- and LA-ICP-MS was detected for the different 29 whereas Si does not show any variation (Fig. 0.0 27 neously distributed elements (n=306 and n=65, elements of approx. 30%. This is not surprising 285 0.0 24 Par31c). Ca- and Na-concentration revealed an 0.0 RSD < 5 % for both techniques) were calculated because lighter elements (atomic weight below Al) 22 0.0 “inner triangle” which was not evident in the micro- 19 (Data from Tab. Par01 and Tab. Par03). Using this are not measured with this relatively in-expensive 0.1 2441 17 scope (Fig. Par31d-e). In this “inner triangle”, the 0.5 14 approach, Na concentration of 13500 + 570 mg/kg ED-XRF instrument. A correction of the ED-XRF 6000 1.1 Ca-concentrations are depleted and 12 5.9 and Si concentration of 196800 + 2460 mg/kg data was carried out based on the linear regres- 9 Na-concentrations are enriched (Fig. Par31d-e). 10.4 7 (EPMA) were closely matched to Na 13800 + 740 sion coefficient to lower values (See Fig. Par82d). 28.7 4 Higher Ca- and lower Na-concentrations are 3428 20.5 mg/kg and Si 181100 + 8140 mg/kg. Even the We plotted the corrected ED-XRF results of 112 2 32.4 found in the zone of highest Cu-concentrations 0 copper concentration was determined to be tourmalines of known origin and compared the 0.0 (compare Fig. Par31d and Par31k). 4 approx within 8 % when comparing LA-ICP-MS results derived by the different methods (See Fig. and EPMA. Par82a-c, Par90a-b and Lit. Par01). 22 Electron Microprobe (EMPA) and LA-ICP-MS Analysis

ELECTRON MICROPROBE ELEMENT Bi-concentrations are highest at border of the coupled to a DRCII + ICP-MS (Perkin Elmer, CHEMICAL COMPOSITION LIBS ANALYSIS 3 DISTRIBUTION MAPPING Cu-rich outer core towards the inner rim of the Norwalk, USA). A 20 cm ablation cell and a 1.5 The major, minor and trace elements of tourma- Laser induced breakdown spectroscopy (LIBS) Fig. Par31 Elemental distribution maps were crystal. The Bi distribution resembles an intense m tube were used as transport system for the lines from Paraiba and Mozambique were ana- was used for direct analysis of the tourmalines. produced by electron microprobe analysis of impact at the latest stage of the “neon”-blue laser-generated aerosols. Helium was used as lyzed and sorted accordingly to the color of the Therefore, a 30 mJ frequency double 266 nm important elements. The analyzed sample is a growth phase that gradually faded away during carrier gas and merged with argon in front of the individual growth zones. The most pronounced Nd:YAG (Continuum, USA) with a pulse width of 6 “Paraiba” tourmaline from the Batalha mine. The further crystal growth (Fig. Par31a). ICP-MS torch to provide optimum excitation changes in color representative for the chemical ns was coupled to an in-house built ICCD/Echelle tourmaline has been cut perpendicular to the F-concentrations are lowest in the core of the conditions within the ICP. The calibration was evolution of the tourmalines are accompanied by spectrometer with a working range of 190-900 nm. c-axis (compare Fig. Par28-29). The trail of the crystal and increase gradually to the mantle of the carried out using the NIST 610 glass. The element a significant change of the minor element concen- The ICCD detector works in a wavelength range craters are form LA-ICP-MS analysis (Compare crystal (Fig. Par31i). They are well correlated with concentrations of NIST 610 were taken from Lit. trations of Cu, Mn, Bi (See Fig. Par36a, 46a-b, between 180-800 nm. The crater ablated on the Fig. Par32-39). The picture of the tourmaline is the backscattered image. Darker parts in the Par03. The acquisition protocol included always 2 55a-b, 59a, 62a, 66a, 75a-b, 78a-b, 90a-b and sample and every element was acquired using 20 shown in Fig. Par31 for comparison of the visual BSE-image match with low F-concentrations. NIST 610 analyses at the beginning and the end 91c-d). This chemical transition can also be spectra (single pulse). Single element spectra and the electron microprobe electron concentra- Higher F-concentrations correlate with higher of each run and allowed to analyze 16 sample extracted from the Pb-Zn-Mg correlation (Fig. were acquired for Cu (324.754 nm), Be (313.042 tion mappings. The colors of the pictures shown in Par34, 59b, 62b, 66b-c, 76b and 91b). These nm) and Mn (403.076 nm). Ablation crater were Fig. Par31a-l are artificial and arbitrary chosen to concentrations of Mn, Cu and Bi (See Fig. positions in-between. Since tourmaline are Par28c). Mg, Ti and Zn show a similar distribution heterogeneous systems and consist of a large trends can further be supported by the elements generated closely matched to the position of achieve maximum contrast to show the differ- such as Be, and Fe and Ti (Fig. Par33b, 41a, LA-ICP-MS analysis. The concentrations were ences in element concentrations. To calibrate the like those observed for Mn. They increase number of major elements, the normalization towards the mantle of the crystal with very distinct procedures for metallic samples (Lit. Par06) and 43a-b, 49b, 59c,e, 62b,f, 66b,d, 76a, 78f, 84, 85, correlated using the LA-ICP-MS data. Crater chemical concentrations, average chemical analy- 86 and 87). In addition to the major and minor diameters using LIBS were selected in the same oscillations at certain positions (compare Fig. oxides (Lit. Par04) were applied. The analysis and ses by LA-ICP-MS (Tab. Par02) are projected into elements, 1-5 μg/g concentrations were deter- order of magnitude as applied for LA-ICP-MS to Par31f, Par31g, Par31h and Par31j). A similar data reduction were carried out following an the picture (μg/g). mined for Sr, Nb, U, Th, La, Ce, Pr, V and Ta. Con- ensure similar destruction of the sample. The element concentration pattern was measured by acquisition, data reduction and quantification Fig. Par31a Back scattered electron image centrations between 0.01 and 1 μg/g were deter- results on the LIBS-measurement in comparison LA-ICP-MS. However, the detection capabilities of protocol (Lit. Par07). (BSE) mined for Sn, Cr, Co, Rb, Zr, Mo, Ag, Cs, Ba, Nd, to the LA-ICP-MS of same samples are shown in LA-ICP-MS allowed to expand the analysis of the 427 individual LA-ICP-MS analysis were carried Sm, Eu, Gd, Tb, Er, Ho, Tm, Yb and Lu, whereas Fig. Par85 and 86. The BSE-image provides different grey tones that elemental distribution in “Paraiba”-tourmalines by out on 6 Paraiba tourmalines (Samples 2079*, 0.01 represents the lowest limits of detection are produced by the different atoms present. focusing into other elements at μg/g concentra- 2965*, 2972*, 2976.2*, 2976*, 3111-a*) and 260 determined throughout this study (See table Higher total number of heavy atoms result in tions that are below the limits of detection of elec- individual analyses were acquired from 8 Mozam- Par02-05 and corresponding figures on pages brighter grey tones. Fig. Par31a shows a dark tron microprobe analysis. bique samples (Samples 2939, 2942, 2942.2, 25-40 and pages 48-53). core and lighter rim. This can be explained by the 2943, 3134*, 3138, 3143, 7782* (*traverse). The increase of heavy elements from the core to the LA-ICP-MS ANALYSIS ACCURACY ED-XRF ANALYSIS samples were surface polished prior to the rim of the crystal. Lighter grey tones can be corre- Laser Ablation-Inductively Coupled Plasma Mass Testing of the accuracy was carried out using ED-XRF analysis are carried with a Fischer Instru- lated with increase in Mn, Cu and Bi (Fig. Par31k). LA-ICP-MS analysis. On each sample, 60 μm Spectrometry analysis were carried out using a craters were place next to each other to provide EPMA concentration and LA-ICPMS concentra- ment (XAN-DP) using a 50kV acceleration The dark-grey core can be correlated with low 193 nm ArF Excimer laser ablation system tion profiles across the Paraiba Tourmaline voltage, a 1000micron Al-Filter, using different concentrations of Mn and Cu (Fig. Par31j). The spatial resolution across different growth zones of (GeoLasM, Lambda Physik, Göttingen, Germany) the tourmalines. sample 2976 (compare Fig. Par28b with Fig. beam collimators (0.2mm-2mm, smaller collima- outer core is dominated by elevated copper- (Cu) Par36a-b). The accuracy of the quantification tors with longer measuring time) and a drift correc- and low Mn-concentrations in the BSE image (Fig. Tab. Par01 EMPA-Analysis approach using NIST 610 for calibration applied tion mode. The measurement was carried out for Par31k) correlates well with the visual color for LA-ICP-MS was carried out using different minimum of 50-100 seconds. A standard-less zoning (Fig. Par32). “Neon”-blue colors are found Minimum Maximum Average Sigma spatial resolution for the two independent, but element calculation procedure provided by the in the areas of the crystal at these elevated Cu SiO2 36.88 38.46 37.74 0.44 complementary techniques (EPMA approx. 10 μm manufacturer was used to obtain element concen- and depleted Mn-concentrations. Elemental distri- TiO2 bd 0.08 0.02 0.03 and LA-ICP-MS approx. 60 μm). Based on the trations of Al, Cu, Mn, Bi, Fe, Zn and Ga. For bution of other elements such Si, Al, Ca, Na Mg, difference in the spatial resolution, 65 data points validation purpose, we measured 12 LA-ICP-MS Zn, F and Bi may not be directly correlated with Al2O3 40.05 42.75 41.77 1.07 (LA-ICP-MS) and 306 data points (EPMA) were standards with ED-XRF analyses. The sampling the visible color zoning as they are not the cause FeO bd 0.37 0.08 0.12 acquired on the same traverse shown in Fig. volume of the LA-ICP-MS and ED-XRF are differ- of blue color in the tourmaline (e.g. Lit Par10, 11, Par28b-c and 36a. It can be seen that the concen- ent and the number of measured points by MnO 0.01 1.57 0.45 0.58 Tab Par01 Electron 33). tration profiles (Na, Ca, Ti, Fe, Cu, Bi and Mn) are LA-ICP-MS had to be averaged (Tab. Par02-05), microprobe analysis of MgO bd 0.04 0.01 0.01 in very good agreement between the two indepen- before they could be compared to ED-XRF analy- Fig. Par 31b-l Element distribution mapping of sample 2976 (in wt.-%). various elements CaO 0.03 0.31 0.13 0.10 B O assumed as 11 for dently calibrated techniques. For example, the ses. A linear regression was made for each 2 3 profile of Mn starts for both methods at very simi- element measured by 2 different methods (LA- The element distribution mapping shows that Na2O 1.71 1.95 1.83 0.07 correction purposes. lar concentrations (EPMA 12000 mg/kg, LA-ICP- ICP-MS versus ED-XRF) on the basis of 12 stan- Al-concentrations are slightly higher in the core Lowest and highest value K2O bd 0.17 0.02 0.04 MS 11500 mg/kg). For further comparison, the dards. A consistent difference between ED-XRF than in the rim of the tourmaline (Fig. Par28a, 31b) for each element and average concentrations of the most homoge- and LA-ICP-MS was detected for the different whereas Si does not show any variation (Fig. CuO 0.30 1.17 0.55 0.27 average are given. More neously distributed elements (n=306 and n=65, elements of approx. 30%. This is not surprising Par31c). Ca- and Na-concentration revealed an ZnO bd 0.26 0.07 0.09 details see Fig. Par28. RSD < 5 % for both techniques) were calculated because lighter elements (atomic weight below Al) “inner triangle” which was not evident in the micro- Same sample is analyzed Bi2O3 bd 0.41 0.13 0.16 (Data from Tab. Par01 and Tab. Par03). Using this are not measured with this relatively in-expensive scope (Fig. Par31d-e). In this “inner triangle”, the by LA-ICP-MS (See Fig. approach, Na concentration of 13500 + 570 mg/kg ED-XRF instrument. A correction of the ED-XRF Ca-concentrations are depleted and F 0.49 1.09 0.72 0.22 Par35). Difference to total of 100% due to non- and Si concentration of 196800 + 2460 mg/kg data was carried out based on the linear regres- Na-concentrations are enriched (Fig. Par31d-e). Cl bd 0.012 0.003 0.004 measured element (EPMA) were closely matched to Na 13800 + 740 sion coefficient to lower values (See Fig. Par82d). Higher Ca- and lower Na-concentrations are B2O3 11 11 11 concentrations of Li O mg/kg and Si 181100 + 8140 mg/kg. Even the We plotted the corrected ED-XRF results of 112 found in the zone of highest Cu-concentrations 2 and H O (bd = below copper concentration was determined to be tourmalines of known origin and compared the (compare Fig. Par31d and Par31k). Total 93.4 95.0 95.0 2 detection). approx within 8 % when comparing LA-ICP-MS results derived by the different methods (See Fig. and EPMA. Par82a-c, Par90a-b and Lit. Par01). 23 LA-ICP-MS, LIBS and ED-XRF Analysis (Methods)

ELECTRON MICROPROBE ELEMENT Bi-concentrations are highest at border of the coupled to a DRCII + ICP-MS (Perkin Elmer, CHEMICAL COMPOSITION LIBS ANALYSIS 3 DISTRIBUTION MAPPING Cu-rich outer core towards the inner rim of the Norwalk, USA). A 20 cm ablation cell and a 1.5 The major, minor and trace elements of tourma- Laser induced breakdown spectroscopy (LIBS) Fig. Par31 Elemental distribution maps were crystal. The Bi distribution resembles an intense m tube were used as transport system for the lines from Paraiba and Mozambique were ana- was used for direct analysis of the tourmalines. produced by electron microprobe analysis of impact at the latest stage of the “neon”-blue laser-generated aerosols. Helium was used as lyzed and sorted accordingly to the color of the Therefore, a 30 mJ frequency double 266 nm important elements. The analyzed sample is a growth phase that gradually faded away during carrier gas and merged with argon in front of the individual growth zones. The most pronounced Nd:YAG (Continuum, USA) with a pulse width of 6 “Paraiba” tourmaline from the Batalha mine. The further crystal growth (Fig. Par31a). ICP-MS torch to provide optimum excitation changes in color representative for the chemical ns was coupled to an in-house built ICCD/Echelle tourmaline has been cut perpendicular to the F-concentrations are lowest in the core of the conditions within the ICP. The calibration was evolution of the tourmalines are accompanied by spectrometer with a working range of 190-900 nm. c-axis (compare Fig. Par28-29). The trail of the crystal and increase gradually to the mantle of the carried out using the NIST 610 glass. The element a significant change of the minor element concen- The ICCD detector works in a wavelength range craters are form LA-ICP-MS analysis (Compare crystal (Fig. Par31i). They are well correlated with concentrations of NIST 610 were taken from Lit. trations of Cu, Mn, Bi (See Fig. Par36a, 46a-b, between 180-800 nm. The crater ablated on the Fig. Par32-39). The picture of the tourmaline is the backscattered image. Darker parts in the Par03. The acquisition protocol included always 2 55a-b, 59a, 62a, 66a, 75a-b, 78a-b, 90a-b and sample and every element was acquired using 20 shown in Fig. Par31 for comparison of the visual BSE-image match with low F-concentrations. NIST 610 analyses at the beginning and the end 91c-d). This chemical transition can also be spectra (single pulse). Single element spectra and the electron microprobe electron concentra- Higher F-concentrations correlate with higher of each run and allowed to analyze 16 sample extracted from the Pb-Zn-Mg correlation (Fig. were acquired for Cu (324.754 nm), Be (313.042 tion mappings. The colors of the pictures shown in Par34, 59b, 62b, 66b-c, 76b and 91b). These nm) and Mn (403.076 nm). Ablation crater were Fig. Par31a-l are artificial and arbitrary chosen to concentrations of Mn, Cu and Bi (See Fig. positions in-between. Since tourmaline are Par28c). Mg, Ti and Zn show a similar distribution heterogeneous systems and consist of a large trends can further be supported by the elements generated closely matched to the position of achieve maximum contrast to show the differ- such as Be, and Fe and Ti (Fig. Par33b, 41a, LA-ICP-MS analysis. The concentrations were ences in element concentrations. To calibrate the like those observed for Mn. They increase number of major elements, the normalization towards the mantle of the crystal with very distinct procedures for metallic samples (Lit. Par06) and 43a-b, 49b, 59c,e, 62b,f, 66b,d, 76a, 78f, 84, 85, correlated using the LA-ICP-MS data. Crater chemical concentrations, average chemical analy- 86 and 87). In addition to the major and minor diameters using LIBS were selected in the same oscillations at certain positions (compare Fig. oxides (Lit. Par04) were applied. The analysis and ses by LA-ICP-MS (Tab. Par02) are projected into elements, 1-5 μg/g concentrations were deter- order of magnitude as applied for LA-ICP-MS to Par31f, Par31g, Par31h and Par31j). A similar data reduction were carried out following an the picture (μg/g). mined for Sr, Nb, U, Th, La, Ce, Pr, V and Ta. Con- ensure similar destruction of the sample. The element concentration pattern was measured by acquisition, data reduction and quantification Fig. Par31a Back scattered electron image centrations between 0.01 and 1 μg/g were deter- results on the LIBS-measurement in comparison LA-ICP-MS. However, the detection capabilities of protocol (Lit. Par07). (BSE) mined for Sn, Cr, Co, Rb, Zr, Mo, Ag, Cs, Ba, Nd, to the LA-ICP-MS of same samples are shown in LA-ICP-MS allowed to expand the analysis of the 427 individual LA-ICP-MS analysis were carried Sm, Eu, Gd, Tb, Er, Ho, Tm, Yb and Lu, whereas Fig. Par85 and 86. The BSE-image provides different grey tones that elemental distribution in “Paraiba”-tourmalines by out on 6 Paraiba tourmalines (Samples 2079*, 0.01 represents the lowest limits of detection are produced by the different atoms present. focusing into other elements at μg/g concentra- 2965*, 2972*, 2976.2*, 2976*, 3111-a*) and 260 determined throughout this study (See table Higher total number of heavy atoms result in tions that are below the limits of detection of elec- individual analyses were acquired from 8 Mozam- Par02-05 and corresponding figures on pages brighter grey tones. Fig. Par31a shows a dark tron microprobe analysis. bique samples (Samples 2939, 2942, 2942.2, 25-40 and pages 48-53). core and lighter rim. This can be explained by the 2943, 3134*, 3138, 3143, 7782* (*traverse). The increase of heavy elements from the core to the LA-ICP-MS ANALYSIS ACCURACY ED-XRF ANALYSIS samples were surface polished prior to the rim of the crystal. Lighter grey tones can be corre- Laser Ablation-Inductively Coupled Plasma Mass Testing of the accuracy was carried out using ED-XRF analysis are carried with a Fischer Instru- lated with increase in Mn, Cu and Bi (Fig. Par31k). LA-ICP-MS analysis. On each sample, 60 μm Spectrometry analysis were carried out using a craters were place next to each other to provide EPMA concentration and LA-ICPMS concentra- ment (XAN-DP) using a 50kV acceleration The dark-grey core can be correlated with low 193 nm ArF Excimer laser ablation system tion profiles across the Paraiba Tourmaline voltage, a 1000micron Al-Filter, using different concentrations of Mn and Cu (Fig. Par31j). The spatial resolution across different growth zones of (GeoLasM, Lambda Physik, Göttingen, Germany) the tourmalines. sample 2976 (compare Fig. Par28b with Fig. beam collimators (0.2mm-2mm, smaller collima- outer core is dominated by elevated copper- (Cu) Par36a-b). The accuracy of the quantification tors with longer measuring time) and a drift correc- and low Mn-concentrations in the BSE image (Fig. approach using NIST 610 for calibration applied tion mode. The measurement was carried out for Par31k) correlates well with the visual color for LA-ICP-MS was carried out using different minimum of 50-100 seconds. A standard-less zoning (Fig. Par32). “Neon”-blue colors are found spatial resolution for the two independent, but element calculation procedure provided by the in the areas of the crystal at these elevated Cu complementary techniques (EPMA approx. 10 μm manufacturer was used to obtain element concen- and depleted Mn-concentrations. Elemental distri- and LA-ICP-MS approx. 60 μm). Based on the trations of Al, Cu, Mn, Bi, Fe, Zn and Ga. For bution of other elements such Si, Al, Ca, Na Mg, difference in the spatial resolution, 65 data points validation purpose, we measured 12 LA-ICP-MS Zn, F and Bi may not be directly correlated with (LA-ICP-MS) and 306 data points (EPMA) were standards with ED-XRF analyses. The sampling the visible color zoning as they are not the cause acquired on the same traverse shown in Fig. volume of the LA-ICP-MS and ED-XRF are differ- of blue color in the tourmaline (e.g. Lit Par10, 11, Par28b-c and 36a. It can be seen that the concen- ent and the number of measured points by 33). tration profiles (Na, Ca, Ti, Fe, Cu, Bi and Mn) are LA-ICP-MS had to be averaged (Tab. Par02-05), Fig. Par 31b-l Element distribution mapping of in very good agreement between the two indepen- before they could be compared to ED-XRF analy- various elements dently calibrated techniques. For example, the ses. A linear regression was made for each profile of Mn starts for both methods at very simi- element measured by 2 different methods (LA- The element distribution mapping shows that lar concentrations (EPMA 12000 mg/kg, LA-ICP- ICP-MS versus ED-XRF) on the basis of 12 stan- Al-concentrations are slightly higher in the core MS 11500 mg/kg). For further comparison, the dards. A consistent difference between ED-XRF than in the rim of the tourmaline (Fig. Par28a, 31b) average concentrations of the most homoge- and LA-ICP-MS was detected for the different whereas Si does not show any variation (Fig. neously distributed elements (n=306 and n=65, elements of approx. 30%. This is not surprising Par31c). Ca- and Na-concentration revealed an RSD < 5 % for both techniques) were calculated because lighter elements (atomic weight below Al) “inner triangle” which was not evident in the micro- (Data from Tab. Par01 and Tab. Par03). Using this are not measured with this relatively in-expensive scope (Fig. Par31d-e). In this “inner triangle”, the approach, Na concentration of 13500 + 570 mg/kg ED-XRF instrument. A correction of the ED-XRF Ca-concentrations are depleted and and Si concentration of 196800 + 2460 mg/kg data was carried out based on the linear regres- Na-concentrations are enriched (Fig. Par31d-e). (EPMA) were closely matched to Na 13800 + 740 sion coefficient to lower values (See Fig. Par82d). Higher Ca- and lower Na-concentrations are mg/kg and Si 181100 + 8140 mg/kg. Even the We plotted the corrected ED-XRF results of 112 found in the zone of highest Cu-concentrations copper concentration was determined to be tourmalines of known origin and compared the (compare Fig. Par31d and Par31k). approx within 8 % when comparing LA-ICP-MS results derived by the different methods (See Fig. and EPMA. Par82a-c, Par90a-b and Lit. Par01). 24 LA-ICP-MS Chemical Analysis Profiles of Paraiba Tourmaline, Batalha Mine Sample No. GRS-Ref2976

Fig. Par32 Photograph of a multicolored tourmaline from Brazil (Paraiba mine Source RC Gemmas). The tourmaline has been cut perpendicular to the c-axis (thin parallel plate, both sides polished). The sample is from the lot shown in Fig. Par29. Fig. Par32 The string of craters visible in the picture is induced by LA-ICP-MS 300 analysis.Different color zones Fig. Par33a are visible. Mg max Be 250 Mg Mg max Sb Fig. Par33a Variation in Sb-, Pb Mg-, Pb- and 200 Be-concentrations The maximum of the 150 Mg-concentrations is well ppm purple core correlated with the end of the 100 “neon”-blue growth phase. The Sb max Sb max Mg-influx coincides with the first Pb max 50 Be>Pb Be>Pb major increase in Mn and the trend of increasingly higher Mn/Cu-ratios with continuous 0 1 6 11 16 21 26 31 36 41 46 51 56 61 growth after the “neon-blue” growth stadium (Fig. Par33a, 3000 and Par36b). Fe, Zn, Ti Ca Fe, Zn, Ti Sb-concentrations are particu- max K max 2500 Fe larly low in the center of the Ca max Zn crystals (purple growth phase) Ca max 2000 Ti and increase with the beginning Ga of “neon-blue” growth phase. 1500 Be-concentrations increase in ppm this color zone as well as the 1000 Pb/Be ratios (See also Fig. Par36b). 500 Ga max Ga max Ca min Fig. Par33b Variation in Ca-, Ga min Fe-, Ti- and Zn-concentrations 0 1 6 11 16 21 26 31 36 41 46 51 56 61 These elements are enriched in Fig. Par33b measured points along profile the green rim. Ca is depleeted in the core and enriched in the rim Pb (compare wiht EMPA, Fig. Par28b)

A purple C B mix purple/neon-blue C neon-blue B Fig. Par34 Ternary Mg-Pb-Zn diagram (LA-ICP-MS Trend 1 D mix green/neon-blue analysis, in μg/g) E green inner rim The chemical variations in the relative amount of Mg-, Pb- F yellowish-green and Zn-concentrations can be correlated with growth G greenz (middle rim) zones in tourmalines. From the core to the rim the trend is H green outer rim A marked by highly variable concentrations along the Pb-Zn boundary, with a short dominance of the Pb- relative to the Zn-concentrations in the “neon-blue” copper growth phase. Mg-concentrations are in generally low in compari- Trend 2 son to the Zn- and Pb-concentrations. Note that the trend reverses from the core to the rim of the crystal (follow red arrow). In a first step the trend points towards the Pb-concentrations (high) and in a second step towards the Mg Zn D-H Zn-concentrations (high). 25 LA-ICP-MS Chemical Analysis Profiles of Paraiba Tourmaline, Batalha Mine Sample No. GRS-Ref2976

Fig. Par35 Photograph of a Paraiba tourmaline analyzed with LA-ICP-MS perpendicular to the color zoning. Correla- tion with profile analysis aims at reconstructing the chemical variations of the tourmaline in different growth stadiums Fig. Par35 (details see Fig. Par32).

16000 Fig. Par 36a Variation in Fig. Par36a Mn Mn-, Cu- and 14000 Cu Bi-concentrations. Bi Mn>>Cu Mn>>Cu Purple growth zone: 12000 Mn-concentrations are higher purple core 10000 than Cu-concentrations and Cu-concentrations are higher

8000 Cu, Bi max than the Bi-concentrations.

ppm “Neon”-blue growth zone: Cu- 6000 concentrations are higher than Mn-concentrations, Bi- 4000 increases to equal those of 2000 Bi min the Cu-concentrations. Mn high Compare with EMPA analyses 0 Fig. Par28b. 1 6 11 16 21 26 31 36 41 46 51 56 61 5.00 Fig. Par36b Variation of Fig. Par36b Mn/Cu 4.50 Mn/Cu-, Bi/- and Pb/Be- Pb/Be concentration ratios 4.00 Bi/Cu Pb/Be-ratios are highest in the 3.50 purple core of the tourmaline 3.00 and decrease with increase in Mn/Cu-ratios. Higher Mn/Cu- ratio 2.50 ratios are found in the purple 2.00 core and the green rim. 1.50 Mn/Cu-ratios constantly 1.00 increase towards the rim but 0.50 decrease at the outer green rim. The highest Bi/Cu-ratios 0.00 1 6 11 16 21 26 31 36 41 46 51 56 61 are found at the beginning of measured points along profile the trend of higher Mn/Cu- ratios at the transition to the Cu green rim.

A purple B mix purple/neon-blue B C neon-blue A D mix green/neon-blue E green inner rim C Fig. Par37 Ternary Cu-Mn-Bi diagram showing the F yellowish-green variation of Cu-, Mn, and Bi-concentrations from the G green (middle rim) core (A) to the rim (H) (LA-ICP-MS analysis, in μg/g) H green outer rim D A: High Cu-concentrations and Mn-concentrations, G low Bi-concentrations (Cu-Mn-dominated growth phase) H E A to C: Mn-concentrations depleted, Cu-concentrations enriched, and Bi-concentrations F increase (Cu-dominated-growth phase”) C to H: Increase of Mn-concentrations, decrease in Cu- and Bi-concentrations (Mn-dominated growth Mn Bi phase) 26 LA-ICP-MS Chemical Analysis Profiles of Paraiba Tourmaline, Batalha Mine Sample No. GRS-Ref2976

Fig. Par38 Photograph of a Paraiba tourmaline with color zoning is correlated with LA-ICP-MS analyses (in ppm) of rare earth elements (REE), strontium (Sr) and calcium (Ca) (See Fig. Par39a, b and Par41a-d) Fig. Par38 Fig. Par39a-b 1.8 Concentrations of the REE Fig. Par39a La elements La, Ce, Pr, Nd, Gd 1.6 Ce and Nd were detected in the 1.4 Pr REE max green rim of the Paraiba REE max Nd tourmalines. These REE- 1.2 Gd elements were not detected in 1 Nd the “neon-blue” growth phase (Fig. Par39a). Ce and La 0.8 ppm purple core dominate the concentrations of 0.6 REE. The sum of all REE concentrations (Fig. Par39b) 0.4 correlate well with increasing 0.2 Sr- and Ca-concentrations along the measured profile. 0 1 6 11 16 21 26 31 36 41 46 51 56 61 They are found in the rim of crystal. 4 Fig. Par39b REE 3.5 Sr*10 Ca/1000 3 Ca, Sr max 2.5 Ca, Sr max Sr>Ca 2 ppm 1.5 1 Sr>Ca 0.5 0 1 6 11 16 21 26 31 36 41 46 51 56 61 measured points along profile

REE Fig. Par40 Ternary Mn-Cu-REE diagram showing the trend of total REE-concentrations in the tourmaline from the core (A) to the rim (H) in A purple B mix purple/neon-blue relation to variations in Cu- and Mn-concentrations C neon-blue D mix green/neon-blue (LA-ICP-MS analyses, in μg/g). E green inner rim F yellowish-green G green (middle rim) The changes in chemical compositions from core H green outer rim E to rim of the tourmaline define a trend that is indicated by the arrow. REE-concentrations increase sharply at the end of the Cu-dominated D (“neon”-blue) growth phase. REE-concentrations

C increase along with Mn-concentrations in the green rim of the tourmaline.

B Mn/10,000 Cu/10,000 A 27 LA-ICP-MS Chemical Analysis Profiles of Paraiba Tourmaline, Batalha Mine Sample No. GRS-Ref2976

60 Fig. Par41a Variation in V- and Fig. Par41a V Cr Cr-concentrations Ta

50 Nb Cr max A very distinctly localized growth zone Sr with Cr-concentrations is found at the Sn Pb onset of the “neon-blue” growth phase 40 Be (see also Fig. Par 41b). Be, Pb max V-concentrations are not correlated with the occurrence of the 30 Cr-concentrations in the tourmaline. ppm V-concentrations can only be found in Cr high the green rim. These 20 Cr-concentrations are found symmetrically along the chemical profile at the same position at the 10 border of the purple core to the V max V max neon-blue zone. They are therefore not the product of a contamination. 0 4 Fig. Par41b Variation inTh- and Fig. Par41b Th U-concentrations 3.5 U Cr/100 Distinct Th- and U-concentrations 3 occur in certain growth zones of the tourmaline. The elevated Th-U- 2.5 concentrations are not correlated with Th, U max those of the isolated 2 ppm Cr-concentrations. The Th- and U anomaly is localized at the final stage 1.5 of the "neon"-blue (Cu-dominated) growth phase and at the beginning of 1 Th high the dramatic increase in Mn-concentrations at the border to the 0.5 green rim. During the growth phase of the green rim, however, Th- and 0 U-concentrations decrease sharply. 5 Fig. Par41c Ta 4.5 Cu max Fig. Par41c Variation in Ta- and Nb Nb-concentrations 4 Cu/2000 Cu high 3.5 Ta-concentrations were detected in the "neon"-blue growth zone of the 3 tourmalines. High Ta/Nb-ratios (>1) are found in the same position of first 2.5 ppm appearance of high Cu-concentrations 2 from the core to the rim in the crystal. Ta>Nb Ta and Nb show opposite concentra- 1.5 tion trends in the measured profile. 1 Nb>Ta Nb>Ta Ta-concentrations are higher than Nb-concentrations in the purple and 0.5 Ta>Nb "neon"-blue growth zone; 0 Nb-concentrations are higher than those of Ta in the green rim. 500 Fig. Par41d Ga Par41d Variation in K-,Ti- and 450 Ti Ga-concentrations 400 K An increase in K-,Ti- and 350 Ga-concentrations occur at the 300 transition to the green rim. It can be correlated with the increase of REE-, 250 Ca- and Sr-concentrations (Fig. ppm Ga max Ga max Par39b) and Ti-, Fe- and 200 Zn-concentrations (Fig. Par33b).

150 Ga min Ga min Towards the end of the crystal growth, in the outer dark green rim, the 100 concentration of Ti, Fe and Zn are 50 slightly decreasing. This trend is opposite to the general increase in 0 Nb-, Ca-, REE- and 1 6 11 16 21 26 31 36 41 46 51 56 61 Sr-concentrations. These elements measured points along profile continuously increase towards the outer rim. 28 LA-ICP-MS Chemical Analysis Profiles of Paraiba Tourmaline, Batalha Mine Sample No. GRS-Ref2976.2

Fig. Par42 Photograph of a multicolored tourmaline from the series of similar sections of same lot and same origin (Fig. Par29). The tourmaline has been cut perpendicular to the c-axis (thin parallel plate, both sides polished). The string of craters visible in the picture represent LA-ICP-MS analysis. The profile has been positioned across the “neon”-blue growth zone and green rim without targeting the purple core of the sample. It is aimed to verify the trends found in another sample from the same lot, which had only narrow zones of “neon”-blue colors (Fig. Par32). It can be shown below that the trends can be reproduced. Chemical analysis profiles see Fig. Par43a-b, 46a-b, 49a-b and 51b-d. A second profile through the purple core of the same sample is shown in Fig. Par 52. It is aimed to also verify the chemical trends in the purple core in a second sample.

Fig. 43a-b, Variation in Fe-, Ti-, Zn-, Pb-, Mg-, Be- and Sb-concentrations

The maximum of the Mg-concentrations are found at the end of the “neon”-blue growth phase. During the “neon”-blue growth phase, Zn- and Mg-concentrations are depleted. High Mg-values are found at the position of high Bi-concentrations in the profile (compare Fig. Par46b).The increase of Mg-concentrations coincides with the first major increase in Mn-concentrations and higher Mn/Cu-ratios in the green rim (Fig. 46b). 5000 The concentrations of other elements Pb, Be, Zn, Ca, 4500 Ca K, Fe and Ti show major changes as well: K 1.) Pb and Be is high along with high Cu in the 4000 Fe, Zn,Ti Fe “neon”-blue growth zone (Fig. Par43b) 3500 Zn Fe, Zn,Ti max Ti 2.) Zn increases in the green rim along with Ca, K, Fe 3000 max and Ti (Fig. Par43a). 2500 Pb ppm Neon blue 2000 outer core 1500 1000 C 500 0 1 6 11 16 21 26 31 36 41 46 51 56 61 66 71 76 81 Fig. Par43a

800 Be 700 Mg Mg>Be, Pb C neon-blue (inner zone) Mg>Be, Pb Sb 600 Pb D mix green/neon-blue 500 E-H yellowish-green/green 400 D ppm Be>>Pb 300 200 Mg Zn E-H 100 Be max Fig. Par44 Mg-Pb-Zn Triangle (LA-ICP-MS analysis in 0 μg/g) 1 6 11 16 21 26 31 36 41 46 51 56 61 66 71 76 81 The chemical variations in the relative amount of Mg-, measured points along profile Pb- and Zn-concentrations can be correlated with Fig. Par43b transition of the “neon”-blue to green growth zones in the tourmaline. The trend (red line) from the “neon”-blue zone to the rim is marked by an increase in Zn and Mg in the outer rim. 29 LA-ICP-MS Chemical Analysis Profiles of Paraiba Tourmaline, Batalha Mine Sample No. GRS-Ref2976.2

Fig. Par45 Photograph of a multicolored copper- bearing tourmaline in cross section and the trail of craters induced by LA-ICP-MS (detailed description see Fig. Par42).

Fig. Par 46a. Variation in Cu-, Mn- and Bi-concentrations.

In the “neo-blue growth zone, the Cu dominates Mn and Bi. A sharp increase in Bi occurs towards the end of the ”neon-blue” growth phase. This confirms the ealier findings in a section of the same lot (Fig. Par36a).

Fig. Par46b Variation of Mn/Cu-, Pb/Be- and Bi/Cu-ratios

Pb/Be ratios are approximately 1 in the neon-blue growth phase of the Paraiba tourmaline and decrease towards the inner rim and finally increase in the outer rim. The highest Bi/Cu-ratio is found at the transition of the “neon”-blue to the green rim. Higher Mn/Cu- ratios are present at the end of the crystal growth.

25000 C neon-blue (inner zone) Mn neon-blue (middle zone) Mn max Cu Mn max neon-blue (outer zone) 20000 Bi D mix green/neon-blue E-H yellowish-green/green 15000 Neon blue outer core Cu ppm 10000 Bi max 5000 Bi max Cu>>Mn

0 C 1 6 11 16 21 26 31 36 41 46 51 56 61 66 71 76 81 Fig. Par46a 4.0 Mn/Cu D 3.5 Pb/Be Bi/Cu 3.0 2.5 2.0 ratio E-H 1.5 1.0 Mn Bi 0.5 Fig. Par47 Ternary diagram showing the chemical 0 1 6 11 16 21 26 31 36 41 46 51 56 61 66 71 76 81 variation of Cu-, Mn, and Bi-concentrations from the measured points along profile “neon”-blue growth zone (C) to the rim (H) (LA-ICP- Fig. Par46b MS analysis, μg/g) C to H: Increase of Mn-concentrations, decrease in Cu- and Bi-concentrations (Mn-dominated growth phase) 30 LA-ICP-MS Chemical Analysis Profiles of Paraiba Tourmaline, Batalha Mine Sample No. GRS-Ref2976.2

Fig. Par48 Photograph of a multicolored copper- bearing tourmaline in a cross- section and the trail of craters induced by LA-ICP-MS (detailed description see Fig. Par42). Growth and color zones are corre- lated with chemical profile analyses (LA-ICP-MS) focusing on the concentrations of REE (Fig. Par 49a), Pb- and Be-concentrations (Fig. Par49b).

Fig. Par49a REE are mainly found in the second half of the Paraiba tourmaline growth phase (green sector) with a slight increase in the center of the “neon-blue” growth phase. Ce and La dominate the concentrations of REE.

Fig. Par49b Pb- and Be-concentrations are highly variable over the “neon”-blue growth sector and with a high Pb/Be-ratio (highest Pb/Be-ratio is found in the rim).

C neon-blue (inner zone) neon-blue (middle zone) neon-blue (outer zone) D mix green/neon-blue 2.5 E-H yellowish-green/green La Pr REE max REE 2 Nd REE max Gd Ce 1.5

ppm Neon blue 1 outer core

0.5

0 1 6 11 16 21 26 31 36 41 46 51 56 61 66 71 76 81 Fig. Par49a E-H 180 Pb 160 Be D 140 Pb/Be*100 C

120 Pb/Be max Pb/Be high Pb/Be max 100 Mn Cu 80 2967 Fig. Par50 Ternary Mn-Cu-REE diagram ppm and ratio 60 showing the trend of total REE-concentrations in the 40 tourmaline from the “neon”-blue growth zone (C) to 20 the rim (H) in relation to variations in Cu- and Mn-concentrations (LA-ICP-MS analyses, in μg/g) 0 1 6 11 16 21 26 31 36 41 46 51 56 61 66 71 76 81 The triangle shows that the REE do occur within and measured points along profile after the termination of the “neon”-blue growth phase. Fig. Par49b Increase in REE-concentrations is correlated with increasing Mn-and decreasing Cu-concentrations.

31 LA-ICP-MS Chemical Analysis Profiles of Paraiba Tourmaline, Batalha Mine Sample No. GRS-Ref2976.2

80 Neon blue V Fig. Par51a Variation in V- and 70 Cr Cr-concentrations outer core Ta Nb 60 A very distinctly localized Cr-concentration is Be Sr 50 Sn found only within the “neon”-blue growth phase. Pb V is not correlated with Cr and can only be found 40 Be ppm in the rim. 30 Cr 20 Pb 10

0 Fig. Par51a 6 Th Fig. Par51b Variation in Th- and U U-concentrations 5 Bi/1000 Th- and U- concentrations are symmetrically 4 Bi max

Bi max detected in the profile and the positions are not identical. They can be correlated with the maxi- 3 ppm mum of the Bi-concentrations. The Th-concentrations were formed first, before the 2 high Bi-concentrations occurred.

1

U Th max Th max 0 Fig. Par51b 5 Ta Fig. Par51c Variation in Ta- and 4.5 Nb Cu/2000 Nb-concentrations 4

3.5

Cu max Ta- and Nb-concentrations show an opposite Cu max 3 distribution in the crystal. Highest Ta- and lowest

2.5 Nb-concentrations are found within the ppm “neon”-blue growth phase of the tourmalines. 2 Ta>Nb 1.5 Nb>Ta Nb>Ta 1

0.5

0 Fig. Par51c 700 Fig. Par51d Variation in Zn-, Fe-, Ti- and Ti max Ga Ga-concentrations 600 Ti max Ti A sharp increase in Ti-, Zn- and 500 Fe-concentrations occur at the beginning of the

400 Mn-dominated growth phase. It can correlated with the increase of REE, Ca and Sr. Ti-, Fe- and ppm 300 Zn-concentrations are highest at the contact to the green rim. Towards the end of the crystal 200 growth, their concentrations are constantly

Ga max Ga min 100 Ga min Ga max decreasing. This trend is opposite to the general increase of Nb, Ca, REE and Sr, which increase 0 towards the outer rim. Slightly elevated 1 6 11 16 21 26 31 36 41 46 51 56 61 66 71 76 81 Ga-concentrations are found in the green rim of Fig. Par51d measured points along profile the tourmaline.

32 LA-ICP-MS Chemical Analysis Profiles of Paraiba Tourmaline, Batalha Mine Sample No. GRS-Ref2976.2 Crators Fig. Par32 Fig. Par 52 Photograph of a multicolored tourmaline analyzed by LA-ICP-MS. Two profiles of craters are visible in the picture. One targeting the chemical composition in the “neon”-blue color zone (See Crators this profile Fig. Par42) and one through the purple core. 5 mm Fig. Par53a 2.5 Th max Fig. Par53a-d Variation of Pb-, Mg-, Be- and Th Th max U Sb-concentrations 2 Rim Core Rim The maximum of the Mg-concentrations are well 1.5 correlated with the end of the “neon”-blue growth phase. During the “neon”-blue growth phase, Zn- and

ppm Mg-concentrations are depleted. The increase in 1 Mg-concentrations is in coincidence with the first major increase in concentrations of Mn. This observa- 0.5 U tion confirms the findings of another sample (Fig. U Par33a). The following observation do also confirm the previous findings in the first sample: 0 2000 1.) Pb and be are enriched in the “neon”-blue growth 1800 Mg Fig. Par53b Pb zone (Fig. Par53b, d) 1600 Zn 2.) Zn increases in the green rim along with Mg (Fig. 1400 Par 53b) 1200 3.) Th- and U-concentrations are slightly enriched in Zn, Mg max Zn, Mg max the “neon”-blue growth zone. Th-concentrations are

ppm 1000 higher than U-concentrations (Fig. Par53b). The 800 highest U-concentrations appear before the 600 Th-maximum in the profile from the core to the rim 400 (See also Fig. Par51b). 200 Mg, Pb, Zn 4.) The Ca- and Sr-maximum is correlated with the min 0 REE-maximum (Fig. Par53c). 25 REE Fig. Par53c Ca max Sr*10 20 Ca/100

Ca max Pb 15 ppm

10 REE max

5 Ca min

REE max A purple 0 B purple/greenish-blue 450 C "neon"-greenish-blue Mg>Be Be Fig. Par53d 400 Mg F yellowish-green 350 Mg>Be 300 250

ppm 200 150 100 Mg Zn 50 Fig. Par54 Ternary Mg-Pb-Zn Diagram 0 The same trend in the concentration variations of Mg, 1 6 11 16 21 26 31 36 41 Pb and Zn was found as described in Fig. Par 34. measured points along profile 33 LA-ICP-MS Chemical Analysis Profiles of Paraiba Tourmaline, Batalha Mine Sample No. GRS-Ref2976.2

12000 Fig. Par55 Variations in Mn Cu-, Mn- and Cu Bi-concentrations 10000 Bi Lowest Cu- and Rim Rim Bi-concentrations are 8000 found in the purple core Core and highest concentra- Bi, Cu tions of these elements ppm Bi, Cu 6000 max max are found in the outer rim of the “neon”-blue colored growth zone. The 4000 Bi, Cu highest min Mn-concentrations are found in the rim. 2000

0 Mn max Mn max 1 6 11 16 21 26 31 36 41 measured points along profile 2.0000 25 Pb/Be max 1.8000 Mn/Cu As Pb/Be Cd 1.6000 Bi/Cu 20 Cd max 1.4000 1.2000 Mn/Cu max Pb/Be max 15

1.0000 Mn/Cu max ppm ratio 0.8000 10 0.6000 0.4000 5 0.2000 As min 0.0000 0 1 6 11 16 21 26 31 36 41 11 16 21 26 31 36 41 measured points along profile measured points along profile Fig. Par55b Variation in Mn/Cu-, Pb/Be-and Bi/Cu- Fig. Par56 Variations in As- and Cd-concentrations ratios The highest Cd-concentrations and lowest Pb/Be ratios are approximately 1 in the neon-blue As-concentrations are found at the same position as growth phase of the Paraiba tourmaline and decrease the maximum of the Cu- and Bi-concentrations (See towards the inner rim. It finally increases in the outer Fig. Par55). rim. The highest Bi/Cu-ratio is found at the transition of the neon-blue to the green rim. Higher Mn/Cu ratios Cu are present at the end of the crystal growth. This confirms earlier findings in another sample of the same lot (Compare Fig. Par36b). B

A C

A purple B mix purple/greenish-blue C "neon"-greenish-blue E/F E/F yellowish-green Fig. Par57 Ternary Cu-Mn-Bi diagram

The same trends were found in another sample from the same lot. See Fig. Par37 for explanations. Mn Bi 34 LA-ICP-MS Chemical Analysis Profiles of Paraiba Tourmaline, Batalha Mine Sample No. GRS-Ref2965

Fig. Par58 Photograph of a multi- Sample No. GRS-Ref2965 colored tourmaline from Brazil from another source (Paraiba, Batalha mine, source: Wagoner)

Note: Intense purple-, blue- and Core green color zoning is visible from core to the rim. The trail of craters is from LA-ICP-MS analysis. Chemical analysis profiles see Fig. Par59a-d and Fig. Par60a-d.

Rim

Fig. Par58 Fig. Par59a Fig. Par59b 20000 16000 Zn max 18000 Mn Mn>Cu Mg Mn>Cu 14000 16000 Cu Zn Cu max 12000 14000 Bi Pb 12000 10000 10000 Rim 8000 ppm Cu>Mn ppm 8000 Core 6000 6000 4000 4000 Bi max 2000 2000 Mg max Zn low 0 0 1 6 11 16 21 26 31 36 41 46 1 6 11 16 21 26 31 36 41 46 Fig. Par59c Fig. Par59d 900 50 Be>Pb Be V Be max 800 Mg max 45 Mg Cr 700 40 Sb Pb Pb>Be 35 600 Pb Pb>Be Be 30 500 25 ppm 400 Be>Mg Mg>Be ppm V max 20 300 15 200 10 100 Sb max 5 0 0 1 6 11 16 21 26 31 36 41 46 1 6 11 16 21 26 31 36 41 46 measured points along profile measured points along profile Fig. Par59a-d Chemical analysis profile by LA-ICP-MS. Chemical variations are correlated with color zoning. The “neon”-blue color zone is characterized by a decrease in Mn- and an increase in Cu- and Bi-concentrations (Fig. Par59a). The inner core of the crystal is characterized by high concentrations of Mn, followed by a sudden decrease in Mn-concentrations in the “neon”-blue growth zone. The Mn-concentrations resume their concentra- tion level during crystal growth towards the rim. A very similar profile has been published in the literature from the same type locality (Lit. Par16) with almost identical results regarding the Mn- and Cu-trends. Other trace element concentrations can be correlated with these changes in the minor elements. Be is enriched in the “neon”-blue zone (Fig. Par59d) and Zn and Mg in the green rim (Fig. Par59b-c). 35 LA-ICP-MS Chemical Analysis Profiles of Paraiba Tourmaline, Batalha Mine Sample No. GRS-Ref2965

Fig. Par60a 600 Fig. Par60a Variation in Ga- and Ga Ti max Rim Ti-concentrations 500 Ti K Ga and Ti are enriched at the same positions in 400 the green rim. Core K max 300 ppm Ga max 200

100

0 1 6 11 16 21 26 31 36 41 46 Fig. Par60b 4.5 Fig. Par60b Variation in Ta- and Nb>Ta Ta 4 Nb-concentrations Nb 3.5 Sr The variations of these elements can be 3 correlated with the variations in concentrations 2.5 of Cu and Mn: Ta>Nb Nb>Ta Nb- and Ta-concentrations are enriched in the ppm 2 core and the rim of the tourmaline crystal and 1.5 they are depleted in the Cu-rich growth zone. The Ta/Nb-ratio changes across the profile with Sr max 1 highest Ta/Nb in the copper-rich growth zone of 0.5 the tourmaline with “neon”-blue color. The ratio reverses in the green rim. 0 1 6 11 16 21 26 31 36 41 46 Fig. Par60c 1.2 Fig. Par60c Variation in REE-concentrations La 1 Nd REE max REE-concentrations (La, Nd and Ce) are Ce enriched at the transition from the “neon”-blue 0.8 color zone to the green rim.

0.6 ppm Fig. Par60d Variation in Ge- and 0.4 Sc-concentrations

Ge-concentrations are highest in the transition 0.2 zone from the “neon”-blue to the green color zoning. 0 1 6 11 16 21 26 31 36 41 46 Fig. Par60d In conclusions, the following typical chemical 60 composition can be found in the “neon”-blue Ge max Sc blue color zone in the tourmaline: 50 Ge Cu-, Bi- and Be-concentrations are enriched 40 and Nb, Ga-, Zn-, Pb- and Mg-concentrations are depleted. 30 Sr, Ti, Zn, Pb and Mg concentrations along with ppm 20 Fe (not plotted, concentrations see Tab. Par03) are enriched in the green part of the crystal. 10 The “green” rim is also characterized by an increase in the concentrations of Ti and Ga 0 1 6 11 16 21 26 31 36 41 46 (Fig. Par60a), Pb (Fig.59d) and Sr (Fig. Par 60b). measured points along profile 36 LA-ICP-MS Chemical Analysis Profiles of Paraiba Tourmaline, Batalha Mine 1988, Pavlik Collection, Sample No. GRS-Ref3111

Photograph of multi-colored tourmaline Sample No. GRS-Ref3111 Fig. Par61 from Brazil (Paraiba, Batalha mine, Heitor mine, 1988, source: Pavlik), Sample No.GRS-Ref3111. Note: blue, violet and green color-zoning (from core to rim). Laser ablation crater visible. Chemical analysis profiles see Rim Fig. Par 62a-j

Fig. Par62a-j Variation in Th-, U-, Ta-, Cu-, Mn-, Bi, Core Be- and Pb-concentrations. Chemical variations are correlated with the color zoning. The following elements are enriched in the blue core of the crystal: Th, U (Fig. Par62h); Ta (Fig. Fig. Par61 Par62d); Cu, Mn and Bi (Fig. Par62a), Be and Pb (Fig. Par62e). Elements enriched in the green rim: Mg (Fig. Par62f); Sr and V (Fig. Par62d, g);

30000 20 Rim Ta violet zone 18 Cu max Nb Core 25000 16 Sr Rim Mn 14 20000 Cu Ta>Nb 12 Nb>Ta Bi 15000 10 ppm ppm 8 Fig. Par62d 10000 6 4 5000 2 Fig. Par62a 0 0 1 6 11 16 21 26 31 36 41 46 51 56 61 1 6 11 16 21 26 31 36 41 46 51 56 61 25000 70 V Fe Rim Core Zn Core 60 Pb 20000 Ti Be 50 Rim

15000 40 Fe Pb>Be Be>Pb ppm ppm 30 10000 20 Zn 5000 10 Fig. Par62e Fig. Par62b Ti 0 0 1 6 11 16 21 26 31 36 41 46 51 56 61 1 6 11 16 21 26 31 36 41 46 51 56 61 80 4000 Sc Core Be Core Rim 70 Ge Rim 3500 Mg Ge max 60 3000

50 2500

40 2000 Mg max ppm ppm 30 1500

20 1000

10 Fig. Par62c 500 Fig. Par62f

0 0 1 6 11 16 21 26 31 36 41 46 51 56 61 1 6 11 16 21 26 31 36 41 46 51 56 61 measured points along profile measured points along profile 37 LA-ICP-MS Chemical Analysis Profiles of Paraiba Tourmaline, Batalha Mine 1988, Pavlik Collection, Sample No. GRS-Ref3111

70 1.6 Core V La REE max 60 Ta 1.4 Nd Sr Ce Core Pb 1.2 50 Be 1 40 Rim 0.8 ppm 30 ppm 0.6 ppm 20 0.4 Fig. Par62g Fig. Par62i 10 0.2 0 0 1 6 11 16 21 26 31 36 41 46 51 56 61 1 6 11 16 21 26 31 36 41 46 51 56 61

0.4 200 Th Th max U REE U 180 Sr max 0.35 Sr*10 Core 160 Ca/100 0.3 140 Fig. Par62j 0.25 120 0.2 100 ppm ppm 0.15 80 Rim 60 0.1 40 Ca max 0.05 20 Fig. Par62h 0 0 1 6 11 16 21 26 31 36 41 46 51 56 61 1 6 11 16 21 26 31 36 41 46 51 56 61 measured points along profile measured points along profile Rare Earth elements (Fig. Par62i, j and Fig. Par63) and Fe, Zn and Ti (Fig. Par62b). “Ge”-enrichment is found in the transition zone from the violet to the green rim of the crystal (Fig. Par62c). A similar situation was observed in another sample (See Fig. Par60d). Higher Pb/Be-ratios (Fig. Par 62e) and higher Nb/Ta-ratios (Fig. Par62d) are found in the green rim of the crystal. REE (La, Ce, Nd)-Concentration Variations in Tourmalines from Brazil

REE REE

A Blue A Violetish-blue B Purple Batalha Quintos B 'neon'-greenish-blue C Yellowish-Green C Green D Dark Green

MN/10,000 Cu/10,000 MN/10,000 Cu/10,000 Fig. Pa63a Sample No. GRS-Ref3111 Sample No. GRS-Ref2079 Fig. Par63b

Fig. 63a-b Triangular plot of Mn, Cu (concentrations divided by 10000) and Rare Earth Elements (REE) in two multicolored copper-bearing tourmaline from two different mines in Brazil (Batalha, Paraiba State and Quintos, Rio Grande do Norte). Chemical compositions are measured in a profile from the core to the rim of the crystal (A-D). The chemical compositions show a trend towards higher REE along with higher Mn/Cu-ratios regardless of the origin. Towards the end of the crystal growth, REE-concentrations are highest (Details see cross section profiles Fig. Par60c and 62j). 38 LA-ICP-MS Chemical Analysis Profiles of “Paraiba”-Tourmaline, Rio Grande Do Norte Quintos Mine (P. Wild), Sample No. GRS-Ref2079

Sample No. GRS-Ref2079 Fig. Par64 Photograph of multi-colored tourmaline from Brazil Rio Grande do Norte, Quintos mine (P. Wild), sample GRS- Ref 2079. Note: Violet, blue and green color zoning (from core to rim). Laser ablation craters are visible (size 60 micrometers). Chemical analysis profiles see Fig. Par66a-j.

Chemical analysis profile of “Paraiba”-tourmaline from Brazil (Sample No. GRS-Ref2079, GRS collection. Chemical variations are correlated with the color zoning (see Fig. Par66a-j). Fig. Par64 Fig. Par66a. Variations of Cu-, Bi- and Mn-concentrations. The concentrations of Cu and Mn gradually change Fig. Par66a over the measured profile (Fig. Par66a). Higher 18000 Rim concentrations of Cu than Mn were found in the core 16000 Mn Core of the crystal (Cu/Mn-ratio is greater than 1). In the rim Cu 14000 of the crystal, the Cu/Mn-ratio is less than 1. Bi 12000 Fig. Par66b-j Variations in REE-, Ta-, Nb-, Ti-, Fe-, 10000 Zn-, U-, Th- and Mg-concentrations Cu>Mn Mn>Cu ppm 8000 From the core towards the rim, other element concentrations of Ti, Fe and Zn (Fig. Par66b), Th, U concentrations also increase, such as rare earth (Fig. Par66f) and Mg (Fig. Par66c) were detected at 6000 element La and Ce (Fig. Par66i and Fig.66j). A particular growth stages of the crystal. Fe, Ti and Zn 4000 decrease in element concentrations over the same increase towards the rim of the crystal (Fig. Par66b). 2000 profile is observed for Ta and Nb (Fig. Par66e, g) and Pb- and Be-concentrations remain constant along the Ge (Fig. Par66h). Isolated increase of higher element measured profile at low levels (Fig. Par66d). 0 1 6 11 16 21 26 31 36 41 46 51 56

Fig. Par66b Fig. Par66d 3000 35 Core Pb Rim 30 2500 Be Pb>Be 25 Rim 2000 Be>Pb 20 1500 ppm ppm Ca 15 1000 Fe 10 Zn 500 Ti 5

0 0 1 6 11 16 21 26 31 36 41 46 51 56 1 6 11 16 21 26 31 36 41 46 51 56

Fig. Par66c Fig. Par66e 1600 35 Cr Mg 1400 30 Ta Pb Nb Rim 1200 Sr Zn 25 Pb 1000 20 Be 800 Rim ppm ppm 15 600 10 400

200 5

0 0 1 6 11 16 21 26 31 36 41 46 51 56 1 6 11 16 21 26 31 36 41 46 51 56 measured points along profile measured points along profile 39 LA-ICP-MS Chemical Analysis Profiles of “Paraiba”-Tourmaline, Rio Grande Do Norte Quintos Mine (P. Wild), Sample No. GRS-Ref2079

Fig. Par64 Photograph of multi-colored tourmaline Fig. Par65 A spectacular unheated copper-bearing from Brazil Rio Grande do Norte, Quintos mine Fig. Par65 tourmaline from Brazil (P. Wild, Quintos mine, Rio (P. Wild), sample GRS- Ref 2079. Note: Violet, blue Grande do Norte). Size: 378.65ct, length= 52mm and and green color zoning (from core to rim). Laser width= 36mm. ablation craters are visible (size 60 micrometers). Chemical analysis profiles see Fig. Par66a-j. Note the violet-blue color in the center of the crystal, followed by a “neon”-blue color of the main part and a Chemical analysis profile of “Paraiba”-tourmaline from green rim. Brazil (Sample No. GRS-Ref2079, GRS collection. Chemical variations are correlated with the color The tourmaline fragment that has been measured by zoning (see Fig. Par66a-j). LA-ICP-MS is from another sample that showed a more distinct color zoning developed over a shorter Fig. Par66a. Variations of Cu-, Bi- and distance (Fig. Par64). Mn-concentrations. The concentrations of Cu and Mn gradually change over the measured profile (Fig. Par66a). Higher Fig. Par66h 16 concentrations of Cu than Mn were found in the core of the crystal (Cu/Mn-ratio is greater than 1). In the rim 14 of the crystal, the Cu/Mn-ratio is less than 1. 12

Fig. Par66b-j Variations in REE-, Ta-, Nb-, Ti-, Fe-, 10 Core Rim Zn-, U-, Th- and Mg-concentrations 8

From the core towards the rim, other element concentrations of Ti, Fe and Zn (Fig. Par66b), Th, U ppm concentrations also increase, such as rare earth (Fig. Par66f) and Mg (Fig. Par66c) were detected at 6 element La and Ce (Fig. Par66i and Fig.66j). A particular growth stages of the crystal. Fe, Ti and Zn Sc 4 decrease in element concentrations over the same increase towards the rim of the crystal (Fig. Par66b). Ge profile is observed for Ta and Nb (Fig. Par66e, g) and Pb- and Be-concentrations remain constant along the 2 Ge (Fig. Par66h). Isolated increase of higher element measured profile at low levels (Fig. Par66d). 0 1 6 11 16 21 26 31 36 41 46 51 56

Fig. Par66f Fig. Par66i 0.9 1.8 0.8 Core 1.6 La Rim 0.7 1.4 Nd Ce 0.6 1.2 0.5 Th 1 ppm 0.4 U ppm 0.8 0.3 0.6 0.2 0.4 0.1 0.2 0 0 1 6 11 16 21 26 31 36 41 46 51 56 1 6 11 16 21 26 31 36 41 46 51 56

Fig. Par66g Fig. Par66j 12 30 Ta 10 25 Nb Rim

8 20 Ta>Nb 6 Nb>Ta 15 REE ppm ppm Sr*10 4 10 Ca/100 2 5

0 0 1 6 11 16 21 26 31 36 41 46 51 56 1 6 11 16 21 26 31 36 41 46 51 56

measured points along profile measured points along profile 40 Inclusion Research Case Study of a Copper-Bearing Tourmaline from Mozambique: Materials

873 ct Fig. Par67a

Fig. Par67b

Fig. Par67a-b An example of a large copper-bearing tourmaline rough from Mozambique is shown. It has been experimentally faceted in our own GRS cutting studio into a set of 13 faceted gemstones for this report (Fig. Par68a). The rough of 983ct was acquired from an African supplier in 2007. The largest tourmaline obtained after faceting is over 103 ct and the smaller pear-shapes are between 3 to 7 ct. A small portion of the stones was of a “Paraiba”-type green-blue color. The remaining stones were bluish-green, green and yellowish-green. All faceted stones are in GRS collection. An inclusion case study was performed on these samples that all originated from the same rough (See Fig. Par68-71).

41 Inclusion Research Case Study of a Copper-Bearing Tourmaline from Mozambique: Orange Growth Tubes and purple “Halo”

Fig. Par68a Yellow-orange colored growth tubes in a bluish-green copper-bearing tourmaline from Mozambique.

Tube

Purple “Halo”

Fig. Par68c

Fig. Par68b-c Same growth tubes such as shown in Fig. Par68a but observed in another faceted stone from the lot shown in Fig. Par67b (all faceted stones originally from the same rough, See Fig. Par67a). Narrow purple “halos” were present Fig. Par68b around these particular orange growth tubes.

42 Inclusion Research Case Study of a Copper-Bearing Tourmaline from Mozambique: Orange Growth Tubes and Cracks with Purple “Halos”

Fig. Par69a

Fig. Par69b

43 Inclusion Research Case Study of a Copper-Bearing Tourmaline from Mozambique: Orange Growth Tubes and Cracks with Purple “Halos”

Fig. Par69d Fig. Par69a-d Microphotographs showing growth tubes in copper- bearing tourmaline from Mozam- bique. View in direction perpendicu- lar to the c-axis (Fig. Par69a-c). Note the presence of purple “halos” around the orange growth tubes. This purple “halos” was also found adjacent to fissures in the tourmaline that also contained the same orangey material fillings in extremely thin films. The purple “halos” are interpreted as the result of natural irradiation (See Box Par1 and Lit Par48). Composition of orangy materials: The orange substance in the growth tubes has been measured by LA-ICP-MS in two other samples. Increased concentrations of Fe, REE (Dominated by Ce, see Fig. Par76e), Mg, Cr, V, Pb and Ba (See Fig. Par76a and 76d) occurred along with U (Fig. 76g and 78g). No Cu- or Mn-enrichments were detected in Fig. Par69c these zones (Fig. Par75b).

44 Inclusion Research Case Study of a Copper-Bearing Tourmaline from Mozambique: Opaque Inclusions

Fig. Pat70a

Fig. Par70a-b 3-phase inclusions are found in the cooper-bearing tourmaline from Mozambique (Fig. 67a). The solid daughter minerals in the fluid inclusions are highly reflective and of a color typical for “native copper”. No further attempts have been made yet to identify them by more sophisticated methods (e.g. SEM-EDS or Raman).

Fig. Pat70c Fig. Par70c Microphotograph of a highly reflecting opaque inclusion in a bluish-green copper-bearing tourmaline from Mozambique (Type C). The opaque inclusion shows a narrow purple “halo” around it. This “halo” is interpreted as Fig. Pat70b induced by irradiation (See also Lit. Par48). It is therefore most likely that the inclusion is radioactive. 45 Inclusion Research Case Study of a Copper-Bearing Tourmaline from Mozambique: Summary and Interpretation

BOX PAR1: SUMMARY AND INTERPRETATION OF INCLUSIONS IN BLUISH-GREEN TOURMALINES FROM MOZAMBIQUE (FIG. PAR69-71):

The following inclusion features were found: of the tourmalines of this inclusion case study Orangy filled growth tubes and cracks (Fig. see the inlayed table. These tourmalines are Par68a-c and 69d) without or with purple halos characterized by high Mn-concentrations. (Fig. Par68b-c and 69a-d), opaque inclusions A theory of the formation of the “purple” halos with purple halos (Fig. Par70c) and 2- and was published at the printing date of this report 3-phase fluid inclusions (solid, liquid and (Lit. Par48). It is believed that these halos were vapor) (Fig. Par71a-c). All observation was produced by irradiation. During LA-ICP-MS made in faceted samples (Fig. Par67b) origi- analysis of orangy contaminations in the tubes nating from the same unheated tourmaline and cracks, we detected isolated uranium- rough (Fig. Par67a-b). These tourmalines were concentrations that are 10x higher than the classified as Type C (See Fig. Par90a-b). For concentrations found in the tourmaline matrix the chemical compositions of minor elements and about 30-60x above the detection limit (0.01ppm) in two different samples (Fig. Chemical Concentrations of Minor and Par76g and 78g). The presence of this radioac- Trace Elements of “Type C”- Tourmalines tive element in the orange materials is support (See Fig. Par67b) for the theory of formation of the “halos” by bluish-green pastel-green green yellowish-green irradiation (Lit. Par48). Furthermore, “halos” Mn (in %) 3.23 (6) 4.69 (2) 4.46 (4) 3.88 (1) are also observed around isolated solid inclu- STDEV 1.09 0.17 0.33 sions that are not associated to cracks and Cu (in %) 0.16 (6) 0.22 (2) 0.22 (4) 0.22 (1) tubes (Fig. Par70c). This is further supporting STDEV 0.07 0.04 0.05 the theory. The “halos” around these inclu- Fe (in %) 0.03 (6) 0.03 (2) 0.03 (4) 0.06 (1) sions, however, occur from the radiation that STDEV 0.03 0.01 0.04 are produced by the mineral inclusion itself and Bi (in %) 0.02 (6) 0.02 (2) 0.02 (4) 0.02 (1) not from contaminated orange colored STDEV 0.01 0.00 0.00 substances. Elevated Cu-concentrations were not found in the orange zones (Other elements ED-XRF analysis in wt.-%, averaged from a number of measurements (in brackets) and divided into present, see Fig. Par76a-f and 78c-g). color groups (Definition Type C, see Fig. Par90)

Fig. Par71a

Fig. Par71a-b Fluid inclusions were frequently present in these Mozambique tourmalines. The picture shows 2-phase inclusions found in a sample originating from the same rough of Fig. Par67a. Note that the fluid inclusion tubes do not have any expansion cracks. Therefore, no indications are present that the tourma- Fig. Par71b line has been subjected to a heat-treatment.

46 Color-Zoning in Copper-Bearing Tourmalines from Mozambique

Sample No. GRS-Ref S0147 Type B (ED-XRF) (24.463 ct) Mn = 0.66 (wt.-%) Rim Cu = 0.34 Fe = 0.05 Bi = 0.11

Core (ED-XRF) Type B Type C (ED-XRF) Mn = 1.27 (wt.-%) Mn = 1.33 (wt.-%) Cu = 0.15 Type C Cu = 0.27 Fe = 0.03 Fe = 1.44 Bi = 0.01 Bi = 0.07

Core

Fig. Par72a

Purple (ED-XRF) Sample No. GRS-Ref S0146 Mn = 0.31 (wt.-%) (26.738 ct) Cu = 0.30 Fe = 0.00 Bi = 0.17

Greenish-Blue (ED-XRF) Mn = 0.01 (wt.-%) Cu = 0.23 Fe = 0.07 Bi = 0.45 Fig. Par72b

Fig. Par72a-b Color-zoned unheated copper-bearing tourmalines from Mozambique (GRS collection). Note the typical succession of colors from the core to the rim: Purple core, greenish-blue and blue intermediate growth zone and green rim. The outermost rim may be yellowish-green followed by a dark green outer layer. The same type of materials was also described in the literature (Lit. Par33). ED-XRF chemical analyses of the color zones are included. According to our classification (Fig. Par90a), the outer green rim in Fig. Par72a is a “Type C”-tourmaline.

Fig. Par73a Fig. Par73b Fig. Par73a-b Microphotograph of two Mozambique tourmalines with vivid green and vivid purple color. Both faceted stones contained growth tubes with orange colors. Purple “halos” were absent. 47 LA-ICP-MS Analysis Profiles of Multicolored Tourmaline from Mozambique Sample No. GRS-Ref3134.

Type A (ED-XRF) Rim (ED-XRF) Mn = 0.14 (wt.-%) Rim Mn = 0.61 (wt.-%) Cu = 0.31 Cu = 0.05 Fe = 0.00 Fe = 1.05 Bi = 0.14 Type B Bi = 0.32

Core Type A Last LA-ICP-MS crater

Fig. Par74 Photograph of multi- Type B (ED-XRF) colored tourmaline from Mozam- bique, Sample No. GRS-Ref3134 Mn = 0.005 (wt.-%) (20.378 ct). Violet, blue and green Cu = 0.27 color zoning is present (from core to Fe = 0.01 rim). Laser ablation craters are visible (size 60 micrometers). Bi = 0.27 Chemical analysis profiles see Fig. Par 75a-f.

6000 Fig. Par 75a Variation in Cu-, Mn- and Mn Bi-concentrations. Cu Bi max 5000 Bi The color-zoning can be correlated with the chemical Cu>Mn variations as measured by LA-ICP-MS (in ppm) and by 4000 ED-XRF (Fig. Par74, 75a-b and 76a-f). Low Cu-concentrations are found in the purple core. 3000

ppm They increase towards the blue part of the crystal and Mn max Mn>Cu decrease towards the rim. 2000 Mn-concentrations are high in the purple core and decrease towards the blue color zone. In the rim, they 1000 increase to the highest measured value in the entire Bi low profile. Highest Mn/Cu-ratios are found in the purple core 0 and in the outer rim (Fig. Par75b). 1 6 11 16 21 26 31 36 41 46 51 56 61 66 71 76 81 86 91 96 101106111 116 121126 Fig. Par75a Lowest Bi-concentrations are found in the core of the crystal. Towards the rim, the Bi-concentrations constantly 5 increase. Highest Bi/Mn-ratios are found in the transition Mn/Cu 4.5 from the blue to the green color zone Pb/Be Rim 4 Bi/Cu The trend of variations in Bi-concentrations is opposite to the trend observed in tourmalines from Brazil (See Fig. 3.5 Neon-blue Par59a, 62a and 66a). 3 In the outer dark green rim of the crystal, the 2.5 Mn-concentrations increase along with ratio

2 Fe-concentrations (not measured by LA-ICP-MS, ED-XRF data, see Fig. Par74). 1.5 Fig. Par75b Variation in Mn/Cu-, Bi/Cu- and Pb-Be- 1 Core ratios 0.5 Pb/Be-ratio decrease toward the rim and an opposite 0 1 6 11 16 21 26 31 36 41 46 51 56 61 66 71 76 81 86 91 96 101 106 111 116 121 trend is observed for the Mn-Cu-ratio and Bi/Cu-ratio. measured points along profile They increase towards the rim. Note a sudden change of ratios is found at the transition zone from the purple core Fig. Par75b to the “neon”-blue color zone. 48 LA-ICP-MS Analysis Profiles of Copper-Bearing Tourmaline from Mozambique Sample No. GRS-Ref3134

100 Fig. Par76a-b Variation in chemi- Be “Neon”-blue 90 cal compositions of minor and Mg trace elements in relation to 80 Sb Rim color zoning (LA-ICP-MS analy- ses) Pb 70 Pb>Be Sn Regarding the concentrations of 60 V Be and Pb, a sudden change can be observed from the purple core 50 Cr to the violet/blue part of the crystal. ppm Both elements increase in 40 concentrations in this part of the crystal. Towards the green rim, 30 Pb-concentrations decrease and Be-concentrations increase. 20 Core Mg-values remain at or below the 10 detection limit in large parts of the crystal. In the outer rim, however, 0 1 6 11 16 21 26 31 36 41 46 51 56 61 66 71 76 81 86 91 96 101 106 111 116 121 126 the Mg-concentrations increase. Fig. Par76a In the green rim Mg-concentrations increase along with Sn (Fig. Par76a). 100

90 Mg Fig. Par76b-c Variation in Fe-, Pb Zn- and Ti-concentrations 80 Zn Fe-, Zn- and Ti-concentrations are 70 Pb max enriched in the green rim of the 60 tourmaline crystal. At isolated 50 positions, they are enriched to ppm relatively high values. These 40 concentrations can be correlated 30 with contaminated orange cracks or tubes. 20

10 Traces of V and Cr are not present as in the tourmaline. They are 0 Zn high 1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89 93 97101105109113117121125129 restricted to contaminated tubes or Fig. Par76b cracks as well (Fig. Par76a).

Variation in Ge- and 1800 Sc-concentrations (See Tab. 1600 Fe/10 Fe, Ti, Zn Par05) max Ti 1400 Ge-concentrations constantly Znx5 1200 increase from the core to the rim. Sc remains low over the entire 1000 Core Rim profile and increase towards the ppm 800 outer rim only (Ge- and Sc-concentrations see Tab. 600 Par05). The increase of Sc in the 400 green rim can be correlated with 200 the increase of Mg- and Sn-concentrations. 0 1 6 11 16 21 26 31 36 41 46 51 56 61 66 71 76 81 86 91 96 101 106 111 116 121 126 measured points along profile Fig. Par76c

49 LA-ICP-MS Analysis Profiles of Copper-Bearing Tourmaline from Mozambique Sample No. GRS-Ref3134

5000 16000 Fig. Par76d-g.Variations of chemi- Mg (L) Sb, Sn, Mg, cal compositions in correlation to 4500 Be max Cr (L) 14000 color zoning). Ba*10 (L) 4000 Very high Fe-concentrations are Fe (R) 12000 found in tubes and cracks in several 3500 (L) = left scale Mg, Cr, Ba, (R) = right scale positions inside the tourmaline. They Fe contam 10000 are not part of the chemical composi- 3000 ppm (R) tion of tourmaline. These localized 2500 8000 “contaminated zones” do also contain higher concentrations such as Ba ppm (L) 2000 and REE (Rare earth elements). 6000 These element concentrations are 1500 not correlated to the color zoning in 4000 the tourmaline. Other changes in 1000 element concentrations, however, can be correlated with the different 2000 500 growth zones in the tourmaline:

0 0 An increase in Ca is found at the 1 6 11 16 21 26 31 36 41 46 51 56 61 66 71 76 81 86 91 96 101106111 116121126 transition from the purple core to the Fig. Par76d 5 0.9 bluish part of the crystal. In the rim, the concentrations of Ca strongly La (L) La 4.5 0.8 increase (Fig. Par76f). This increase Ce (L) Nd in Ca-concentrations in the rim is 4 Nd Pr (L) Nd 0.7 correlated with an increase of Fe- Nd (R) REE contam 3.5 and Mg-concentrations (Fig. Par76d). Gd (R) 0.6 ppm (R) 3 (L) = left scale Ce REE elements increase slightly in the (R) = right scale 0.5 outer rim. 2.5 Nd Among the rare earth elements ppm (L) 0.4 2 present, La, Ce and Nd are dominant Gd 0.3 (Fig. Par76e). Localized enrichments 1.5 can be correlated with orange cracks La 0.2 and tubes. 1 Gd 0.5 La 0.1

0 0 1 6 11 16 21 26 31 36 41 46 51 56 61 66 71 76 81 86 91 96 101106111 116121126 Fig. Par76e 2800 1.4 Ba Ba Ca Ca max Th (R) Fe max 2300 K 1.2 Ba U Fe 1 U Th, Ba, U contam 1800

0.8 1300 ppm ppm 0.6 U 800 0.4 K, Fe contam 300 0.2

0 0 1 11 21 31 41 51 61 71 81 91 101 111 121 1 11 21 31 41 51 61 71 81 91 101 111 121 Fig. Par76g measured points along profile Fig. Par76f measured points along profile

Fig. Par78g Variation in Ba-, Th- and U-concentrations Th-concentrations can be correlated with the color zoning in the tourmaline. Lowest Th- concentrations are found in the purple growth zone. They increase in the “neon”-blue growth zone. The U-concentrations are located at extremely small isolated areas that may also contain concentrations of Ba, REE (La, Ce, Nd and Gd, see Fig. Par76e), as well as Fe, Cr, Mg (Fig. Par76d), Pb, V (Fig. Par76a), Ti (Fig. 76c) and K (Fig. Par76f). These element concentrations are localized in areas with orangy cracks or tubes in the tourmaline. 50 LA-ICP-MS Analysis Profiles of Multicolor Tourmaline from Mozambique Sample No. GRS-Ref7782

Rim

Core

Fig. Par77 Photograph of a multi-colored tourmaline from Mozambique, Sample No. GRS-Ref3134. Violet, greenish-blue and green color zoning is present (from core to rim). Laser ablation craters are visible (size 60 micrometers). Chemical analysis profiles see Fig. Par78a-f. 6000 Fig. Par78a Variations in Cu-, Mn and Mn Bi, Mn High

Bi dropping, Mn increasing: Bi- concentrations Cu Type B 5000 Concentrations of Cu, Mn and Bi are Bi shown in a profile across a Mozambique Trend to Type C tourmaline. From the core to the rim the 4000 following chemical variations are Cu>Mn Type A Cu max observed: 3000 Cu-concentrations are high in the purple

ppm core. Abrupt increase in the violet to greenish-blue part of the crystal and 2000 decreasing concentrations towards the rim. 1000 Mn-concentrations are relatively high in the core and decrease towards the middle part of the tourmaline. In the rim, 0 manganese values increase to their 1 11 21 31 41 51 61 71 81 91 101 111 121 131 highest measured values. Fig. Par78a Bi-concentrations are high over the entire 6 measured profile. Highest concentrations Mn/Cu are found in the rim of the crystal. Lowest Pb/Be Bi concentrations are found along with 5 Bi/Cu low Mn-concentrations in the greenish- Rim blue part of the crystal. 4 Fig. Par78a Variations in Mn/Cu-, Core Bi/Cu-and Pb/Be-ratios 3 High Mn/Cu-ratios are measured in the green colored rim. Lowest Mn/Cu-ratios are formed in the greenish-blue color 2 zone. Bi/Cu-ratios continuously increase

ratio (based on ppmw) from the core to the rim. In the middle of 1 the blue color zone, Bi/Cu-ratios are continuously increasing towards the rim. Highest Bi/Cu-ratios are found in the 0 1 11 21 31 41 51 61 71 81 91 101 111 121 131 green rim. measured points along profile Pb/Be-ratios are well above 1 (Pb higher than Be). During the growth phase Fig. Par78b producing green colors, Be dominates Pb and therefore, Pb/Be-ratios are decreas- 51 ing (Fig. Par78b). LA-ICP-MS Analysis Profiles of Copper-Bearing Tourmaline from Mozambique Sample No. GRS-Ref7782

Fig. Par78c-f Variations of chemical element concentrations in relation to color zoning. In the chemical profile analysis of the Mozambique tourmaline GRS-Ref7782, the following elements increased in the rim: Fe, Ti, Zn (Fig. Par78d), REE-elements (Fig. Par78d) and Mg (Fig. Par78c). Extremely low Mg-concentrations were present in the greenish-blue and purple color zones. Among the REE- elements, Ce shows the highest concentrations. However, in comparison to the concentrations found in Brazil, the Mg- and REE-concentrations found in the samples from Mozambique are low. Isolated high concentrations of Fe, Ti, Zn, Mg, Cr and Ba are found in the area of the orangy zones, which are interpreted as contaminations that occurred after the formation of the tourmalines (Fig. Par78e; See also Box Par1). A similar situation was found in the other sample from Mozambique (Sample No. GRS-Ref3134, e.g. See Fig. Par76g).

Fig. Par78c Fig. Par78e 160 90 4000 Mg (L) Mg, Fe Mg 80 Cr (L) 3500 Pb max Ba*10 (L) max 140 Pb 70 Fe (R) 3000 (L) = left scale Zn 60 (R) = right scale 2500 ppm (R) 120 50 Mg, Cr, 2000 40 ppm (L) Ba, Fe 100 1500 30 contam Core Zn max 1000 80 20

ppm Rim 10 500 60 Mg, Pb, Zn 0 0 contam 1 11 21 31 41 51 61 71 81 91 101 111 121 131 measured points along profile 40

20

0 1 11 21 31 41 51 61 71 81 91 101 111 121 131 Fig. Par78d measured points along profile Fig. Par78f 1.6 400 REE max Fe/10 La 350 Fe, Ti, Zn Ti 1.4 Ce La max 300 Znx5 Nd Rim 1.2 250 1 200 Ce ppm Core Ce 150 Fe, Ti, Zn 100 0.8 contam ppm 50

0.6 Ce 0 Ce 1 11 21 31 41 51 61 71 81 91 101 111 121 131 measured points along profile 0.4 Fig. Par78g Variations in Th- and 0.2 U-concentrations

0 Th-concentrations can be correlated with 1 11 21 31 41 51 61 71 81 91 101 111 121 131 the color zoning in the tourmaline. 3 Fig. Par78g U U Highest concentrations are found in the 2.5 U purple growth zone. The Ba, U contam Th U-concentrations are found at extremely Ba 2 small isolated areas along with other elements not related to tourmaline (Fig. 1.5 ppm Par78c-f) and are localized in the areas 1 of orangy contaminated cracks and tubes. Isolated enrichments of the REE 0.5 elements Ce and La (Fig. Par78d) occur 0 in the isolated zones containing U. 1 11 21 31 41 51 61 71 81 91 101 111 121 131 measured points along profile 52 Comparison of Chemical Analysis Profiles: Ga- and Pb-Concentrations LA-ICP-MS Analysis

BOX Par2 COMPARISON OF VARIATION OF PB- AND GA-CONCENTRATIONS IN MULTICOLORED COPPER-BEARING TOURMALINES FROM BRAZIL AND MOZAMBIQUE Brazil (Paraiba) Mozambique 250 Ga GRS-Ref2976-2 Pb 600 GRS-Ref3134 200 Rim Core Rim 500

150 400 Core Neon-blue Rim

ppm ppm Ga 300 100 Pb 200 50 100

0 0 1 6 11 16 21 26 31 36 41 46 51 56 61 66 71 76 81 1 5 9 13 17 21 25 29 33 37 41 45 49 53 57 61 65 69 73 77 81 85 89 93 97101105109113117121125129 Fig. Par79a Fig. Par80a

400

350 200 Ga 180 300 Pb GRS-Ref2965 160 250 140 Core Rim Ga 120 Core Rim 200 Pb GRS-Ref7782 100 ppm ppm 150 80 60 100 40 50 20 0 0 1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49 1 11 21 31 41 51 61 71 81 91 101 111 121 131 Fig. Par79b Fig. Par80b

250 Fig. Par79a-c and 80a-b Chemical profile analysis of 2 Ga Rim Pb GRS-Ref3111-a copper-bearing tourmalines from Mozambique and 3 samples from Brazil (Paraiba) are shown. A different 200 trend in the concentrations of Pb and Ga was found. The minimum of the Ga-concentrations is found in the 150 bluish-green growth zones of the Brazilian tourmalines. Core This is not observed in tourmalines from Mozambique.

ppm In general, higher Ga-concentrations are found in the 100 Mozambique tourmalines. The highest Ga-concentrations in the Brazilian tourmalines are found in the transition zone of the bluish-green to green 50 growth sectors (overlapping area see Fig. Par79a-b). Pb-concentrations are highest in the purple core of the Brazilian tourmalines. In Mozambique tourmalines, the 0 Pb-concentrations are at its maximum in the greenish- 1 6 11 16 21 26 31 36 41 46 51 56 61 blue growth zone. Ga and Pb-concentrations are measured points along profile Fig. Par79c therefore useful for the distinction of these two tourma- line groups from the two different origin (Fig. Par81 and 82). However, the sum of the concentrations (Ga+Pb) as proposed in the literature (Lit. Par11) may not always be sufficient for origin determination.

53 The Ga-Pb Diagram for Origin Determination of Tourmalines LA-ICP-MS Analysis

Ga-Pb-Diagram (LA-ICP-MS) "neon"-greenish-blue ~ Paraiba blue ~ Mozambique blue ~ Paraiba blue green ~ Mozambique 140 dark-green ~ Paraiba green ~ Mozambique green ~ Paraiba neon-blue ~ Paraiba 120 purple ~ Mozambique purple ~ Paraiba violet ~ Mozambique violet ~ Paraiba violetish-blue ~ Paraiba 100 vivid green ~ Mozambique yellowish-green/green ~ Paraiba yellowish-green ~ Mozambique yellowish-green/green ~ Paraiba 80 neon-blue ~ Nigeria Mozambique Lit Par32

Mozambique Pb (ppm) 60

40 Brazil

20

Fig. Par81a 0 0 100 200 300 400 500 600 700 Ga (ppm) Ga-Pb-Diagram (LA-ICP-MS)

1200

1000 Nigeria

800

Pb (ppm) 600

400

200

Fig. Par81b 0 0 100 200 300 400 500 600 700 Ga (ppm) Fig. Par81a-b Pb-Ga diagram of different tourmalines from Brazil, Mozambique and Nigeria. The two elements Pb and Ga were found to be suitable for origin determination of copper-bearing tourmalines, provided the color-zones are separately considered. Pb-concentrations are considerable higher in Nigerian tourmalines (Fig. Par81b and Par82a). 54 The Ga-Pb and Cu-Ga-Diagram for Origin Determination of Tourmalines ED-XRF Analysis

2000 "neon"-greenish-blue ~ Paraiba Ga-Pb-Diagram (ED-XRF) blue to neon-blue ~ Mozambique blue to neon-blue ~ Paraiba 1800 bluish-green ~ Mozambique green ~ Mozambique 1600 green ~ Paraiba purple ~ Mozambique purple ~ Paraiba 1400 violet ~ Mozambique violet ~ Paraiba yellowish-green ~ Paraiba 1200 yellowish-green ~ Mozambique greenish-blue ~ Nigeria greenish-blue ~ Mozambique 1000 blue ~ Nigeria pastel-violet ~ Nigeria Pb (ppm) Nigeria purple ~ Nigeria 800 blue ~ Rio Grande do Norte blue-green ~ Rio Grande do Norte green ~ Rio Grande do Norte 600 yellowish-green ~ Rio Grande do Norte violet ~ Rio Grande do Norte 400

200 Fig. Par82a 0 0 100 200 300 400 500 600 700 Ga (ppm)

Cu-Ga-Diagram (ED-XRF)

600

500

400 Mozambique

Ga (ppm) 300

200 Nigeria Brazil

100

Fig. Par82b 0 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000 Cu (ppm) Fig. Par82a-b Pb-Ga and Cu-Ga diagram based on ED-XRF analysis (in ppm) after correction against LA-ICP- MS analysis (See Fig. Par82d). The number of samples was extended with this method to 112 samples. The measured area for ED-XRF analysis was between 0.2 and 2mm for ED-XRF analysis and 60 microns for LA-ICP-MS analysis. More spots were measured on same samples by LA-ICP-MS analysis and more samples by ED-XRF (112 samples, 172 measured spots). Maximum Cu-concentrations were measured by ED-XRF in a tourmaline from Brazil (Batalha, Paraiba) with almost 2 wt.-%. The results of the ED-XRF analysis are in good agreement with those of the LA-ICP-MS analysis (compare Fig. Par82b with Fig. Par82c and Fig. Par81b with Fig. Par82a). 55 The Cu-Ga-Diagram for Origin Determination of Tourmalines Comparison of ED-XRF with LA-ICP-MS Analysis

Cu-Ga-Diagram (LA-ICP-MS) Fig. Par82c The 700 Cu-Ga diagram based "neon"-greenish-blue ~ Paraiba on LA-ICP-MS blue ~ Mozambique analysis (Averages blue ~ Paraiba blue green ~ Mozambique see Tab. Par03-06). 600 dark-green ~ Paraiba green ~ Mozambique green ~ Paraiba This test was found to neon-blue ~ Paraiba be useful, because purple ~ Mozambique the Cu-concentrations 500 purple ~ Paraiba violet ~ Mozambique are often higher in the violet ~ Paraiba Brazilian tourmalines violetish-blue ~ Paraiba than in the counter- Mozambique vivid green ~ Mozambique yellowish-green/green ~ Paraiba parts from Mozam- 400 yellowish-green ~ Mozambique bique. An opposite yellowish-green/green ~ Paraiba neon-blue ~ Nigeria trend was observed Mozambique Lit Par32 for the Ga (ppm) 300 Ga-concentrations. (See Box Par2). Brazil 200

100 Nigeria

0 0 2000 4000 6000 8000 10000 12000 14000 Cu (ppm)

ED-XRF calibration by LA-ICP-MS (Mn) ED-XRF calibration by LA-ICP-MS (Bi) 1.4 0.6 0.5 y = 0.740x 3 (wt-%) R² = 0.32 y = 0.589x 0.4 2 R² = 0.939 0.3 0.2 1 0.1 Bi (LA-ICP-MS) Mn (LA-ICP-MS) (wt-%) 0 0 0 1 2 3 4 5 6 7 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 Mn ED-XRF (wt.-%) Bi ED-XRF (wt.-%)

ED-XRF calibration by LA-ICP-MS (Cu) ED-XRF calibration by LA-ICP-MS (Ga) 1.4 0.5 1.2 0.4 (wt-%) 1 y = 0.694x 0.8 0.3 R² = 0.713 y = 0.740x 0.6 0.2 0.4 R² = �0.32 0.2 0.1 Cu (LA-ICP-MS) 0 Ga (LA-ICP-MS) (wt-%) 0 0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 Cu ED-XRF (wt.-%) Ga ED-XRF (wt.-%)

Fig. Par82d Shows the linear regression of ED-XRF concentrations against LA-ICP-MS data from the same measuring spot. The ED-XRF needed to be corrected to lower values by a factor (0.6-0.7) due to the technical specifications and the calculation routine of the particular ED-XRF instrument. The LA-ICP-MS standard set was used to calibrate the ED-XRF data (See methods and calibration protocol in Box Par03). Similar regression slopes were found for different elements (slightly different for the element Mn).

56 Origin Determination of Copper-Bearing Tourmalines: Flow Chart of Methods

BOX PAR3 CALIBRATION FLOW CHART FOR DIFFERENT METHODS (A-D) USEFUL FOR ORIGIN OF COPPER-BEARING TOURMALINES (E)

(A) EMPA ANALYSIS Determination of major and minor (1)* elements to generate matrix (B) LA-ICP-MS ANALYSIS matched calibration standards (master set) Determination of major, minor and trace elements using NIST 610 and by EMPA Fig. Par28a-c determined major elements for internal Tab. Par01 standardization (e.g. Al) to generate a large quantitative data set for tourma- lines. The data sets contain concentra- (1) tions and their variability expressed as relative standard deviation. (2) (C) ED-XRF ANALYSIS Compare Fig. 28a-c (EMPA) with Establishing of calibration function Fig. Par33a-b and Par36a (LA-ICP-MS) for Fe, Cu, Zn, Pb, Bi, Mn, Ga by ED-XRF using the by EMPA and Tab. Par02-05 LA-ICP-MS characterized matrix matched calibration materials. (2) Cu/Ga, Pb/Ga and the ternary Bi-Cu-Mn diagrams are used for a (3) first evaluation. (D) LIBS ANALYSIS Fig. Par82b and Fig. Par90b Establishing a calibration function for Be, Mg and Si, Cu, Mn using the same calibration materials as used for ED-XRF analysis to provide semi- quantitative data for the light elements. Use Mn-Cu-Be diagram. (E) ORIGIN DETERMINATION Fig. Par85 Origin determination of Copper- bearing tourmalines based on ED-XRF and LIBS generated analysis of "unknown samples"

* (1)-(3) Legend: Step 1 and 2 are based on a research project to generate a large data set on selected tourmaline samples, which can be successively used for major, minor and trace element determinations by analytical techniques well known in gemology.

57 Comparison of Variation of Pb- and Be-Concentrations in Multicolored Copper-Bearing Tourmalines from Brazil and Mozambique

BOX PAR4 COMPARISON OF PB- AND BE-CONCENTRATIONS IN MULTICOLORED COPPER-BEARING TOURMALINES FROM BRAZIL AND MOZAMBIQUE

Brazil (Paraiba, Batalha) Brazil (Quintos, Rio Grande do Norte) 80 35 GRS-Ref2079 Pb GRS-Ref2967 Fig. Par83a Pb 70 30 “Neon”-Blue Be Be 60 25 Core Rim Rim Rim 50 20 40 ppm ppm 15 30 10 20 10 Inner rim 5 (no core) Fig. Par83d 0 0 1 6 11 16 21 26 31 36 41 46 51 56 61 66 71 76 81 1 6 11 16 21 26 31 36 41 46 51 56 Mozambique 50 140 45 GRS-Ref2965 GRS-Ref7782 120 40 35 Core Rim 100 Core Rim 30 80 25 ppm ppm 20 60 15 40 10 20 5 Fig. Par83b Fig. Par83e 0 0 1 6 11 16 21 26 31 36 41 46 1 11 21 31 41 51 61 71 81 91 101 111 121 131

Brazil (Paraiba, Batalha 1988) 80 350 Pb GRS-Ref3134 Fig. Par83f Pb GRS-Ref3111-a Fig. Par83c 70 Be 300 Be 60 250 (Pb/Be)x100 50 200 Rim Core 40 ppm Core Rim 150 30

100 20 ppm and Pb/Be-ratios 50 10

0 0 1 6 11 16 21 26 31 36 41 46 51 56 61 1 11 21 31 41 51 61 71 81 91 101 111 121 measured points along profile measured points along profile Fig. Par83a-f Comparison of Variation of Be- and Pb-concentrations in tourmalines from different origins. Pb- and Be-concentrations vary within the samples and are different between samples from different origins. This results in different ratios of Pb/Be within the same sample. The use of Pb/Be-ratios as a critical value for origin determination (See Fig. 88a-d) as published in the literature (Lit. Par11) must be therefore used with caution. For the variations of Be-concentrations in different color zones see Fig. Par84a-c and Fig. Par86.

58 The Be-(Mn+Cu)-Diagram for Origin Determination of Copper-Bearing Tourmalines (LA-ICP-MS Analysis)

(Cu+Mn)-Be-Diagram: Violet and Purple Colors (LA-ICP-MS) Fig. Par84a-c Cu+Mn-Be-Diagram 80 separated for different Paraiba-2965-Violet color groups of copper- Paraiba-2972-purple bearing tourmalines from 70 Paraiba-2976-2-purple Brazil, Mozambique and Paraiba-3111-a-purple Nigeria (LA-ICP-MS, in Mozambique-2939-Violet µg/g). The fields of tow 60 Mozambique-3134-violet Mozambique-3143-Purple different mining areas in Mozambique-7782-purple Brazil (Batalha and 50 Mozambique Mozambique-7782-violet Quintos) are separately shown.

40 Note that the samples from the Batalha mine have highest Cu+Mn- Be (ppm) 30 concentrations in the group Batalha Brazil of purple and blue colors (Fig. 84a-b). 20 Batalha The highest Cu+Mn-values 10 in the samples from Mozambique are found in Fig. Par84a the group of various green 0 colors (Fig. Par84c). 0 5000 10000 15000 20000 25000 30000 35000 40000 Cu + Mn (ppm) The Be-concentrations are different according to the (Cu+Mn)-Be-Diagram: Greenish-Blue, Violetish-Blue and Blue Colors color-zone of the mea- (LA-ICP-MS) 80 sured tourmaline: Fig. Par84b In the group of violet to Mozambique purple colors, the tourma- 70 lines from Mozambique had higher Be-values than the Brazilian counterparts (Fig. 84a). 60 Lower Be-concentrations were found in the blue and 50 greenish-blue colored tourmalines from the Batalha Quintos mine (Brazil) in Batalha comparison to the concen- 40 Brazil trations found in the B e (ppm) samples from Mozambique (Fig. Par84b). 30

Paraiba-2079-"neon"-greenish-blue Paraiba-2079-violetish-blue 20 Paraiba-2965-Blue Quintos Paraiba-2972-neon-blue Paraiba-2976-2-"neon"-greenish-blue Paraiba-2976-Blue 10 Paraiba-3111-a-Blue Mozambique-3134-blue Mozambique-Moz 7782-Blue 0 0 5000 10000 15000 20000 25000 30000 35000 40000 45000 Cu + Mn (ppm) 59 Ternary Be-Mn-Cu Diagram for Origin Determination of Copper-Bearing Tourmalines (LA-ICP-MS Analysis)

(Cu+Mn)-Be-Diagram: Yellowish-Green and Green Colors (LA-ICP-MS) 90 Paraiba-2079-green Paraiba-2965-Yellowish-green 80 Paraiba-2972-green Paraiba-2972-yellowish-green Paraiba-2976-yellowish green/green 70 Paraiba-2976-2-yellowish-green Batalha Paraiba-3111-a-dark-green Paraiba-3111-a-yellowish-green 60 Mozambique-2942-green Mozambique-2942.2-Yellowish-green Mozambique-2943-blue green Mozambique-3134-blue green 50 Mozambique-3134-yellowish green Mozambique-3138-vivid green Brazil Mozambique-7782-yellowish-green e (ppm)

B 40 Mozambique Mozambique 30

20 Quintos

10 Fig. Par84c 0 0 5000 10000 15000 20000 25000 30000 35000 40000 45000 Cu + Mn (ppm)

Cu-Mn-Be-Diagram: LIBS Fig. Par85 and 86 Shows the ternary Cu-Mn-Be- diagram based on all data measured with LA-ICP-MS Be x 5 (in µg/g, Be-concentrations are multiplied by 50) and by Fig. Par85 LIBS-analyses of same samples with less measuring points (in counts, Be-concentrations are multiplied by 5). Comparing the two methods, it can be seen that the LIBS counts for Be (relative to those of Cu and Mn) was Mozambique much higher than those obtained by LA-ICP-MS Brazil analysis. Therefore, a series of LA-ICP-MS analyzed standards are needed if semi-quantitative data from LIBS-analysis are required (Box Par3). It can be seen in Fig. Par85, 86 that a field of high Be-concentrations in relation to Cu- and Mn-concentrations is occupied by samples from Mozambique. For certain samples, this provides additional information for origin determination. Cu Mn Cu-Mn-Be-Diagram: LA-ICP-MS Be x 50 Be x 50

Fig. Par86

Blue colors only Mozambique Mozambique Brazil Brasil Nigeria

Cu Mn Cu Mn

60 The (Cu+Mn)-Pb/Be-Diagram for Origin Determination of Copper-Bearing Tourmalines (LA-ICP-MS Analysis)

Be-Mg-Diagram (LA-ICP-MS)

100 Fig. Par87 In addition "neon"-greenish-blue ~ Paraiba blue ~ Mozambique to differences in 90 blue ~ Paraiba Be-concentrations, blue green ~ Mozambique the Mg-concentrations dark-green ~ Paraiba green ~ Mozambique are helpful in separat- 80 green ~ Paraiba ing green copper- neon-blue ~ Paraiba purple ~ Mozambique bearing tourmalines 70 purple ~ Paraiba from those of Mozam- violet ~ Mozambique bique with same color. violet ~ Paraiba violetish-blue ~ Paraiba Mg-concentrations 60 vivid green ~ Mozambique were found to be yellowish-green/green ~ Paraiba yellowish-green ~ Mozambique higher in green yellowish-green/green ~ Paraiba copper-bearing 50 neon-blue ~ Nigeria tourmalines from Mozambique Lit Par32 Be (ppm) Brazil. 40 Brazil Green Colors 30

20

10

Fig. Par87 0 0 500 1000 1500 2000 2500 3000 3500 4000 Mg (ppm) (Cu+Mn)-Pb/Be-Diagram (LA-ICP-MS) 45000

Paraiba-2079-"neon"-greenish-blue 40000 Paraiba-2079-violetish-blue Paraiba-2965-Blue Paraiba-2972-neon-blue 35000 Paraiba-2976-2-"neon"-greenish-blue Paraiba-2976-Blue Paraiba-3111-a-Blue 30000 Mozambique-3134-blue Mozambique-Moz 7782-Blue Mozambique Nigeria-N1533-neon-greenish-blue 25000 + Nigeria-N0671-pastel-greenish-blue Brazil Nigeria-2877-pastel-greenish-blue Nigeria-2876-pastel-greenish-blue 20000 Nigeria-N0441-pastel-greenish-blue Cu + Mn (ppm)

15000 Nigeria 10000

5000

0 Fig. Par88a 0 10 20 30 40 50 60 70 Pb / Be (ratio) 61 The (Cu+Mn)-Pb/Be-Diagram for Origin Determination of Copper-Bearing Tourmalines: Different Color Groups (LA-ICP-MS Analysis)

(Cu+Mn)-Pb/Be-Diagram: Violet and Purple Colors (LA-ICP-MS) 40000

35000 Paraiba-2965-Violet Paraiba-2972-purple Paraiba-2976-2-purple 30000 Paraiba-3111-a-purple Mozambique-2939-Violet 25000 Mozambique-3134-violet Brazil Mozambique-3143-Purple Mozambique-7782-purple n (ppm) 20000 M

Mozambique-7782-violet +

u C 15000 Mozambique

10000

5000

Fig. Par88b 0 0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 Pb / Be (ratio) (Cu+Mn)-Pb/Be-Diagram: Greenish-Blue and Blue Colors (LA-ICP-MS) 45000

Paraiba-2079-"neon"-greenish-blue 40000 Paraiba-2079-violetish-blue Paraiba-2965-Blue Paraiba-2972-neon-blue 35000 Paraiba-2976-2-"neon"-greenish-blue Paraiba-2976-Blue Paraiba-3111-a-Blue 30000 Batalha Mozambique-3134-blue Mozambique-Moz 7782-Blue 25000 n (ppm) M

+ Brazil

u 20000 C

15000

10000 Quintos 5000 Mozambique

Fig. Par88c 0 0 0.5 1.0 1.5 2.0 2.5 3.0 Pb / Be (ratio) Fig. Par88a-d The Cu+Mn versus Pb/Be-diagram from the literature (Lit. Par 11) was tested. It is seen, that distinctive fields for Mozambique, Brazil and Nigeria can be defined. It is important to separate the plots accord- ing to color of the tourmalines. High Pb/Be-ratio characterize the bluish Nigerian and Mozambique tourmalines of green colors split into two fields and can be separated from the Brazilian counterparts. This is mostly due to the fact that the Mn-concentrations in the green rim are strongly increasing (See Fig. Par75a, 78a). In the greenish-blue to blue colors, the Mozambique tourmalines have distinctive lower Cu+Mn-concentrations at overlapping Pb/Be-ratios. This observation may also explain the same spread of the data that were reported in the literature (Lit. Par11).

62 (Cu+Mn)-Pb/Be-Diagram:fier Origin Determination of Copper-Bearing Tourmalines: Different Color Groups (LA-ICP-MS Analysis)

(Cu+Mn)-Pb/Be-Diagram: Yellowish-Green and Green Colors (LA-ICP-MS) 45000 Mozambique 40000

35000

30000

25000 Quintos n (ppm) M

+

u 20000 C Brazil 15000 Paraiba-2079-green Mozambique-2942-green Paraiba-2965-Yellowish-green Mozambique-2942.2-Yellowish-green Paraiba-2972-green Mozambique-2943-blue green 10000 Paraiba-2972-yellowish-green Mozambique-3134-blue green Paraiba-2976-yellowish green/green Mozambique-3134-yellowish green Paraiba-2976-2-yellowish-green Mozambique-3138-vivid green 5000 Paraiba-3111-a-dark-green Mozambique-7782-yellowish-green Paraiba-3111-a-yellowish-green Mozambique Fig. Par88d 0 0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 Pb / Be (ratio)

(Ga+Pb)-(Cu+Mn)-Diagram: Violet and Purple Colors (LA-ICP-MS) 600 Paraiba-2965-Violet Paraiba-2972-purple 500 Paraiba-2976-2-purple Paraiba-3111-a-purple Mozambique-2939-Violet 400 Mozambique-3134-violet Mozambique Mozambique-3143-Purple Mozambique-7782-purple

b (ppm) Mozambique-7782-violet

P 300

+

a G

200 Brazil

100

Fig. Par89a 0 0 5000 10000 15000 20000 25000 30000 35000 40000 Cu + Mn (ppm)

63 (Ga+Pb)-(Cu+Mn)-Diagram for Origin Determination of Copper-Bearing Tourmalines: Different Color Groups (LA-ICP-MS Analysis)

(Ga+Pb)-(Cu+Mn)-Diagram: Greenish-Blue and Blue Colors (LA-ICP-MS) 500

450 Paraiba-2079-"neon"-greenish-blue Paraiba-2079-violetish-blue Paraiba-2965-Blue 400 Mozambique Paraiba-2972-neon-blue Paraiba-2976-2-"neon"-greenish-blue Paraiba-2976-Blue 350 Paraiba-3111-a-Blue Mozambique-3134-blue 300 Mozambique-Moz 7782-Blue Quintos

(ppm) 250

Ga + Pb 200 Brazil

150 45000 Fig. Par89b Batalha 100

50

0 0 5000 10000 15000 20000 25000 30000 35000 40000 Cu + Mn (ppm)

(Ga+Pb)-(Cu+Mn)-Diagram: Yellowish-Green and Green Colors (LA-ICP-MS) 500

450 Mozambique 400 Paraiba-2079-green Paraiba-2965-Yellowish-green 350 Paraiba-2972-green 45000 Paraiba-2972-yellowish-green Paraiba-2976-yellowish green/green 300 Paraiba-2976-2-yellowish-green Paraiba-3111-a-dark-green

(ppm) Quintos 250 Paraiba-3111-a-yellowish-green Mozambique-2942-green Mozambique-2942.2-Yellowish-green Ga + Pb 200 Mozambique-2943-blue green Mozambique-3134-blue green 150 Mozambique-3134-yellowish green Mozambique-3138-vivid green Batalha Mozambique-7782-yellowish-green 100 Brazil 50

0 Fig. Par89c 0 5000 10000 15000 20000 25000 30000 35000 40000 Cu + Mn (ppm) Fig. Par89a-c The (Ga+Pb)-(Cu+Mn) diagram for origin determination of cooper-bearing tourmalines of different origin (Lit. Par11) is tested. This critical test was found to be useful if the data are arranged into different color groups. The values of Nigeria are out of the range at highest Ga+Pb-concentrations. The field of Mozambique tourmalines splits into two different fields for the yellowish green colors (Fig. Par89c).

64 Classification of Copper-Bearing Tourmalines Using Mn- and Bi-Concentrations (LA-ICP-MS and ED-XRF Analysis )

Bi-Mn-Diagram for Classification of Copper-Bearing Tourmalines (LA-ICP-MS) 40000 "neon"-greenish-blue ~ Paraiba blue ~ Mozambique blue ~ Paraiba 35000 blue green ~ Mozambique Type C dark-green ~ Paraiba green ~ Mozambique Low Bi and High Mn green ~ Paraiba Mozambique neon-blue ~ Paraiba 30000 purple ~ Mozambique purple ~ Paraiba violet ~ Mozambique violet ~ Paraiba 25000 violetish-blue ~ Paraiba vivid green ~ Mozambique yellowish-green/green ~ Paraiba yellowish-green ~ Mozambique 20000 yellowish-green/green ~ Paraiba Intermediate Bi and neon-blue ~ Nigeria Mn (ppm) Mozambique Lit Par32 Intermediate Mn Brazil Type A 15000 Fig. Par90a The Bi-Mn High Bi and Intermediate Mn diagram as derived from Mozambique LA-ICP-MS analyses (total 10000 15 samples) of copper- bearing tourmalines from different origins

5000 High Bi and Low Mn Mozambique (Mozambique, Brazil and Type B Nigeria) and from the literature (Lit Par32). Highest Bi-concentrations 0 0 1000 2000 3000 4000 5000 6000 are found in tourmalines Bi (ppm) from Mozambique and Brazil that have the lowest Mn-concentrations. Three different types of Mozambique tourmalines have bee indicated based on Bi- and Mn-concentrations (Type A, B and C). Type B is found in the samples with low Cu-concentrations in the outer green rim of the crystals (Tab. Par05, Fig. Par74 and Fig. Par78a) and has low Mn- and high Bi-concentrations. Intermedi- ate Mn- and Bi-concentrations were observed in Brazilian tourmalines (rarely occupied by tourmalines from Mozambique and Nigeria. “Type C”- tourmalines are characterized by extremely high Mn- and low Bi-concentrations. This type of tourmaline is typically found in Mozambique.

Bi-Mn-Diagram for Classification of Copper-Bearing Tourmalines (ED-XRF) = 4.5 wt.-% 45000 "neon"-greenish-blue ~ Paraiba Fig. Par90b shows the blue to neon-blue ~ Mozambique Bi-Mn diagram based on blue to neon-blue ~ Paraiba ED-XRF analyses. In 40000 bluish-green ~ Mozambique green ~ Mozambique comparison to LA-ICP-MS green ~ Paraiba analysis, a larger number of 35000 Type C purple ~ Mozambique samples (over 112 samples, purple ~ Paraiba including those measured by 30000 violet ~ Mozambique LA-ICP-MS, total 174 violet ~ Paraiba yellowish-green ~ Paraiba analyses) were measured. 25000 yellowish-green ~ Mozambique greenish-blue ~ Nigeria Note that the same trends greenish-blue ~ Mozambique are found by the two differ-

Mn (ppm) 20000 blue ~ Nigeria pastel-violet ~ Nigeria ent methods LA-ICP-MS purple ~ Nigeria and ED-XRF. The samples 15000 blue ~ Rio Grande do Norte from Nigeria occupy the blue-green ~ Rio Grande do Norte area of low Mn- and 10000 green ~ Rio Grande do Norte Bi-concentrations. Definition yellowish-green ~ Rio Grande do Norte violet ~ Rio Grande do Norte of Type A and C see Fig. 5000 Par90a. Type A+B 0 0 2000 4000 6000 8000 10000 Bi (ppm) = 1 wt.-% 65 Conclusions

CONCLUSIONS (Fig. Par88 and Fig. Par89). However, the lines from the different locations and could be by natural irradiation (Lit. Par48). are also reported from Mozambique tourma- areas in critical diagrams, See Fig. Par82a-b). data of Abduriyim et al. (Lit. Par11) could not correlated to the different color zones in these lines (Lit. Par33). The element distribution It is important, however, that a “Standard-Set” High valuable copper-bearing tourmalines be plotted in some of our diagrams as they did tourmalines (Fig. Par91c-d). However, only Ba-contaminations were also found on the mapping in tourmalines are also important to (matrix matched calibration materials) is avail- occur in different color and large size and are only publish concentration ranges and ratios Cu and Mn are responsible for the color, not surface of rough tourmalines from Mozam- compare them with any future patterns that able that has been measured by both, EMPA produced in Brazil, Mozambique and Nigeria. and no individual quantitative results and the Bi. The Bi-Cu-Mn trends can be combined bique (See Tab. Par05). may occur in relation to potential new treat- and LA-ICP-MS (See Box Par3). We have The sizes and distribution of these gemstones standard deviation, respectively. However, with other elements, such as other minor or ments. presented only the data on unheated samples in the gem market were studied and a statistic the trends between different colored copper- trace elements. For example, in general much Our approach on chemical profile analyses in our charts and classified them according to about the trade has been published in this bearing Mozambique tourmalines including higher Cu-concentrations are found in tour- allowed us furthermore to identify some new Regarding the importance of different meth- color. It must be kept in mind that heat- report. These types of tourmalines include the variations in Fe and Ti as published in the malines from Brazil and much higher Ga- chemical evolution trends in copper-bearing ods useful for provenance determination of treatment may have been applied to tourma- many different color varieties and are found literature (Lit. Par 33) were plotted in concentrations are found in Mozambique tourmalines from different origins (e.g. REE- tourmalines, the following conclusions can be lines that may have changed their original as heated as well as unheated gems (Fig. diagrams and confirmed (Fig. Par76c, 78f, 81, tourmalines. The Cu/Ga-ratio was found a trends) that have not been reported in such made (See Box Par3). LA-ICP-MS in combi- color (See for example Lit. Par11 and 33). Par07 and 12). Unusual large sizes have 82 and 88). Because we focused on chemical very promising critical test. In a large number details in the literature. For example, the nation with EMPA analyses was most impor- Based on the experiments published in the been found from the mines in Mozambique. profile analyses (LA-ICP-MS) and chemical of samples (See Fig. Par82b-c for overlapping occurrence of U and Th-concentrations tant for the creation of a sample set (matrix literature and observations that can be made The majority of the stones have been heat- distribution mapping (EMPA-analyses) of area), the Cu/Ga-ratios (in weight-ppm) were appeared at different growth stages (Fig. matched) applicable as calibration materials using a microscope (e.g. heated tourmalines treated in the greenish-blue to blue colors, chemical zoning within single tourmalines, found to be greater than 12 in tourmalines Par41b) and increasing concentration of Rare for other and more matrix-dependent tech- have extensive cracks around tubes and fluid whereas the purple and green colors are however, it was possible to investigate the from Brazil. Earth Elements (REE’s) were measured in niques commonly used for gem testing. We inclusions), it is possible, according to our more frequently spared of thermal enhance- chemical evolution of the copper-bearing tour- the tourmaline rims (Fig. Par40, 49a, 50, found that heavy elements such Ti, Fe, Cu, experience, to reconstruct these color- ment (Fig. Par07). These findings are in good malines of samples from Mozambique and Based on our Mn-, Bi- and Cu-concentrations, 63a-b, 76e and 78d). Furthermore, it can be Zn, Mn, Bi, Pb and Ga can be routinely mea- changes. Our test procedure is presented as agreement with the findings from heat- Brazil (Fig. Par91) in more detail. We corre- it was possible to classify certain copper- shown that the growth of Brazilian tourma- sured by ED-XRF analyses, while light flow chart in Box Par3 for laboratories that do treatment experiments (Lit. Par33), which lated different zones of different tourmalines bearing tourmalines as type A, B and C (Fig. lines can be divided in a Nb and Ta-dominated elements such as Be and Mg can be mea- not have routinely access to LA-ICP-MS or predicted that heat-treatment of green colors, with the chemical evolution within the tourma- Par90a). Of particular interest were “Type growth phase (Fig. Par41c, 51c, 60b, 62d and sured by LIBS, which has been more recently EMPA. is possible with limited success only. Copper- lines. Different evolution patterns were found C”-tourmalines that are characterized by very 66g) and some other elements, such as Be introduced into gem testing. Box Par3 shows bearing tourmalines from Brazil such as from in Brazilian and Mozambique tourmalines high Mn-concentrations and low Bi- and Cu- and Pb, are differently enriched in various a test procedure that summarizes our protocol This study indicates that the general conclu- the state of “Paraiba” were more often found (Fig. Par91). This helped us to explain the concentrations. Different types of Mozam- growth sectors (Fig. Par33a, 43b, 59d, 62e, for chemical testing for tourmaline aiming at sion made in the literature (Lit. Par11) that the to be unheated than Mozambique tourma- spread of the data published elsewhere (Lit. bique tourmalines (Type A-C) were found 66d; Box Par2 and 4). The concentrations of determining their origin and authenticity. For origin of tourmalines can only be determined lines. Gem quality “Paraiba”-tourmalines does Par 11), such as in the Mg-Zn-Pb ternary within single multicolored crystals (Fig. Sb, Sc and Ge (Fig. Par33a, 43b, 60d, 62c, example, a test is based on the Cu/Ga- and by LA-ICP-MS is not valid anymore. Our occur in much smaller sizes than the African diagram that are proposed for use of origin Par72a) or as individual large samples almost 66h and 76a) are also variable within single Pb/Ga-ratios. The Cu-, Ga- and Pb- EMPA and LA-ICP-MS generated database counterparts, but they are generally more determination. With chemical profile analyses entirely forming “Type C”-tourmalines (Fig. tourmaline crystals depending on measuring concentrations can be determined by allows using commonly applied gem-testing saturated in color. According to our opinion, it was possible to evaluate the limitations of Par67). “Type C”-tourmalines were also position in different growth and color zones. ED-XRF analyses (C, Box Par3). This test methods (ED-XRF and LIBS) for origin deter- large-sized unheated gem-quality tourmalines the diagrams proposed for origin determina- discovered from one particular source in 2005 can be combined with LIBS-analyses to deter- minations of copper-bearing tourmalines. from Brazil (Paraiba or Rio Grande do Norte) tion in the literature (Lit. Par11). It can be (Bank, Tab. Par05, Lit Par36). It is well pos- Element distribution patterns as determined mine Be-concentrations (D, Box Par3). For with intense “neon”-blue colors can be shown that sudden changes of ratios and sum sible that these Bi-poor tourmalines of high with EMPA analysis detected chemical varia- example, Cu and Mn-values are measured described as extremely rare (See Fig. Par07, of elements occurred within the same crystal Mn-concentrations and low Cu- tions within a single crystal of the elements Al, first by ED-XRF. The obtained Cu- and Mn- 08, 11 and 12). depending on the different growth zones (e.g. concentrations are more often found in some Ca, Na, Mg, Ti, Zn, F, Mn, Cu and Bi. The values can than be re-measured by LIBS- see Box Par2 and 4). The diagrams based on mining spots in Mozambique (Lit. 30, 33, 34 variations detected by this method can analysis along with light elements such as Be. We found it useful to investigate the origin Cu, Mn, Pb, Ga and Be should be used for ,36 and 39). Some inclusion features that we provide additional important information on Based on the calibrated LIBS-analyses and based on chemical fingerprints using different each color group separately. In the light of found in these tourmalines (e.g. purple halos the genesis of copper-bearing tourmalines. on LA-ICP-MS generated in-house and matrix methods, including EMPA, LIBS, LA-ICP-MS strong variations within single tourmalines, around orange growth tubes and cracks, See For example, it was found that the tourma- matched calibration materials, a ternary Mn- and ED-XRF analyses. Based on these analy- the generalization about the chemical differ- Lit. Par48) have created some controversy on lines have a distinct chemical zoning in fluo- Cu-Be diagram can be obtained that provides ses, it was found that the chemical composi- ences regarding Ga, Ge, Pb, Mg, Zn, Sb, Sc the issue of treatments of copper-bearing rine, along with other elements (Fig. Par28c additional results useful for origin determina- tion of copper-bearing tourmalines from and Bi in tourmalines (See abstract Lit. Par tourmalines. We have therefore included a and 31i). The F-concentrations increased with tion (See Fig. Par85 and 86). Further combi- Mozambique, Nigeria and Brazil show distinct 11) are not useful for origin determination case study focusing on these type of inclu- the concentrations of heavy elements such as nations of light and heavy element analyses differences, which are sufficient selective to purposes. sions (Interpretations and summary, See Box Cu, Mn and Bi. These observations will may be necessary, depending on the color determine their origin. The findings on LA- Par1). With detailed pinpointing LA-ICP-MS become important for the interpretation of the variety of the copper-bearing tourmalines. In ICP-MS-analyses are in agreement with For example, due to the different approach of analysis, we detected the presence of radio- sudden enrichment of copper and other conclusion, with the combined use of LIBS- earlier work in the literature (Lit. Par11 and Lit concentrating the research on studies within active trace element concentrations of elements in copper-bearing tourmalines and (for testing of light elements such as Mg and Par33). The usefulness of diagrams from single crystals, it was possible to find different uranium in the orange cracks and tubes along for the interpretation of what kind of fluids Be), and ED-XRF analyses (for testing of these earlier works (Lit. Par11) were tested trends regarding the element Bi (See Fig. with other element concentrations such as were present (See Lit. Par09). While we have elements at concentrations higher than and found to be mostly applicable, such as Par91d). High Bi-concentrations were found barium, iron and rare earth elements (Details only reported on the example of a Brazilian 0.001%, such as Pb, Zn, Bi, Cu, Mn, Fe and the ternary diagram Mg-Zn-Pb (See Fig. Par in tourmalines from both, Brazil and Mozam- See Fig. Par76 and 78). These findings sup- tourmaline, such F-analysis can be expanded Ga), it is possible to derive a conclusive infor- 91a-b), the Cu+Mn versus Ga+Pb-diagram bique, respectively. Different Bi-Cu-Mn- port the recent theory that the purple “halos” to copper-bearing tourmalines from other mation about the origin of copper-bearing and the Cu+Mn versus Pb/Be-ratio-diagram concentration trends were found in tourma- in tourmalines from Mozambique are induced origins. For example, high F-concentrations tourmalines in most cases (See overlapping 66 Mg-Pb-Zn Chemical Evolution Trends in Copper-Bearing Tourmalines

CONCLUSIONS (Fig. Par88 and Fig. Par89). However, the Mg-Pb-Zn Chemical Evolution Trends in Tourmalines lines from the different locations and could be by natural irradiation (Lit. Par48). are also reported from Mozambique tourma- areas in critical diagrams, See Fig. Par82a-b). data of Abduriyim et al. (Lit. Par11) could not from Mozambique and Brazil (Pb-Mg-Zn-Diagram) correlated to the different color zones in these lines (Lit. Par33). The element distribution It is important, however, that a “Standard-Set” High valuable copper-bearing tourmalines be plotted in some of our diagrams as they did tourmalines (Fig. Par91c-d). However, only Ba-contaminations were also found on the mapping in tourmalines are also important to (matrix matched calibration materials) is avail- occur in different color and large size and are only publish concentration ranges and ratios Cu and Mn are responsible for the color, not surface of rough tourmalines from Mozam- compare them with any future patterns that able that has been measured by both, EMPA produced in Brazil, Mozambique and Nigeria. and no individual quantitative results and the Pb Bi. The Bi-Cu-Mn trends can be combined bique (See Tab. Par05). may occur in relation to potential new treat- and LA-ICP-MS (See Box Par3). We have The sizes and distribution of these gemstones standard deviation, respectively. However, Fig. Par91a-d with other elements, such as other minor or ments. presented only the data on unheated samples in the gem market were studied and a statistic the trends between different colored copper- A-C Triangular plots of Mg- trace elements. For example, in general much Our approach on chemical profile analyses in our charts and classified them according to about the trade has been published in this bearing Mozambique tourmalines including A-C Pb-Zn (Fig. Par91a) and higher Cu-concentrations are found in tour- allowed us furthermore to identify some new Regarding the importance of different meth- color. It must be kept in mind that heat- report. These types of tourmalines include the variations in Fe and Ti as published in the Mn-Bi-Cu (Fig. Par91c) of malines from Brazil and much higher Ga- chemical evolution trends in copper-bearing ods useful for provenance determination of treatment may have been applied to tourma- C many different color varieties and are found literature (Lit. Par 33) were plotted in A purple chemical compositions in concentrations are found in Mozambique tourmalines from different origins (e.g. REE- tourmalines, the following conclusions can be lines that may have changed their original as heated as well as unheated gems (Fig. diagrams and confirmed (Fig. Par76c, 78f, 81, B mix purple/neon-blue B multicolored copper- tourmalines. The Cu/Ga-ratio was found a trends) that have not been reported in such made (See Box Par3). LA-ICP-MS in combi- color (See for example Lit. Par11 and 33). Par07 and 12). Unusual large sizes have 82 and 88). Because we focused on chemical C neon-blue bearing tourmaline from very promising critical test. In a large number details in the literature. For example, the nation with EMPA analyses was most impor- Based on the experiments published in the been found from the mines in Mozambique. profile analyses (LA-ICP-MS) and chemical D mix green/neon-blue Mozambique and Brazil of samples (See Fig. Par82b-c for overlapping E green inner rim occurrence of U and Th-concentrations tant for the creation of a sample set (matrix literature and observations that can be made The majority of the stones have been heat- distribution mapping (EMPA-analyses) of F yellowish-green are shown (LA-ICP-MS area), the Cu/Ga-ratios (in weight-ppm) were appeared at different growth stages (Fig. matched) applicable as calibration materials using a microscope (e.g. heated tourmalines treated in the greenish-blue to blue colors, chemical zoning within single tourmalines, G green (middle rim) D 2976 analysis, in µg/g). 5 found to be greater than 12 in tourmalines Par41b) and increasing concentration of Rare for other and more matrix-dependent tech- have extensive cracks around tubes and fluid whereas the purple and green colors are however, it was possible to investigate the H green outer rim chemical profile analysis from Brazil. Earth Elements (REE’s) were measured in niques commonly used for gem testing. We inclusions), it is possible, according to our more frequently spared of thermal enhance- chemical evolution of the copper-bearing tour- A of tourmalines from Brazil the tourmaline rims (Fig. Par40, 49a, 50, found that heavy elements such Ti, Fe, Cu, experience, to reconstruct these color- ment (Fig. Par07). These findings are in good malines of samples from Mozambique and D and 2 from Mozambique Based on our Mn-, Bi- and Cu-concentrations, 63a-b, 76e and 78d). Furthermore, it can be Zn, Mn, Bi, Pb and Ga can be routinely mea- changes. Our test procedure is presented as agreement with the findings from heat- Brazil (Fig. Par91) in more detail. We corre- are shown in the same it was possible to classify certain copper- shown that the growth of Brazilian tourma- sured by ED-XRF analyses, while light flow chart in Box Par3 for laboratories that do treatment experiments (Lit. Par33), which lated different zones of different tourmalines 7782 3134 diagrams. Chemical bearing tourmalines as type A, B and C (Fig. lines can be divided in a Nb and Ta-dominated elements such as Be and Mg can be mea- not have routinely access to LA-ICP-MS or predicted that heat-treatment of green colors, with the chemical evolution within the tourma- E compositions from the Par90a). Of particular interest were “Type growth phase (Fig. Par41c, 51c, 60b, 62d and sured by LIBS, which has been more recently EMPA. is possible with limited success only. Copper- lines. Different evolution patterns were found core to the rim are C”-tourmalines that are characterized by very 66g) and some other elements, such as Be introduced into gem testing. Box Par3 shows bearing tourmalines from Brazil such as from in Brazilian and Mozambique tourmalines 2079 mapped (A-H). For each high Mn-concentrations and low Bi- and Cu- and Pb, are differently enriched in various a test procedure that summarizes our protocol This study indicates that the general conclu- the state of “Paraiba” were more often found (Fig. Par91). This helped us to explain the studied sample, a chemi- concentrations. Different types of Mozam- growth sectors (Fig. Par33a, 43b, 59d, 62e, for chemical testing for tourmaline aiming at sion made in the literature (Lit. Par11) that the cal trend is obtained that to be unheated than Mozambique tourma- spread of the data published elsewhere (Lit. Mg Zn bique tourmalines (Type A-C) were found 66d; Box Par2 and 4). The concentrations of determining their origin and authenticity. For origin of tourmalines can only be determined lines. Gem quality “Paraiba”-tourmalines does Par 11), such as in the Mg-Zn-Pb ternary D-H shows the chemical varia- within single multicolored crystals (Fig. Sb, Sc and Ge (Fig. Par33a, 43b, 60d, 62c, example, a test is based on the Cu/Ga- and by LA-ICP-MS is not valid anymore. Our occur in much smaller sizes than the African diagram that are proposed for use of origin Fig. Par91a tions of the tourmalines Par72a) or as individual large samples almost 66h and 76a) are also variable within single Pb/Ga-ratios. The Cu-, Ga- and Pb- EMPA and LA-ICP-MS generated database counterparts, but they are generally more determination. With chemical profile analyses from the core to the rim entirely forming “Type C”-tourmalines (Fig. tourmaline crystals depending on measuring concentrations can be determined by allows using commonly applied gem-testing saturated in color. According to our opinion, it was possible to evaluate the limitations of Pb (“Chemical evolution Par67). “Type C”-tourmalines were also position in different growth and color zones. ED-XRF analyses (C, Box Par3). This test methods (ED-XRF and LIBS) for origin deter- large-sized unheated gem-quality tourmalines the diagrams proposed for origin determina- trends” marked with red discovered from one particular source in 2005 can be combined with LIBS-analyses to deter- minations of copper-bearing tourmalines. from Brazil (Paraiba or Rio Grande do Norte) tion in the literature (Lit. Par11). It can be Core and green lines, Fig. (Bank, Tab. Par05, Lit Par36). It is well pos- Element distribution patterns as determined mine Be-concentrations (D, Box Par3). For with intense “neon”-blue colors can be shown that sudden changes of ratios and sum Par91b and Par91d). The sible that these Bi-poor tourmalines of high with EMPA analysis detected chemical varia- example, Cu and Mn-values are measured described as extremely rare (See Fig. Par07, of elements occurred within the same crystal sample number is indi- Mn-concentrations and low Cu- tions within a single crystal of the elements Al, first by ED-XRF. The obtained Cu- and Mn- 08, 11 and 12). depending on the different growth zones (e.g. Middle Part cated. concentrations are more often found in some Ca, Na, Mg, Ti, Zn, F, Mn, Cu and Bi. The values can than be re-measured by LIBS- see Box Par2 and 4). The diagrams based on mining spots in Mozambique (Lit. 30, 33, 34 variations detected by this method can analysis along with light elements such as Be. We found it useful to investigate the origin Cu, Mn, Pb, Ga and Be should be used for Trend 1 Trend 1 Different chemical trends ,36 and 39). Some inclusion features that we provide additional important information on Based on the calibrated LIBS-analyses and based on chemical fingerprints using different each color group separately. In the light of were found for tourma- found in these tourmalines (e.g. purple halos the genesis of copper-bearing tourmalines. on LA-ICP-MS generated in-house and matrix methods, including EMPA, LIBS, LA-ICP-MS strong variations within single tourmalines, lines from Mozambique around orange growth tubes and cracks, See For example, it was found that the tourma- matched calibration materials, a ternary Mn- and ED-XRF analyses. Based on these analy- the generalization about the chemical differ- and Brazil. Lit. Par48) have created some controversy on lines have a distinct chemical zoning in fluo- Cu-Be diagram can be obtained that provides ses, it was found that the chemical composi- ences regarding Ga, Ge, Pb, Mg, Zn, Sb, Sc the issue of treatments of copper-bearing rine, along with other elements (Fig. Par28c additional results useful for origin determina- tion of copper-bearing tourmalines from and Bi in tourmalines (See abstract Lit. Par Brazil As sown in Fig. Par91d, tourmalines. We have therefore included a and 31i). The F-concentrations increased with tion (See Fig. Par85 and 86). Further combi- Mozambique, Nigeria and Brazil show distinct 11) are not useful for origin determination tourmalines from Mozam- case study focusing on these type of inclu- the concentrations of heavy elements such as nations of light and heavy element analyses differences, which are sufficient selective to purposes. Mozambique bique evolve towards the sions (Interpretations and summary, See Box Cu, Mn and Bi. These observations will may be necessary, depending on the color determine their origin. The findings on LA- Core Mg-corner. Par1). With detailed pinpointing LA-ICP-MS become important for the interpretation of the variety of the copper-bearing tourmalines. In ICP-MS-analyses are in agreement with For example, due to the different approach of analysis, we detected the presence of radio- sudden enrichment of copper and other conclusion, with the combined use of LIBS- earlier work in the literature (Lit. Par11 and Lit concentrating the research on studies within Rim Trend 2 Brazilian tourmalines active trace element concentrations of elements in copper-bearing tourmalines and (for testing of light elements such as Mg and Par33). The usefulness of diagrams from single crystals, it was possible to find different show a relative trend uranium in the orange cracks and tubes along for the interpretation of what kind of fluids Be), and ED-XRF analyses (for testing of these earlier works (Lit. Par11) were tested trends regarding the element Bi (See Fig. towards higher with other element concentrations such as were present (See Lit. Par09). While we have elements at concentrations higher than and found to be mostly applicable, such as Par91d). High Bi-concentrations were found Rim Zn-concentrations during barium, iron and rare earth elements (Details only reported on the example of a Brazilian 0.001%, such as Pb, Zn, Bi, Cu, Mn, Fe and the ternary diagram Mg-Zn-Pb (See Fig. Par in tourmalines from both, Brazil and Mozam- Mg Zn their growth. A 2-step See Fig. Par76 and 78). These findings sup- tourmaline, such F-analysis can be expanded Ga), it is possible to derive a conclusive infor- 91a-b), the Cu+Mn versus Ga+Pb-diagram bique, respectively. Different Bi-Cu-Mn- Fig. Par91b trend was found. A chemi- port the recent theory that the purple “halos” to copper-bearing tourmalines from other mation about the origin of copper-bearing and the Cu+Mn versus Pb/Be-ratio-diagram concentration trends were found in tourma- in tourmalines from Mozambique are induced origins. For example, high F-concentrations tourmalines in most cases (See overlapping 67 Mn-Cu-Bi Chemical Evolution Trends in Copper-Bearing Tourmalines

CONCLUSIONS (Fig. Par88 and Fig. Par89). However, the Mn-Cu-Bi Chemical Evolution Trends in Tourmalines lines from the different locations and could be by natural irradiation (Lit. Par48). are also reported from Mozambique tourma- areas in critical diagrams, See Fig. Par82a-b). data of Abduriyim et al. (Lit. Par11) could not from Mozambique and Brazil (Mn-Cu-Bi-Diagram) correlated to the different color zones in these lines (Lit. Par33). The element distribution It is important, however, that a “Standard-Set” High valuable copper-bearing tourmalines be plotted in some of our diagrams as they did tourmalines (Fig. Par91c-d). However, only Ba-contaminations were also found on the mapping in tourmalines are also important to (matrix matched calibration materials) is avail- occur in different color and large size and are only publish concentration ranges and ratios Cu and Mn are responsible for the color, not surface of rough tourmalines from Mozam- compare them with any future patterns that able that has been measured by both, EMPA produced in Brazil, Mozambique and Nigeria. and no individual quantitative results and the A purple Cu Bi. The Bi-Cu-Mn trends can be combined bique (See Tab. Par05). may occur in relation to potential new treat- and LA-ICP-MS (See Box Par3). We have The sizes and distribution of these gemstones B mix purple/neon-blue cal trend towards higher standard deviation, respectively. However, C neon-blue with other elements, such as other minor or ments. presented only the data on unheated samples in the gem market were studied and a statistic the trends between different colored copper- D mix green/neon-blue Pb-concentrations is trace elements. For example, in general much Our approach on chemical profile analyses in our charts and classified them according to about the trade has been published in this bearing Mozambique tourmalines including E green inner rim followed by a trend higher Cu-concentrations are found in tour- allowed us furthermore to identify some new Regarding the importance of different meth- color. It must be kept in mind that heat- report. These types of tourmalines include the variations in Fe and Ti as published in the F yellowish-green B towards higher Zn- malines from Brazil and much higher Ga- chemical evolution trends in copper-bearing ods useful for provenance determination of treatment may have been applied to tourma- many different color varieties and are found G green (middle rim) concentrations. literature (Lit. Par 33) were plotted in H green outer rim concentrations are found in Mozambique tourmalines from different origins (e.g. REE- tourmalines, the following conclusions can be lines that may have changed their original as heated as well as unheated gems (Fig. diagrams and confirmed (Fig. Par76c, 78f, 81, B tourmalines. The Cu/Ga-ratio was found a trends) that have not been reported in such made (See Box Par3). LA-ICP-MS in combi- color (See for example Lit. Par11 and 33). A C Par07 and 12). Unusual large sizes have 82 and 88). Because we focused on chemical C The spread of the data in very promising critical test. In a large number details in the literature. For example, the nation with EMPA analyses was most impor- Based on the experiments published in the been found from the mines in Mozambique. profile analyses (LA-ICP-MS) and chemical A the Mg-Pb-Zn-diagram as of samples (See Fig. Par82b-c for overlapping C 2976 occurrence of U and Th-concentrations tant for the creation of a sample set (matrix literature and observations that can be made The majority of the stones have been heat- distribution mapping (EMPA-analyses) of published in the literature area), the Cu/Ga-ratios (in weight-ppm) were appeared at different growth stages (Fig. matched) applicable as calibration materials using a microscope (e.g. heated tourmalines treated in the greenish-blue to blue colors, chemical zoning within single tourmalines, 2965 (Lit Par11) can be found to be greater than 12 in tourmalines Par41b) and increasing concentration of Rare for other and more matrix-dependent tech- have extensive cracks around tubes and fluid whereas the purple and green colors are however, it was possible to investigate the DC explained by our profile from Brazil. Earth Elements (REE’s) were measured in niques commonly used for gem testing. We inclusions), it is possible, according to our 2079 3134 analysis. The variation of more frequently spared of thermal enhance- chemical evolution of the copper-bearing tour- BA,BD C the tourmaline rims (Fig. Par40, 49a, 50, found that heavy elements such Ti, Fe, Cu, experience, to reconstruct these color- ment (Fig. Par07). These findings are in good malines of samples from Mozambique and A G the concentrations can be Based on our Mn-, Bi- and Cu-concentrations, 63a-b, 76e and 78d). Furthermore, it can be Zn, Mn, Bi, Pb and Ga can be routinely mea- changes. Our test procedure is presented as agreement with the findings from heat- Brazil (Fig. Par91) in more detail. We corre- 7782 found within single tour- it was possible to classify certain copper- shown that the growth of Brazilian tourma- sured by ED-XRF analyses, while light flow chart in Box Par3 for laboratories that do treatment experiments (Lit. Par33), which lated different zones of different tourmalines maline crystals. bearing tourmalines as type A, B and C (Fig. H E D lines can be divided in a Nb and Ta-dominated elements such as Be and Mg can be mea- not have routinely access to LA-ICP-MS or predicted that heat-treatment of green colors, with the chemical evolution within the tourma- E/F D Par90a). Of particular interest were “Type growth phase (Fig. Par41c, 51c, 60b, 62d and sured by LIBS, which has been more recently EMPA. is possible with limited success only. Copper- lines. Different evolution patterns were found FE-H The “chemical evolution C”-tourmalines that are characterized by very 66g) and some other elements, such as Be introduced into gem testing. Box Par3 shows bearing tourmalines from Brazil such as from in Brazilian and Mozambique tourmalines E path” of Cu, Mn and Bi is high Mn-concentrations and low Bi- and Cu- and Pb, are differently enriched in various a test procedure that summarizes our protocol This study indicates that the general conclu- the state of “Paraiba” were more often found (Fig. Par91). This helped us to explain the different for samples from concentrations. Different types of Mozam- growth sectors (Fig. Par33a, 43b, 59d, 62e, for chemical testing for tourmaline aiming at sion made in the literature (Lit. Par11) that the to be unheated than Mozambique tourma- spread of the data published elsewhere (Lit. Mozambique and Brazil bique tourmalines (Type A-C) were found 66d; Box Par2 and 4). The concentrations of determining their origin and authenticity. For origin of tourmalines can only be determined lines. Gem quality “Paraiba”-tourmalines does Par 11), such as in the Mg-Zn-Pb ternary Mn Bi (Fig. Par91d). within single multicolored crystals (Fig. Sb, Sc and Ge (Fig. Par33a, 43b, 60d, 62c, example, a test is based on the Cu/Ga- and by LA-ICP-MS is not valid anymore. Our occur in much smaller sizes than the African diagram that are proposed for use of origin Fig. Par91c Par72a) or as individual large samples almost 66h and 76a) are also variable within single Pb/Ga-ratios. The Cu-, Ga- and Pb- EMPA and LA-ICP-MS generated database counterparts, but they are generally more determination. With chemical profile analyses The trends in Mozam- entirely forming “Type C”-tourmalines (Fig. tourmaline crystals depending on measuring concentrations can be determined by allows using commonly applied gem-testing saturated in color. According to our opinion, it was possible to evaluate the limitations of Cu bique tourmalines are Par67). “Type C”-tourmalines were also position in different growth and color zones. ED-XRF analyses (C, Box Par3). This test methods (ED-XRF and LIBS) for origin deter- large-sized unheated gem-quality tourmalines the diagrams proposed for origin determina- found to be similar but discovered from one particular source in 2005 can be combined with LIBS-analyses to deter- minations of copper-bearing tourmalines. from Brazil (Paraiba or Rio Grande do Norte) tion in the literature (Lit. Par11). It can be shifted towards higher (Bank, Tab. Par05, Lit Par36). It is well pos- Element distribution patterns as determined mine Be-concentrations (D, Box Par3). For with intense “neon”-blue colors can be shown that sudden changes of ratios and sum Bi-concentrations. Accord- sible that these Bi-poor tourmalines of high with EMPA analysis detected chemical varia- example, Cu and Mn-values are measured described as extremely rare (See Fig. Par07, of elements occurred within the same crystal ing to the Mn/Bi-ratio, the Mn-concentrations and low Cu- tions within a single crystal of the elements Al, first by ED-XRF. The obtained Cu- and Mn- 08, 11 and 12). depending on the different growth zones (e.g. Middle Part Mozambique tourmalines concentrations are more often found in some Ca, Na, Mg, Ti, Zn, F, Mn, Cu and Bi. The values can than be re-measured by LIBS- see Box Par2 and 4). The diagrams based on have been classified as mining spots in Mozambique (Lit. 30, 33, 34 variations detected by this method can analysis along with light elements such as Be. We found it useful to investigate the origin Cu, Mn, Pb, Ga and Be should be used for Type A, B and C (Fig. ,36 and 39). Some inclusion features that we provide additional important information on Based on the calibrated LIBS-analyses and based on chemical fingerprints using different each color group separately. In the light of Core Par90a-b). Type C is found in these tourmalines (e.g. purple halos the genesis of copper-bearing tourmalines. on LA-ICP-MS generated in-house and matrix methods, including EMPA, LIBS, LA-ICP-MS strong variations within single tourmalines, extremely Mn-rich at low around orange growth tubes and cracks, See For example, it was found that the tourma- matched calibration materials, a ternary Mn- and ED-XRF analyses. Based on these analy- the generalization about the chemical differ- Bi-concentrations. Lit. Par48) have created some controversy on lines have a distinct chemical zoning in fluo- Cu-Be diagram can be obtained that provides ses, it was found that the chemical composi- ences regarding Ga, Ge, Pb, Mg, Zn, Sb, Sc Brazil the issue of treatments of copper-bearing rine, along with other elements (Fig. Par28c additional results useful for origin determina- tion of copper-bearing tourmalines from and Bi in tourmalines (See abstract Lit. Par The trends observed in tourmalines. We have therefore included a and 31i). The F-concentrations increased with tion (See Fig. Par85 and 86). Further combi- Mozambique, Nigeria and Brazil show distinct 11) are not useful for origin determination the tourmalines from case study focusing on these type of inclu- the concentrations of heavy elements such as nations of light and heavy element analyses differences, which are sufficient selective to purposes. Core Core Core Brazil are centered sions (Interpretations and summary, See Box Cu, Mn and Bi. These observations will may be necessary, depending on the color determine their origin. The findings on LA- Type A towards the corner of Cu Par1). With detailed pinpointing LA-ICP-MS become important for the interpretation of the variety of the copper-bearing tourmalines. In ICP-MS-analyses are in agreement with For example, due to the different approach of Rim Mozambique in the Cu-Mn-Bi-triangle. analysis, we detected the presence of radio- sudden enrichment of copper and other conclusion, with the combined use of LIBS- earlier work in the literature (Lit. Par11 and Lit concentrating the research on studies within This due to the generally active trace element concentrations of elements in copper-bearing tourmalines and (for testing of light elements such as Mg and Par33). The usefulness of diagrams from single crystals, it was possible to find different higher Cu-concentrations uranium in the orange cracks and tubes along for the interpretation of what kind of fluids Be), and ED-XRF analyses (for testing of these earlier works (Lit. Par11) were tested trends regarding the element Bi (See Fig. of the Brazilian tourma- with other element concentrations such as were present (See Lit. Par09). While we have elements at concentrations higher than Trend to Type C Type B and found to be mostly applicable, such as Par91d). High Bi-concentrations were found Rim lines. barium, iron and rare earth elements (Details only reported on the example of a Brazilian 0.001%, such as Pb, Zn, Bi, Cu, Mn, Fe and the ternary diagram Mg-Zn-Pb (See Fig. Par in tourmalines from both, Brazil and Mozam- Mn Bi See Fig. Par76 and 78). These findings sup- tourmaline, such F-analysis can be expanded Ga), it is possible to derive a conclusive infor- 91a-b), the Cu+Mn versus Ga+Pb-diagram bique, respectively. Different Bi-Cu-Mn- Fig. Par91d port the recent theory that the purple “halos” to copper-bearing tourmalines from other mation about the origin of copper-bearing and the Cu+Mn versus Pb/Be-ratio-diagram concentration trends were found in tourma- in tourmalines from Mozambique are induced origins. For example, high F-concentrations tourmalines in most cases (See overlapping 68 Conclusions

CONCLUSIONS (Fig. Par88 and Fig. Par89). However, the lines from the different locations and could be by natural irradiation (Lit. Par48). are also reported from Mozambique tourma- areas in critical diagrams, See Fig. Par82a-b). data of Abduriyim et al. (Lit. Par11) could not correlated to the different color zones in these lines (Lit. Par33). The element distribution It is important, however, that a “Standard-Set” High valuable copper-bearing tourmalines be plotted in some of our diagrams as they did tourmalines (Fig. Par91c-d). However, only Ba-contaminations were also found on the mapping in tourmalines are also important to (matrix matched calibration materials) is avail- occur in different color and large size and are only publish concentration ranges and ratios Cu and Mn are responsible for the color, not surface of rough tourmalines from Mozam- compare them with any future patterns that able that has been measured by both, EMPA produced in Brazil, Mozambique and Nigeria. and no individual quantitative results and the Bi. The Bi-Cu-Mn trends can be combined bique (See Tab. Par05). may occur in relation to potential new treat- and LA-ICP-MS (See Box Par3). We have The sizes and distribution of these gemstones standard deviation, respectively. However, with other elements, such as other minor or ments. presented only the data on unheated samples in the gem market were studied and a statistic the trends between different colored copper- trace elements. For example, in general much Our approach on chemical profile analyses in our charts and classified them according to about the trade has been published in this bearing Mozambique tourmalines including higher Cu-concentrations are found in tour- allowed us furthermore to identify some new Regarding the importance of different meth- color. It must be kept in mind that heat- report. These types of tourmalines include the variations in Fe and Ti as published in the malines from Brazil and much higher Ga- chemical evolution trends in copper-bearing ods useful for provenance determination of treatment may have been applied to tourma- many different color varieties and are found literature (Lit. Par 33) were plotted in concentrations are found in Mozambique tourmalines from different origins (e.g. REE- tourmalines, the following conclusions can be lines that may have changed their original as heated as well as unheated gems (Fig. diagrams and confirmed (Fig. Par76c, 78f, 81, tourmalines. The Cu/Ga-ratio was found a trends) that have not been reported in such made (See Box Par3). LA-ICP-MS in combi- color (See for example Lit. Par11 and 33). Par07 and 12). Unusual large sizes have 82 and 88). Because we focused on chemical very promising critical test. In a large number details in the literature. For example, the nation with EMPA analyses was most impor- Based on the experiments published in the been found from the mines in Mozambique. profile analyses (LA-ICP-MS) and chemical of samples (See Fig. Par82b-c for overlapping occurrence of U and Th-concentrations tant for the creation of a sample set (matrix literature and observations that can be made The majority of the stones have been heat- distribution mapping (EMPA-analyses) of area), the Cu/Ga-ratios (in weight-ppm) were appeared at different growth stages (Fig. matched) applicable as calibration materials using a microscope (e.g. heated tourmalines treated in the greenish-blue to blue colors, chemical zoning within single tourmalines, found to be greater than 12 in tourmalines Par41b) and increasing concentration of Rare for other and more matrix-dependent tech- have extensive cracks around tubes and fluid whereas the purple and green colors are however, it was possible to investigate the from Brazil. Earth Elements (REE’s) were measured in niques commonly used for gem testing. We inclusions), it is possible, according to our more frequently spared of thermal enhance- chemical evolution of the copper-bearing tour- the tourmaline rims (Fig. Par40, 49a, 50, found that heavy elements such Ti, Fe, Cu, experience, to reconstruct these color- ment (Fig. Par07). These findings are in good malines of samples from Mozambique and Based on our Mn-, Bi- and Cu-concentrations, 63a-b, 76e and 78d). Furthermore, it can be Zn, Mn, Bi, Pb and Ga can be routinely mea- changes. Our test procedure is presented as agreement with the findings from heat- Brazil (Fig. Par91) in more detail. We corre- it was possible to classify certain copper- shown that the growth of Brazilian tourma- sured by ED-XRF analyses, while light flow chart in Box Par3 for laboratories that do treatment experiments (Lit. Par33), which lated different zones of different tourmalines bearing tourmalines as type A, B and C (Fig. lines can be divided in a Nb and Ta-dominated elements such as Be and Mg can be mea- not have routinely access to LA-ICP-MS or predicted that heat-treatment of green colors, with the chemical evolution within the tourma- Par90a). Of particular interest were “Type growth phase (Fig. Par41c, 51c, 60b, 62d and sured by LIBS, which has been more recently EMPA. is possible with limited success only. Copper- lines. Different evolution patterns were found C”-tourmalines that are characterized by very 66g) and some other elements, such as Be introduced into gem testing. Box Par3 shows bearing tourmalines from Brazil such as from in Brazilian and Mozambique tourmalines high Mn-concentrations and low Bi- and Cu- and Pb, are differently enriched in various a test procedure that summarizes our protocol This study indicates that the general conclu- the state of “Paraiba” were more often found (Fig. Par91). This helped us to explain the concentrations. Different types of Mozam- growth sectors (Fig. Par33a, 43b, 59d, 62e, for chemical testing for tourmaline aiming at sion made in the literature (Lit. Par11) that the to be unheated than Mozambique tourma- spread of the data published elsewhere (Lit. bique tourmalines (Type A-C) were found 66d; Box Par2 and 4). The concentrations of determining their origin and authenticity. For origin of tourmalines can only be determined lines. Gem quality “Paraiba”-tourmalines does Par 11), such as in the Mg-Zn-Pb ternary within single multicolored crystals (Fig. Sb, Sc and Ge (Fig. Par33a, 43b, 60d, 62c, example, a test is based on the Cu/Ga- and by LA-ICP-MS is not valid anymore. Our occur in much smaller sizes than the African diagram that are proposed for use of origin Par72a) or as individual large samples almost 66h and 76a) are also variable within single Pb/Ga-ratios. The Cu-, Ga- and Pb- EMPA and LA-ICP-MS generated database counterparts, but they are generally more determination. With chemical profile analyses entirely forming “Type C”-tourmalines (Fig. tourmaline crystals depending on measuring concentrations can be determined by allows using commonly applied gem-testing saturated in color. According to our opinion, it was possible to evaluate the limitations of Par67). “Type C”-tourmalines were also position in different growth and color zones. ED-XRF analyses (C, Box Par3). This test methods (ED-XRF and LIBS) for origin deter- large-sized unheated gem-quality tourmalines the diagrams proposed for origin determina- discovered from one particular source in 2005 can be combined with LIBS-analyses to deter- minations of copper-bearing tourmalines. from Brazil (Paraiba or Rio Grande do Norte) tion in the literature (Lit. Par11). It can be (Bank, Tab. Par05, Lit Par36). It is well pos- Element distribution patterns as determined mine Be-concentrations (D, Box Par3). For with intense “neon”-blue colors can be shown that sudden changes of ratios and sum sible that these Bi-poor tourmalines of high with EMPA analysis detected chemical varia- example, Cu and Mn-values are measured described as extremely rare (See Fig. Par07, of elements occurred within the same crystal Mn-concentrations and low Cu- tions within a single crystal of the elements Al, first by ED-XRF. The obtained Cu- and Mn- 08, 11 and 12). depending on the different growth zones (e.g. concentrations are more often found in some Ca, Na, Mg, Ti, Zn, F, Mn, Cu and Bi. The values can than be re-measured by LIBS- see Box Par2 and 4). The diagrams based on mining spots in Mozambique (Lit. 30, 33, 34 variations detected by this method can analysis along with light elements such as Be. We found it useful to investigate the origin Cu, Mn, Pb, Ga and Be should be used for ,36 and 39). Some inclusion features that we provide additional important information on Based on the calibrated LIBS-analyses and based on chemical fingerprints using different each color group separately. In the light of found in these tourmalines (e.g. purple halos the genesis of copper-bearing tourmalines. on LA-ICP-MS generated in-house and matrix methods, including EMPA, LIBS, LA-ICP-MS strong variations within single tourmalines, around orange growth tubes and cracks, See For example, it was found that the tourma- matched calibration materials, a ternary Mn- and ED-XRF analyses. Based on these analy- the generalization about the chemical differ- Lit. Par48) have created some controversy on lines have a distinct chemical zoning in fluo- Cu-Be diagram can be obtained that provides ses, it was found that the chemical composi- ences regarding Ga, Ge, Pb, Mg, Zn, Sb, Sc the issue of treatments of copper-bearing rine, along with other elements (Fig. Par28c additional results useful for origin determina- tion of copper-bearing tourmalines from and Bi in tourmalines (See abstract Lit. Par tourmalines. We have therefore included a and 31i). The F-concentrations increased with tion (See Fig. Par85 and 86). Further combi- Mozambique, Nigeria and Brazil show distinct 11) are not useful for origin determination case study focusing on these type of inclu- the concentrations of heavy elements such as nations of light and heavy element analyses differences, which are sufficient selective to purposes. sions (Interpretations and summary, See Box Cu, Mn and Bi. These observations will may be necessary, depending on the color determine their origin. The findings on LA- Par1). With detailed pinpointing LA-ICP-MS become important for the interpretation of the variety of the copper-bearing tourmalines. In ICP-MS-analyses are in agreement with For example, due to the different approach of analysis, we detected the presence of radio- sudden enrichment of copper and other conclusion, with the combined use of LIBS- earlier work in the literature (Lit. Par11 and Lit concentrating the research on studies within active trace element concentrations of elements in copper-bearing tourmalines and (for testing of light elements such as Mg and Par33). The usefulness of diagrams from single crystals, it was possible to find different uranium in the orange cracks and tubes along for the interpretation of what kind of fluids Be), and ED-XRF analyses (for testing of these earlier works (Lit. Par11) were tested trends regarding the element Bi (See Fig. with other element concentrations such as were present (See Lit. Par09). While we have elements at concentrations higher than and found to be mostly applicable, such as Par91d). High Bi-concentrations were found barium, iron and rare earth elements (Details only reported on the example of a Brazilian 0.001%, such as Pb, Zn, Bi, Cu, Mn, Fe and the ternary diagram Mg-Zn-Pb (See Fig. Par in tourmalines from both, Brazil and Mozam- See Fig. Par76 and 78). These findings sup- tourmaline, such F-analysis can be expanded Ga), it is possible to derive a conclusive infor- 91a-b), the Cu+Mn versus Ga+Pb-diagram bique, respectively. Different Bi-Cu-Mn- port the recent theory that the purple “halos” to copper-bearing tourmalines from other mation about the origin of copper-bearing and the Cu+Mn versus Pb/Be-ratio-diagram concentration trends were found in tourma- in tourmalines from Mozambique are induced origins. For example, high F-concentrations tourmalines in most cases (See overlapping 69 Conclusions

CONCLUSIONS (Fig. Par88 and Fig. Par89). However, the lines from the different locations and could be by natural irradiation (Lit. Par48). are also reported from Mozambique tourma- areas in critical diagrams, See Fig. Par82a-b). data of Abduriyim et al. (Lit. Par11) could not correlated to the different color zones in these lines (Lit. Par33). The element distribution It is important, however, that a “Standard-Set” High valuable copper-bearing tourmalines be plotted in some of our diagrams as they did tourmalines (Fig. Par91c-d). However, only Ba-contaminations were also found on the mapping in tourmalines are also important to (matrix matched calibration materials) is avail- occur in different color and large size and are only publish concentration ranges and ratios Cu and Mn are responsible for the color, not surface of rough tourmalines from Mozam- compare them with any future patterns that able that has been measured by both, EMPA produced in Brazil, Mozambique and Nigeria. and no individual quantitative results and the Bi. The Bi-Cu-Mn trends can be combined bique (See Tab. Par05). may occur in relation to potential new treat- and LA-ICP-MS (See Box Par3). We have The sizes and distribution of these gemstones standard deviation, respectively. However, with other elements, such as other minor or ments. presented only the data on unheated samples in the gem market were studied and a statistic the trends between different colored copper- trace elements. For example, in general much Our approach on chemical profile analyses in our charts and classified them according to about the trade has been published in this bearing Mozambique tourmalines including higher Cu-concentrations are found in tour- allowed us furthermore to identify some new Regarding the importance of different meth- color. It must be kept in mind that heat- report. These types of tourmalines include the variations in Fe and Ti as published in the malines from Brazil and much higher Ga- chemical evolution trends in copper-bearing ods useful for provenance determination of treatment may have been applied to tourma- many different color varieties and are found literature (Lit. Par 33) were plotted in concentrations are found in Mozambique tourmalines from different origins (e.g. REE- tourmalines, the following conclusions can be lines that may have changed their original as heated as well as unheated gems (Fig. diagrams and confirmed (Fig. Par76c, 78f, 81, tourmalines. The Cu/Ga-ratio was found a trends) that have not been reported in such made (See Box Par3). LA-ICP-MS in combi- color (See for example Lit. Par11 and 33). Par07 and 12). Unusual large sizes have 82 and 88). Because we focused on chemical very promising critical test. In a large number details in the literature. For example, the nation with EMPA analyses was most impor- Based on the experiments published in the been found from the mines in Mozambique. profile analyses (LA-ICP-MS) and chemical of samples (See Fig. Par82b-c for overlapping occurrence of U and Th-concentrations tant for the creation of a sample set (matrix literature and observations that can be made The majority of the stones have been heat- distribution mapping (EMPA-analyses) of area), the Cu/Ga-ratios (in weight-ppm) were appeared at different growth stages (Fig. matched) applicable as calibration materials using a microscope (e.g. heated tourmalines treated in the greenish-blue to blue colors, chemical zoning within single tourmalines, found to be greater than 12 in tourmalines Par41b) and increasing concentration of Rare for other and more matrix-dependent tech- have extensive cracks around tubes and fluid whereas the purple and green colors are however, it was possible to investigate the from Brazil. Earth Elements (REE’s) were measured in niques commonly used for gem testing. We inclusions), it is possible, according to our more frequently spared of thermal enhance- chemical evolution of the copper-bearing tour- the tourmaline rims (Fig. Par40, 49a, 50, found that heavy elements such Ti, Fe, Cu, experience, to reconstruct these color- ment (Fig. Par07). These findings are in good malines of samples from Mozambique and Based on our Mn-, Bi- and Cu-concentrations, 63a-b, 76e and 78d). Furthermore, it can be Zn, Mn, Bi, Pb and Ga can be routinely mea- changes. Our test procedure is presented as agreement with the findings from heat- Brazil (Fig. Par91) in more detail. We corre- it was possible to classify certain copper- shown that the growth of Brazilian tourma- sured by ED-XRF analyses, while light flow chart in Box Par3 for laboratories that do treatment experiments (Lit. Par33), which lated different zones of different tourmalines bearing tourmalines as type A, B and C (Fig. lines can be divided in a Nb and Ta-dominated elements such as Be and Mg can be mea- not have routinely access to LA-ICP-MS or predicted that heat-treatment of green colors, with the chemical evolution within the tourma- Par90a). Of particular interest were “Type growth phase (Fig. Par41c, 51c, 60b, 62d and sured by LIBS, which has been more recently EMPA. is possible with limited success only. Copper- lines. Different evolution patterns were found C”-tourmalines that are characterized by very 66g) and some other elements, such as Be introduced into gem testing. Box Par3 shows bearing tourmalines from Brazil such as from in Brazilian and Mozambique tourmalines high Mn-concentrations and low Bi- and Cu- and Pb, are differently enriched in various a test procedure that summarizes our protocol This study indicates that the general conclu- the state of “Paraiba” were more often found (Fig. Par91). This helped us to explain the concentrations. Different types of Mozam- growth sectors (Fig. Par33a, 43b, 59d, 62e, for chemical testing for tourmaline aiming at sion made in the literature (Lit. Par11) that the to be unheated than Mozambique tourma- spread of the data published elsewhere (Lit. bique tourmalines (Type A-C) were found 66d; Box Par2 and 4). The concentrations of determining their origin and authenticity. For origin of tourmalines can only be determined lines. Gem quality “Paraiba”-tourmalines does Par 11), such as in the Mg-Zn-Pb ternary within single multicolored crystals (Fig. Sb, Sc and Ge (Fig. Par33a, 43b, 60d, 62c, example, a test is based on the Cu/Ga- and by LA-ICP-MS is not valid anymore. Our occur in much smaller sizes than the African diagram that are proposed for use of origin Par72a) or as individual large samples almost 66h and 76a) are also variable within single Pb/Ga-ratios. The Cu-, Ga- and Pb- EMPA and LA-ICP-MS generated database counterparts, but they are generally more determination. With chemical profile analyses entirely forming “Type C”-tourmalines (Fig. tourmaline crystals depending on measuring concentrations can be determined by allows using commonly applied gem-testing saturated in color. According to our opinion, it was possible to evaluate the limitations of Par67). “Type C”-tourmalines were also position in different growth and color zones. ED-XRF analyses (C, Box Par3). This test methods (ED-XRF and LIBS) for origin deter- large-sized unheated gem-quality tourmalines the diagrams proposed for origin determina- discovered from one particular source in 2005 can be combined with LIBS-analyses to deter- minations of copper-bearing tourmalines. from Brazil (Paraiba or Rio Grande do Norte) tion in the literature (Lit. Par11). It can be (Bank, Tab. Par05, Lit Par36). It is well pos- Element distribution patterns as determined mine Be-concentrations (D, Box Par3). For with intense “neon”-blue colors can be shown that sudden changes of ratios and sum sible that these Bi-poor tourmalines of high with EMPA analysis detected chemical varia- example, Cu and Mn-values are measured described as extremely rare (See Fig. Par07, of elements occurred within the same crystal Mn-concentrations and low Cu- tions within a single crystal of the elements Al, first by ED-XRF. The obtained Cu- and Mn- 08, 11 and 12). depending on the different growth zones (e.g. concentrations are more often found in some Ca, Na, Mg, Ti, Zn, F, Mn, Cu and Bi. The values can than be re-measured by LIBS- see Box Par2 and 4). The diagrams based on mining spots in Mozambique (Lit. 30, 33, 34 variations detected by this method can analysis along with light elements such as Be. We found it useful to investigate the origin Cu, Mn, Pb, Ga and Be should be used for ,36 and 39). Some inclusion features that we provide additional important information on Based on the calibrated LIBS-analyses and based on chemical fingerprints using different each color group separately. In the light of found in these tourmalines (e.g. purple halos the genesis of copper-bearing tourmalines. on LA-ICP-MS generated in-house and matrix methods, including EMPA, LIBS, LA-ICP-MS strong variations within single tourmalines, around orange growth tubes and cracks, See For example, it was found that the tourma- matched calibration materials, a ternary Mn- and ED-XRF analyses. Based on these analy- the generalization about the chemical differ- Lit. Par48) have created some controversy on lines have a distinct chemical zoning in fluo- Cu-Be diagram can be obtained that provides ses, it was found that the chemical composi- ences regarding Ga, Ge, Pb, Mg, Zn, Sb, Sc the issue of treatments of copper-bearing rine, along with other elements (Fig. Par28c additional results useful for origin determina- tion of copper-bearing tourmalines from and Bi in tourmalines (See abstract Lit. Par tourmalines. We have therefore included a and 31i). The F-concentrations increased with tion (See Fig. Par85 and 86). Further combi- Mozambique, Nigeria and Brazil show distinct 11) are not useful for origin determination case study focusing on these type of inclu- the concentrations of heavy elements such as nations of light and heavy element analyses differences, which are sufficient selective to purposes. sions (Interpretations and summary, See Box Cu, Mn and Bi. These observations will may be necessary, depending on the color determine their origin. The findings on LA- Par1). With detailed pinpointing LA-ICP-MS become important for the interpretation of the variety of the copper-bearing tourmalines. In ICP-MS-analyses are in agreement with For example, due to the different approach of analysis, we detected the presence of radio- sudden enrichment of copper and other conclusion, with the combined use of LIBS- earlier work in the literature (Lit. Par11 and Lit concentrating the research on studies within active trace element concentrations of elements in copper-bearing tourmalines and (for testing of light elements such as Mg and Par33). The usefulness of diagrams from single crystals, it was possible to find different uranium in the orange cracks and tubes along for the interpretation of what kind of fluids Be), and ED-XRF analyses (for testing of these earlier works (Lit. Par11) were tested trends regarding the element Bi (See Fig. with other element concentrations such as were present (See Lit. Par09). While we have elements at concentrations higher than and found to be mostly applicable, such as Par91d). High Bi-concentrations were found barium, iron and rare earth elements (Details only reported on the example of a Brazilian 0.001%, such as Pb, Zn, Bi, Cu, Mn, Fe and the ternary diagram Mg-Zn-Pb (See Fig. Par in tourmalines from both, Brazil and Mozam- See Fig. Par76 and 78). These findings sup- tourmaline, such F-analysis can be expanded Ga), it is possible to derive a conclusive infor- 91a-b), the Cu+Mn versus Ga+Pb-diagram bique, respectively. Different Bi-Cu-Mn- port the recent theory that the purple “halos” to copper-bearing tourmalines from other mation about the origin of copper-bearing and the Cu+Mn versus Pb/Be-ratio-diagram concentration trends were found in tourma- in tourmalines from Mozambique are induced origins. For example, high F-concentrations tourmalines in most cases (See overlapping 70 About the Authors

Acknowledgments Lit Par04 Guillong M., Günther D. (2001) Quasi ‘non-destructive’ laser ablation-inductively coupled We would like to thank the P. Wild company (Idar- plasma-mass spectrometry fingerprinting of sapphires. Oberstein, Germany) for providing us with numerous Spectrochimica Acta Part B, Vol. 56, pp. 1219-1231. pictures from the mines and supporting us with samples for this research project. Marcus Paul Wild Lit Par05 Günther D., Hattendorf B. (2005) Solid explained us the geological background of some sample analysis using laser ablation inductively Brazilian tourmaline mines. Brian Pavlik from Brian’s coupled plasma mass spectrometry. Trends in Analyti- Fine Gems (Austria) granted us permission to us cal Chemistry, Vol.24, No. 3, pp. 255-265. pictures from the Pavlik Gem History Archive (Vienna, Lit Par06 Leach A.M., Hieftje G.M. (2002) Factors Austria) and donated Paraiba tourmalines from the first affecting the production of fast transient signals in production years (1988). Gebr. Bank (Idar Oberstein) single shot laser ablation inductively coupled plasma donated samples from the first mining period in mass spectrometry. Applied Spectroscopy. Vol. 56, Mozambique and obtained further samples from No. 1, pp. 62-69. Paraiba from Bob von Wagoner (Beija-Flor Gems). Tourmalines from Nigeria were received from Steve Lit Par07 LongerichH.P., Jackson S.E., Günther D. Jaquith and Arnold Silverberg in Bangkok. Hatta New (1996) Laser ablation inductively coupled plasma World company provided us professional jewelry mass spectrometric transient signal data acquisition photography and valuable jewelry sets for testing and analyte concentration calculation. Winter Confer- purposes. Without the support from African miners and ence on Plasma Spectrochemistry. 1996. Ft Lauder- dealers, we would not have been able to acquire multi- dale. colored tourmaline samples from Mozambique. C.H. Lit Par08 Pearce N. J. G., Perkins W. T., Westgate J. Lapidaries from Bangkok assisted us for faceting our A., Gorton M. P., Jackson S. E., Neal C. R., Chenery own rough materials. Miriam Peretti helped for presen- S. P. (1996) Application of new and published major tation of jewelry sets and Elia Menghini assisted in and trace elements data for NIST SRM 610 and NIST ED-XRF analysis. SRM 612 glass reference materials. Geostandards Many thanks to Mr. Tanthadilok for graphic and Newsletter, Vol. 20, No. 2, pp. 115-144. artwork, Ms Anong Kranpaphai from Anong Imaging for photography and Mr. Michael for preparing this report Lit Par09 Peretti A., Mullis J., Mouawad F. (1996) The for the Internet online version, now in translation mode role of fluorine in the formation of color zoning in for over a dozen languages (www.gemresearch.ch). rubies from Mong Hsu (Myanmar, Burma). J. Gemmol. 25: p. 3-19. About the Authors Lit Par10 Rossman G. R., Mattson S. M. (1986) Dr. Peretti is Director of the GRS Gemresearch Yellow, Mn-rich elbaite with Mn-Ti intervalence charge Swisslab Ltd., Lucerne, Switzerland transfer. American Mineralogist, Vol. 71, pp. 599-602. [email protected] Literature review on tourmalines from Brazil Dr. Günther is Professor for Trace Elements and Microanalysis at the Laboratory for Inorganic Chemis- Lit Par11 Abduriyim A., Kitawaki H., Furuya M., try, ETH Zurich, Switzerland Schwarz D. (2006) "Paraiba"-type copper-bearing [email protected] tourmaline from Brazil, Nigeria, and Mozambique: Chemical fingerprinting by LA-ICP-MS. Gems & K. Hametner is Research Assistant for Trace Gemology, Vol. 42, No. 1, pp. 4-21. Elements and Microanalysis at the Laboratory for Inorganic Chemistry, ETH Zurich, Switzerland Lit Par12 Bank H.,Henn U. (1990) Paraiba tourmaline: [email protected] Beauty and rarity. Jewellery News Asia, No.70, 1990, pp. 62, 64. W. Bieri (Bsc. EarthSc.) is Research Gemologist at GRS (Thailand) in Bangkok, Thailand. Lit Par13 Bank H., Henn U., Bank F. H., von Platen H., [email protected] HofmeisterW. (1990) Leuchtendblaue Cu-führendeTurmalineaus Paraiba, Brasilien. Dr. Reusser is Research Scientist at Institute of Zeitschrift der Deutschen Gemmologischen Gesell- Mineralogy and Petrography, ETH Zentrum, CH-8092 schaft, Vol.39, No. 1, pp. 3-11. Zurich, Switzerland [email protected] Lit Par14 Brandstätter F., Niedermayr G. (1994) An extended scientific report of this book is published Copper and tenorite inclusions in cuprian-elbaite under: tourmaline from Paraiba, Brazil. Gems & Gemology, Lit Par01 Peretti A., Reusser E., Bieri W., Hametner K. Vol. 30, No. 3, pp. 178-183. and Guenther D. (in prep.) Provenance studies of Lit Par15 FedermanD. (1990) Gem profile. Paraiba “Paraiba” tourmalines using EMPA and LA-ICP-MS tourmaline: Toast of the trade. Modern Jeweler, analysis. Analytical and Bioanalytical Chemistry. Vol.89, No. 1, p. 48. Literature review on methods Lit Par16 Fritsch E., Shigley J. E., Rossman G. R., Mercer M. E., Muhlmeister S., Moon M. (1990) Lit Par02 ArmstrongJ.T., Caltech 1993, Jeol license of Gem-quality cuprian-elbaite tourmalines from São CITZAF version 3.5. José da Batalha, Paraiba, Brazil. Gems & Gemology, Lit Par03 Gao, S., Liu, X., Yuan, H., Hattendorf, B., Vol. 26, No. 3, pp. 189-205. Günther, D., Chen, L., Hu, S. 2002 Analysis of forty- Lit Par17 Furuya M. (2004) Electric blue tourmaline two major and trace elements of USGS and NIST from Nigeria: Paraiba tourmaline or new name? SRM Glasses by LA-ICPMS Geostandard Newslet- Proceedings of the 29th International Gemmological ters, Vol. 26, 181-195 Conference 2004, Wuhan, China, September 13-17, China University of Geosciences (Wuhan) and Hong Kong Institute of Gemmology, pp. 111-112.

71 Literature

Lit Par18 Furuya M., Furuya M. (2007) Paraiba Lit Par35 Milisenda C. C. (2001) GemmologieAktuell: Tourmaline-Electric Blue Brilliance Burnt into Our Cuprian tourmaline from Nigeria. Gemmologie: Minds. Japan Germany Gemmological Laboratory, Zeitschrift der Deutschen Gemmologischen Gesell- Kofu, Japan, 24 pp. schaft, Vol. 50, No. 3, pp. 121-122. Lit Par19 Kane R.E. (1989) Gem trade lab notes: Blue Lit Par36 Milisenda C. C., Horikawa Y., Emori K., tourmaline from Brazil. Gems &Gemology, Vol. 25, Miranda R., Bank F. H., Henn U. (2006) Neues No. 4, pp. 241-242. Vorkommen kupferführender Turmaline in Mosambik Lit Par20 Karfunkel J., Wegner R. R. (1996) Paraiba [A new find of cuprian tourmalines in Mozambique]. tourmalines: Distribution, mode of occurrence, and Gemmologie: Zeitschrift der Deutschen Gemmolo- geologic environment. Canadian Gemmologist, gischen Gesellschaft, Vol. 55, No. 1-2, pp. 5-24. Vol.17, No. 4, pp. 99-106. Lit Par37 Mozambique Paraiba tourmaline hot in Lit Par21 Kitawaki H. (2005) Journey through Brazil Tucson (2007) jewellery News Asia, No. 272 (April), p. mines: Hometown of "Paraiba" tourmaline. Gemmol- 56. ogy, Vol.36, No. 435, pp. 19-23. Lit Par38 Petsch E. J. (1986) Riesen in Rot, Grün und Lit Par22 Koivula J. I., Kammerling R. C., Eds. (1989) Blau—Die Turmalin-Vorkommen in Mosambik. Miner- Gem News: Unusual tourmalines from Brazil. Gems & alientage München 85—Turmalin, Oct. 18-20, Munich, Gemology, Vol. 25, No. 3, pp. 181-182. Germany. Lit Par39 Rondeau B., Delaunay A. (2007) Les Lit Par23 Koivula J. I., Kammerling R. C., Eds. (1989) tourmalines cuprifères du Nigeria et du Mozambique Gem News: Paraiba tourmaline update. Gems & [Cuprian tourmalines from Nigeria and Mozambique]. Gemology, Vol. 25, No. 4, pp. 248-249. Revue de Gemmologie, No. 160, pp. 8-13. Lit Par24 Koivula J. I., Kammerling R. C., Eds. (1990) Lit Par40 Smith C. P., Bosshart G., Schwarz D. (2001) Gem News: Treated Paraiba tourmaline. Gems & Gem News International: Nigeria as a new source of Gemology, Vol. 26, No. 1, pp. 103-104. copper-manganese-bearing tourmaline. Gems & Lit Par25 Koivula J. I., Kammerling R.C. (1990) Gem Gemology, Vol. 37, No. 3, pp. 239-240. news: The discovery of the Paraiba tourmaline mine. Lit Par41 Wentzell C. Y. (2004) Lab Notes: Copper- Gems & Gemology. Vol. 26, No.2, pp. 164-165. bearing color-change tourmaline from Mozambique. Lit Par26 Koivula J. I., Kammerling R. C., Fritsch E., Gems & Gemology, Vol. 40, No. 3, pp. 250-251. Eds. (1992) Gem News: Tourmaline with distinctive Lit Par42 Wentzell C. Y., Fritz E., Muhlmeister S. inclusions. Gems & Gemology, Vol. 28, No. 3, pp. (2005) Lab Notes: More on copper-bearing color- 204-205. change tourmaline from Mozambique. Gems & Lit Par27 Milisenda C. C. (2005) "Paraiba-Turmaline" Gemology, Vol. 41, No. 2, pp. 173-175. aus Quintos de Baixo, Rio Grande do Norte, Brasilien. Gemmologie: Zeitschrift der Deutschen Gemmolo- Lit Par43 Wise R. W. (2007) Mozambique: The new gischen Gesellschaft, Vol. 54, No. 2-3, pp. 73-84. Paraiba? Colored Stone, Vol. 20, No. 2, pp. 10-11. Lit Par44 Zang J. W., da Fonseca-Zang W. A., Fliss F., Lit Par28 Shigley J. E., Cook B. C., Laurs B. M., Höfer H. E., Lahaya Y. (2001) Cu-haltige Elbaite aus Oliveira Bernardes M. (2001) An update on "Paraiba" Nigeria. Berichte der Deutschen Mineralogischen tourmaline from Brazil. Gems & Gemology, Vol. 37, Gesellschaft, Beihefte zum European Journal of No. 4, pp. 260-276. Mineralogy, Vol. 13, p. 202. Literature review on tourmalines from Africa Literature arrived at printing date Lit Par29 Abduriyim A., Kitawaki H. (2005) Cu- and Lit Par48 Koivula J. I., Nagle K., Shen A. H-T., Owens Mn-bearing tourmaline: More production from Mozam- P. (2009) Solution-Generated Pink Color Surrounding bique. Gems & Gemology, Vol. 41, No. 4, pp. 360- Growth Tubes and Cracks in Blue to Blue-Green 361. Copper-Bearing Tourmalines from Mozambique. Lit Par30 Bettencourt Dias M., Wilson W. E. (2000) Gems & Gemology, Vol. 40, No.1, pp. 44-47. Famous mineral localities: The Alto Ligonha pegma- tites, Mozambique. Mineralogical Record, Vol. 31, pp. 459-497. Lit Par31 Breeding C. M., Rockwell K., Laurs B. M. (2007) Gem News International: New Cu-bearing tourmaline from Nigeria. Gems & Gemology, Vol. 43, No. 4, pp. 384-385. Lit Par32 Henricus J. (2001) New Nigeria tourmaline find excites trade interest. Jewellery News Asia, No.207, pp. 77-78, 87. Lit Par33 Laurs, B.M.,Zwaan J.C., Breeding C.M., Simmons W.B., Beaton D., Rijsdijk K.F., Befi R., Falster A.U. (2008) Copper-bearing (Paraiba-type) tourmaline from Mozambique. Gems & Gemology, 2008. Vol. 44, No. 1: pp. 4-30. Lit Par34 Lächelt S. (2004) The Geology and Mineral Resources of Mozambique. National Directorate of Geology, Maputo, Mozambique, 515 pp.

72 LA-ICP-MS Analysis (inµg/g).SampleNo.GRS-Ref3111, 2079,2965 Table Par02:ChemicalCompositionsofCopper-Bearing Tourmalines fromBrazil 73 O rigin Brazil Sam ple 3111-a 2079 2079_47 2965 "neon"-greenish "neon" Color blue purple yellow ish-green dark-green violetish-blue green -greenish Blue Violet Yellow ish-green blue -blue Q ty 30 18 12 4 40 13 3 1 31 2 17 Avg St Dev Avg St Dev Avg St Dev Avg St Dev Avg St Dev Avg St Dev Avg St Dev Single Avg St Dev Avg St Dev Avg St Dev Al 210000 210000 210000 210000 210000 210000 210000 210000 210000 210000 210000 Si 190807 6017 185328 2782 190583 5228 182675 2304 169928 4456 169423 1150 156200 2138 167600 176900 6421 178300 4525 178547 6582 B 39230 1217 37378 994 37908 994 36350 465 34978 1373 35638 681 33567 643 35000 37465 1347 37800 1273 37159 1906 Li 9804 379 9089 182 8952 261 8335 64 9679 340 9239 142 8453 85 9160 10009 654 10400 424 9794 450 Na 19017 521 17494 333 19158 399 20450 238 13143 536 14262 293 13767 115 14000 14806 800 14900 141 16524 710 M n 27357 1161 23278 554 23125 1566 16275 1266 5379 2413 13546 1832 16167 473 13600 7609 5774 7285 1874 15371 2594 Cu 11439 506 10202 371 6995 1250 6555 281 4955 574 6819 223 6343 50 6660 9839 1965 9185 2001 5763 467 Be 47.0 4 22.7 3 20.69 3 11.7 2.1 16.6 2.5 15.4 2.0 17.1 2 15.5 24.0 7.2 26.6 2.9 16.9 3 M g 59.65 256 15.8 46 2602 958 3495 165 bd to 1530 bd to 1.40 0.94 0.7 bd 4.44 4.3 86.3 53 543 145 K 153 6 137 3 175 62 164 93.5 58 98.6 5.4 103 1 97.2 115 39 114 7 126 8 Ca 2679 52 1316 210 1098 124 715 59 2047 253 1962 75 1897 25 1930 2107 195 2485 134 2014 166 Sc 0.426 0.07 0.380 0.1 0.36 0.1 0.322 0.1 0.449 0.06 0.541 0.09 0.519 0.473 0.411 0.05 0.547 0.08 0.456 0.09 Ti 22.3 18 36.8 52 517 109 953 33 bd to 80.5 174 59 279 18 175 5.15 3.3 332 122 389 163 V 0.742 0.6 1.92 1.8 7.44 1 18.9 3 0.546 0.24 0.694 0.15 0.976 0.1 0.661 0.483 0.1 1.82 0.9 3.00 1.1 Fe 55.0 157 22.8 40 2462 2133 18500 3676 bd to 189 84.1 43 201 55 74.7 bd to 79.80 784 320 1293 182 Zn 342 1399 49.3 88 4877 1798 5880 441 102 132 131 78 347 84 108 338 341 1845 912 9094 4118 G a 124 4 173 27 158 36 79.3 5 290 17 299 5.4 278 3.6 296 104 12 124 22 148 40 G e 37.0 1.9 51.9 11 41.5 9 18.8 2 11.6 2 8.04 0.5 7.51 0.2 7.15 22.8 11 53.5 0.57 33.4 14 Sr 0.617 0.2 0.256 0.05 2.12 3 16.9 2 bd to 1.36 bd to 0.41 0.030 bd 0.217 0.07 0.183 0.08 0.423 0.3 Nb 0.614 0.07 0.458 0.2 0.871 0.2 0.589 0.1 4.14 0.7 2.60 0.2 2.24 0.09 2.61 2.01 1.4 1.29 0.34 2.25 0.6 Sn bd to 0.42 bd to 0.48 bd to 0.51 0.395 0.1 bd to 0.39 bd to 0.32 bd to 0.20 bd bd to 1.25 bd to 0.35 0.438 0.1 Sb 4.57 0.4 3.54 0.9 5.22 0.7 4.31 0.6 7.46 33 0.525 0.07 0.832 0.3 0.598 4.11 4.4 14.3 1 13.6 2.2 Ta 5.77 0.2 1.00 0.25 0.375 0.1 0.121 4.34 1.3 2.28 0.1 2.04 2.24 2.08 0.50 0.934 0.886 0.3 Pb 48.6 3.5 18.7 7.9 13.4 6.9 32.3 1.8 18.8 4.0 14.5 0.4 13.0 0.9 14.2 24.4 3.3 8.5 3 15.3 9 Bi 1702 88 1228 184 630 197 239 16 217 82 91.5 10 70.0 0.8 89.2 980 829.1 1965 431 756 229 Th 0.3 0.04 bd to 0.17 bd to 0.01 0.19 0.1 0.1 0.1 0.10 0.16 0.1 0.15 bd to 0.21 U 0.07 bd to 0.04 bd to 0.38 bd to 0.01 bd to 0.82 bd to 0.04 bd to 0.01 0.008 bd to 0.36 0.154 0.1 0.166 0.1 Cr bd to 4.76 bd to 4.96 bd to 4.96 bd to 3.65 bd to 4.32 bd to 3.59 bd to 2.12 bd bd to 5.48 3.65 0.28 bd to 4.65 Co bd to 0.65 bd to 0.09 0.720 0.7 7.17 1.8 bd to 0.17 bd to 0.62 0.30 bd bd bd tp 0.47 0.1 0.177 0.1 0.511 0.2 Rb bd to 0.16 bd to 0.06 bd to 39.10 bd to 0.02 bd to 1.03 bd to 0.04 bd to 0.03 0.018 bd to 0.86 0.2 0.202 0.1 bd to 0.49 Zr bd to 0.33 bd to 0.04 bd to 0.02 bd to 0.01 bd to 0.33 bd to 0.03 bd tp 0.02 0.021 bd to 0.05 bd to 0.02 bd to 0.03 M o bd to 1.06 bd to 0.86 bd to 0.45 bd to 0.32 bd to 0.24 bd to 0.28 0.242 0.07 0.280 bd to 0.079 0.173 0.1 0.267 0.1 Ag bd to 0.28 0.136 0.179 0.07 0.242 0.140 0.05 0.15 0.162 0.086 0.178 0.115 0.169 Cs bd to 0.90 bd to 0.53 bd to 13.60 0.128 0.1 bd to 8.03 bd to 0.03 bd to 0.004 bd bd to 1.06 bd to 0.11 bd to 0.28 Ba bd to 0.81 bd to 0.06 bd to 0.10 0.047 bd to0.25 bd to 0.03 bd to 0.02 bd bd to 0.20 0.373 0.4 bd to 0.16 La 0.526 0.07 0.146 0.08 0.501 0.2 0.403 0.29 0.2 0.91 0.09 1.31 0.1 0.798 0.200 0.09 0.668 0.1 0.229 0.1 Ce 0.649 0.1 0.243 0.1 0.937 0.4 0.586 0.06 0.413 0.3 0.96 02 1.46 0.07 0.760 0.165 0.09 0.921 0.3 0.261 0.1 Pr 0.056 bd to 0.05 bd to 0.13 0.027 bd to 0.07 0.06 0.093 0.038 bd to 0.15 0.090 0.1 bd to 0.09 Nd bd to 0.36 bd to 0.18 bd to 0.36 0.096 bd to 0.21 bd to 0.20 0.172 0.061 bd to 0.07 bd bd to 0.11 Sm bd to 0.12 bd to 0.14 bd to 0.17 bd bd to 0.08 bd to 0.06 bd to 0.08 0.058 bd to 0.04 bd bd to 0.04 Eu bd to 0.06 bd to 0.01 bd to 0.02 bd bd to0.01 bd to 0.01 bd to 0.01 bd bd to 0.12 0.023 bd to 0.10 G d bd to 0.13 bd to 0.07 bd to 0.07 bd bd to 0.06 bd to 0.03 bd to 0.03 bd bd to 0.04 bd bd to 0.07 Tb bd to 0.02 bd to 0.01 bd to 0.01 bd to 0.01 bd to 0.01 bd to 0.002 bd to 0.002 bd bd to 0.02 bd to 0.01 bd to 0.02 Dy bd to 0.05 bd to 0.04 bd to 0.04 bd bd to0.02 bd to 0.03 bd to 0.001 bd bd to 0.04 bd to 0.01 bd to 0.02 Ho bd to 0.02 bd to 0.01 bd to 0.003 bd to 0.01 bd to 0.01 bd to 0.01 bd bd bd to 0.03 0.012 bd to 0.02 Tm bd to 0.005 bd to 0.01 bd to 0.01 bd to 0.01 bd to 0.004 bd to 0.004 bd to 0.002 bd bd to 0.01 0.005 bd to 0.04 Yb bd to 0.05 bd to 0.04 bd to 0.08 bd bd to 0.03 bd to 0.02 bd bd bd to 0.03 bd to 0.02 bd to 0.06 Lu bd to 0.007 bd to 0.003 bd to 0.003 bd to 0.002 bd to 0.01 bd to 0.003 bd to 0.002 0.002 bd to 0.01 bd to 0.02 bd to 0.02 Pt bd to 0.098 bd to 0.10 bd to 0.13 bd to 0.12 bd to 0.1 bd to 0.05 bd bd bd to 0.09 bd to 0.07 bd to 0.04 Au bd to 0.06 bd to 0.06 bd to 0.02 bd to 0.01 bd to 0.05 bd to 22.7 bd 22.7 bd to 0.03 bd to 0.01 bd to 0.07 O rigin Brazil Sam ple 2976-1 2976 2976-1 2976 2976-2 Color blue yellow ish green/green yellow ish-green purple/greenish-blue "neon"-greenish-blue purple/greenish-blue purple "neon"-greenish-blue yellow ish-green Q ty 28 53 5 1 7 7 1 12 13 5 Table Par03:ChemicalCompositionsofCopper-Bearing Tourmalines fromBrazil Avg St Dev Avg St Dev Avg St Dev Avg Avg St Dev Avg Avg St Dev Avg St Dev Avg St Dev Al 210000 210000 210000 210000 210000 210000 210000 210000 210000 Si 168186 2338 172002 4941 217220 8205 237800 228000 5216 221900 221400 2962 230954 5791 241040 3988 B 34079 567 34715 1429 34960 1412 38900 37257 1103 35400 34675 497 36385 921 36980 559 Li 9492 251 9605 322 9074 351 10500 10087 330 9820 8633 403 9935 379 10098 278 Na 13211 302 14762 585 13240 559 14100 13443 351 13200 13167 242 13500 515 14800 283 M n 189 94 11850 3736 5610 958 2660 296 123 846 1420 270 470 386 4760 1741 Cu 7920 1027 5603 948 3920 512 8040 7879 1135 8590 3487 1780 7560 1011 6268 2000 Be 48.4 10 34.9 10 59.20 2 75.4 46 16 28.1 8.94 7 44.3 16 54.1 14 M g bd to 1.50 230 126 259 102 14.2 bd to 3.60 bd bd to 2.44 4.64 12 161 168 K 83.5 10 102 5 95.8 5 92.8 84 23 81.6 88.2 11 85.8 5.9 95.3 4.4 Ca 752 220 1625 390 1113 450 769 895 386 2110 486 487 984 382 783 115 Sc 0.440 0.06 0.439 0.07 0.357 0.430 0.435 0.36 0.348 0.304 0.333

Ti bd to 19.40 293 156 441 85 49.4 bd to 9.67 1.09 bd to 2.91 bd to 16 307 261 LA-ICP-MS Analysis V 0.45 0.1 2.13 0.80 1.10 0.35 0.440 0.376 0.1 0.28 0.286 0.1 0.428 0.23 0.763 0.35 Fe bd to 36.40 1787 803 2550 459 379 27.4 34 7.29 bd to 8.01 bd to 70 1799 1464 Zn 12.2 12 1564 671 1564 311 428 26.6 27 11.5 14.8 7 112 312 1234 795 G a 111 8.6 153 33 160 13 114 121 8 124 143 6 124 12 142 31 G e 33.7 4.5 33.3 10 42.5 3.3 40.1 34.5 5 n/a 0.00 0.000 0.000 Sr 0.078 0.07 0.189 0.2 0.059 0.166 0.110 0.2 0.127 bd to 0.22 0.097 0.06 0.125 0.07 Nb 0.120 0.918 0.2 0.566 0.11 0.309 0.149 0.1 0.544 0.229 0.1 0.211 0.15 0.668 0.45 Sn bd to 0.94 bd to 0.70 bd to 0.40 bd bd to 0.29 0.188 bd to 0.48 bd to 2.08 0.323 0.11 Sb 7.35 2.9 13.65 2 7.87 0.79 14.4 5.31 1.5 4.14 6.80 11 7.81 3.6 9.82 2.2 Ta 1.03 0.3 0.449 0.1 0.406 0.06 0.412 1.32 0.7 2.32 1.01 0.4 1.40 0.68 0.533 0.18 Pb 33.66 7 17.2 11 7.31 3.3 23.3 34.2 5.6 51.5 8.67 11 35.2 5.3 16.12 10.4 Bi 3600 1207 2702 1250 3428 383 3860 2441 1085 1390 285 385 2455 1201 3524 632 Th bd to 2.03 bd to 0.46 0.776 0.43 0.308 1.26 0.6 0.53 0.07 0.1 1.16 0.61 0.33 0.15 (in µg/g).SampleNo.GRS-Ref2976 U 0.132 0.1 bd to 0.67 0.292 0.41 0.020 0.094 0.1 0.080 bd to 0.17 0.115 0.10 0.027 Cr bd to 20 bd to 43.1 bd to 2.23 bd bd to 2.46 bd bd to 188 12.5 13 7.62 9.9 Co bd to 0.44 0.468 0.3 0.838 0.42 0.242 bd to 0.12 0.035 bd to 0.38 bd to 0.23 bd to 1.08 Rb bd to 0.28 bd to 3.65 bd to 0.14 bd bd to 0.02 0.079 bd to 8.16 bd to 0.78 bd to 0.47 Zr bd to 0.04 bd to 0.07 bd to 0.03 0.021 bd to 0.02 bd bd bd bd M o bd to 0.98 bd to 1.18 bd to 0.15 0.059 bd to 0.09 n/a n/a n/a n/a Ag bd to 0.27 bd to 0.62 0.073 0.154 bd to 0.14 0.223 0.15 bd to 0.26 0.097 Cs bd to 13.90 bd to 0.65 bd to 0.05 0.066 bd to 1.11 0.140 bd to 1.1 1.59 3.1 0.114 0.1 Ba bd tp 3.90 bd to 2.00 bd to 0.02 bd bd to 0.01 bd bd to 1.23 bd to 0.26 bd to 0.05 La bd to 0.04 0.360 0.3 0.119 0.09 0.023 bd to 0.03 0.063 bd to 0.04 bd to 0.10 0.052 0.1 Ce bd to 0.34 0.816 0.6 0.301 0.30 0.014 bd to 0.11 0.043 bd to 0.03 bd to 0.17 bd to 0.37 Pr bd to 0.13 bd to 0.25 bd to 0.03 0.002 bd to 0.003 0.021 bd to 0.01 bd to 0.14 bd to 0.04 Nd bd to 0.04 bd to 0.49 bd to 0.15 bd bd bd bd to 0.03 bd to 0.05 bd to 0.10 Sm bd to 0.06 bd to 0.32 bd to 0.13 bd bd 0.044 bd to 0.04 bd to 0.02 bd to 0.09 Eu bd to 0.09 bd to 0.19 bd to 0.04 bd bd to 0.03 0.022 bd to 0.04 bd to 0.07 bd to 0.01 G d bd to 0.06 bd to 0.28 0.057 bd bd to 0.03 bd bd to 0.04 bd bd Tb bd to 0.02 bd to 0.09 bd to 0.02 0.008 bd to 0.006 n/a n/a n/a n/a Dy bd to 0.08 bd to 0.09 bd to 0.06 bd bd to 0.01 bd bd to 0.02 bd to 0.02 bd Ho bd to 0.03 bd to 0.10 bd bd bd to 0.02 n/a n/a n/a n/a Tm bd to 0.03 bd to 0.04 bd 0.004 bd to 0.001 n/a n/a n/a n/a Yb bd to 0.07 bd to 0.07 bd to 0.01 0.008 bd to 0.01 bd bd to 0.03 bd to 0.01 bd to 0.01

74 Lu bd to 0.04 bd to 0.07 bd 0.006 bd to 0.01 bd bd to 0.004 bd to 0.003 bd Pt bd to 0.07 bd to 0.11 bd bd bd to 0.04 n/a n/a n/a n/a Au bd to 0.04 bd to 0.08 bd to 0.03 bd bd bd bd to 0.05 bd to 0.04 bd to 0.04 LA-ICP-MS Analysis (inµg/g).SampleNo.GRS-Ref7782,3134 Table Par04:ChemicalCompositionsofCopper-Bearing Tourmalines fromMozambique 75 O rigin M ozam bique Sam ple M oz 7782 3134 Color violet purple blue yellow ish-green Blue blue-green deep green green purple violet Q ty 45 25 40 22 27 8 10 6 38 49 Avg St Dev Avg St Dev Avg St Dev Avg St Dev Avg St Dev Avg St Dev Avg St Dev Avg St Dev Avg St Dev Avg St Dev Al 210000 210000 210000 210000 210000 210000 210000 210000 210000 210000 Si 191313 5807 187724 2587 184990 2795 187359 7615 167033 1768 168125 1212 170660 2852 170400 917 184795 8312 168739 2358 B 33298 940 33700 595 32305 1215 36286 1500 36130 839 36013 422 35940 406 36000 358 40553 1920 35122 1144 Li 11023 340 10756 301 10580 194 10727 383 10160 178 10238 130 10310 88 10300 89 10286 491 10178 185 Na 12991 495 13048 171 13508 251 14036 561 13211 222 13300 120 13570 245 13433 82 15116 717 13184 224 M n 1253 33 1078 62 306 251 1794 1196 156 87 253 157 2054 510 707 135 1799 72 1022 562 Cu 3062 135 2167 205 2793 315 1392 273 2786 208 2019 253 1212 83 1535 104 1207 93 2833 141 Be 56.3 4.3 49.3 3.6 43.0 12 71.7 7.6 38.4 8.6 52.2 3.3 56.7 8.6 50.8 4.0 5.94 1.3 25.5 3.1 M g bd to 2.37 bd to 6.14 bd to 12.1 24.1 25 bd to 1.13 bd to 1.18 22.3 11.5 6.55 2.5 bd to 2.85 bd to 7.42 K 113 6.2 99.4 4.3 90.1 6.8 123 29 91.3 1.7 95.9 3.9 103 2.0 102 2.7 122 6.8 93.5 2.5 Ca 4966 70 4146 283 1599.03 758 1396 809 1346 451 436 82 1293 561 646 70 665 33 1939 290 Sc 0.56 0.1 0.489 0.1 0.501 0.1 2.32 1.3 0.284 0.06 0.377 0.12 2.61 0.51 1.02 0.31 0.454 0.08 0.318 0.07 Ti bd to 3.13 bd to 5.69 bd to 25.5 172 106 bd to 1.83 bd to 28.1 240 40 62.2 37 bd to 1.87 bd to 2.81 V 1.00 0.5 0.898 0.4 0.889 0.4 1.12 0.41 0.640 0.19 0.840 0.45 1.04 0.21 0.661 0.07 0.487 0.10 0.762 Fe bd to 32.8 bd to 7.38 bd to 93.4 1601 1030 bd to 5.00 bd to 115 1930 429 673 306 bd to 7.00 bd to 6.87 Zn bd to 1.83 bd to 1.54 bd to 2.63 14.1 7.3 bd to 1.17 bd to 1.23 18.4 3.3 6.97 3.2 bd to 1.22 bd to 1.06 G a 335 11 355 6.3 352 13 313 10 357 11 333 8.8 311 4.2 318 1.7 467 21 378 6.3 G e 11.58 0.8 13.4 0.7 16.9 2.5 20.4 1.0 17.4 1.7 20.8 0.93 19.8 0.44 19.9 0.53 6.67 0.55 12.9 1.5 Sr 0.506 0.1 0.420 0. 0.241 0.20 1.04 0.91 0.155 0.11 0.209 0.11 0.868 0.46 0.352 0.04 bd to 0.088 0.172 0.04 Nb 1.26 0.1 1.65 0.1 0.848 0.48 0.794 0.30 0.647 0.24 0.363 0.08 0.724 0.12 0.446 0.11 0.778 0.07 1.80 0.57 Sn 1.81 0.4 1.75 0.4 1.10 0.46 5.16 2.5 0.924 0.30 1.67 0.56 6.03 1.5 2.86 0.69 1.56 0.15 1.46 0.41 Sb 15.1 0.7 12.4 0.8 11.4 1.8 19.8 6.7 10.4 1.2 12.7 0.91 16.9 1.3 14.6 0.59 1.24 0.21 6.60 0.98 Ta 2.44 0.1 2.91 0.2 1.14 0.37 0.502 0.10 1.08 0.22 0.610 0.06 0.446 0.08 0.526 0.05 0.564 0.05 1.50 0.14 Pb 132 5.1 108 7.2 58.8 12 29.2 2.5 52.0 9.5 28.5 6.7 20.4 1.9 21.5 1.7 9.89 0.58 46.7 3.5 Bi 2584 83 2249 83 2564 1024 4992 454 2308 578 3433 177 3948 478 3530 55 105 8 1102 168 Th 1.21 0.1 1.68 0.1 0.49 0.19 0.35 0.19 0.46 0.15 0.56 0.10 0.24 0.07 0.39 0.06 bd to 0.02 0.21 0.04 U 0.344 0.5 0.440 0.3 0.289 0.50 0.318 0.39 bd to 1.17 bd to 0.268 bd to 0.306 bd to 0.390 bd to 0.144 bd to 0.316 Cr bd to 5.19 bd to 7.58 bd to 12.9 bd to 5.31 bd to 5.39 bd to 4.65 bd to 4.55 bd to 3.84 bd to 5.31 bd to 4.13 Co bd to 0.97 bd to 0.63 bd to 0.56 bd to 1.25 bd to 0.698 bd to 0.055 bd to 0.0109 bd to 0.082 bd to 0.419 bd to 0.731 Rb bd to 0.78 bd to 1.87 bd to 1.05 bd to 0.97 bd to 0.543 bd to 0.280 bd to 0.414 bd to 0.026 bd to 0.283 bd to 0.658 Zr bd to 0.06 bd to 0.06 bd to 0.06 bd to 0.05 bd to 0.062 bd to 0.033 bd to 0.021 bd to 0.021 bd to 0.045 bd to 0.040 M o bd to 2.30 bd to 1.55 bd to 1.34 bd to 1.44 bd to 0.600 bd to 0.123 bd to 0.336 bd to 0.241 bd to 0.347 bd to 0.566 Ag bd to 0.96 bd to 0.32 bd to 0.32 bd to 0.38 bd to 0.609 bd to 0.231 bd to 0.070 bd to 0.086 bd to 0.184 bd to 0.262 Cs bd to 1.19 bd to 2.74 bd to 4.43 bd to 0.84 bd to 0.365 bd to 0.280 bd to 0.162 bd to 0.129 bd to 0.542 bd to 0.707 Ba bd to 0.29 bd to 0.64 bd to 0.65 bd to 0.64 bd to 0.187 bd to 0.269 bd to 0.276 bd to 0.189 bd to 0.096 bd to 0.229 La bd to 0.25 bd to 0.16 bd to 0.06 0.162 0.32 bd to 0.075 bd to 0.087 0.085 0.05 bd to 0.103 bd to 0.033 bd to 0.053 Ce bd to 0.47 bd to 0.25 bd to 0.53 0.355 0.28 bd to 0.646 bd to 0.386 0.153 0.090 0.05 bd to 0.038 bd to 0.288 Pr bd to 0.17 bd to 0.10 bd to 0.11 bd to 0.30 bd to 0.110 bd to 0.234 bd to 0.033 bd to 0.034 bd to 0.119 bd to 0.092 Nd bd to 0.10 bd to 0.06 bd to 0.13 bd to 0.43 bd to 0.101 bd to 0.128 bd to 0.094 bd to 0.025 bd to 0.075 bd to 0.070 Sm bd to 0.11 bd to 0.12 bd to 0.15 bd to 0.14 bd to 0.118 bd to 0.213 bd to 0.111 bd to 0.060 bd to 0.050 bd to 0.111 Eu bd to 0.16 bd to 0.28 bd to 0.09 bd to 0.08 bd to 0.093 bd to 0.008 bd to 0.112 bd to 0.008 bd to 0.105 bd to 0.043 G d bd to 0.07 bd to 0.09 bd to 0.08 bd to 1.15 bd to 0.056 bd bd to 0.080 bd to 0.057 bd to 0.047 bd to 0.068 Tb bd to 0.04 bd to 0.02 bd to 0.02 bd to 0.06 bd to 0.020 bd to 0.013 bd to 0.030 bd to 0.013 bd to 0.018 bd to 0.043 Dy bd to 0.05 bd to 0.05 bd to 0.06 bd to 0.07 bd to 0.079 bd to 0.085 bd to 0.083 bd to 0.082 bd to 0.094 bd to 0.065 Ho bd to 0.04 bd to 0.02 bd to 0.02 bd to 0.03 bd to 0.034 bd bd to 0.009 bd to 0.008 bd to 0.007 bd to 0.008 Tm bd to 0.04 bd to 0.03 bd to 0.03 bd to 0.03 bd to 0.007 bd to 0.008 bd to 0.015 bd to 0.004 bd to 0.009 bd to 0.034 Yb bd to 0.06 bd to 0.05 bd to 0.04 bd to 0.05 bd to 0.074 bd bd to 0.025 bd to 0.121 bd to 0.061 bd to 0.042 Lu bd to 0.02 bd to 0.03 bd to 0.03 bd to 0.05 bd to 0.011 bd bd to 0.024 bd to 0.008 bd to 0.006 bd to 0.012 Pt bd to 0.09 bd to 0.08 bd to 0.12 bd to 0.07 bd to 0.038 bd bd to 0.113 bd to 0.074 bd to 0.098 bd to 0.065 Au bd to 0.09 0.100 bd to 0.09 bd to 0.05 bd to 0.125 bd bd to 0.090 bd to 0.103 bd to 0.117 bd to 0.132 Table Par05:ChemicalCompositionsofCopper-Bearing Tourmalines fromMozambique

Ba contaminationswerefoundinthesurfacelayer O rigin M ozam bique of thefollowingsamples(concentrationsinppm)

Sam ple 2939 2942 2942.2 2943 3138 3143 LA-ICP-MS Analysis

Sample No.Ba-concentrations Color Violet G reen Yellow ish-G reen Blue G reen Vivid G reen Purple Q ty 3 3 3 3 6 6 Avg St Dev Avg St Dev Avg St Dev Avg St Dev Avg St Dev Avg St Dev

33 66.8ppm 44.0ppm 2343 65.8ppm 2939 37.7ppm 2942.2 2942 Al 210000 210000 210000 210000 210000 210000 Si 164967 1966 164467 1498 161867 1401 165967 1069 169633 2038 164767 2482 B 34400 529 35200 300 34233 306 34967 513 34783 850 33233 843 Li 10167 231 8837 110 8197 35 8527 238 7698 187 8442 135 Na 13933 208 18600 173 16967 153 17000 361 16133 398 13750 266 M n 11333 208 37500 346 34867 1747 30367 814 28133 258 7777 1234 Cu 3237 95 2490 35 2427 416 3350 401 1945 69 1802 141 Be 32.6 5.5 28.7 1.7 18.0 2.9 17.5 3.2 7.69 2.9 7.94 2.3 M g 2.16 0.7 3.05 1.0 4.46 6.0 9.95 9.5 2.34 1.5 bd to 142 K 134 8.0 196 7.5 175 5.0 160 17 171 2.3 131 8.5 Ca 4917 90 1860 46 1620 122 1417 170 561 18 780 36 2943,3138,3143 (in µg/g).SampleNo.GRS-Ref2939,2942, Sc 0.421 0.09 9.76 0.21 2.82 0.39 1.04 0.13 2.06 0.12 0.679 0.06 Ti 44.0 12 224 9.7 216 85 103 7.8 267 11 bd to 3.15 V 0.542 0.29 2.35 0.41 1.09 0.15 2.51 1.1 1.54 0.14 0.570 0.45 Fe 56.3 66 355 55 181 45 287 232 189 12 bd to 40.7 Zn 4.35 2.1 6.89 0.88 8.84 0.55 11.7 2.0 17.1 2.0 bd to 2.16 G a 343 6.1 392 6.00 404 13.6 398 4.6 435 6.8 446 12 G e 7.68 0.27 11.1 0.25 8.98 0.53 11.2 0.81 5.59 0.31 7.52 0.45 Sr 0.462 0.28 1.39 0.05 0.231 0.02 0.387 0.09 0.079 0.02 0.130 0.03 Nb 2.81 0.20 1.36 0.14 0.903 0.10 1.78 0.47 0.54 0.05 0.316 0.05 Sn 4.44 0.13 14.7 0.51 8.80 0.16 3.85 0.21 9.17 8 2.53 1.0 Sb 5.91 0.05 3.61 0.24 1.06 0.06 1.90 0.52 0.48 0.11 1.33 0.11 Ta 2.36 0.09 1.63 0.10 1.00 0.17 1.32 0.08 0.41 0.05 0.404 0.03 Pb 80.6 1.2 74.5 1.1 34.2 1.8 49.6 10 8.78 2.2 18.4 6 Bi 967 12 858 4.4 258 19 467 63 27.1 0.71 151 4 Th 0.68 0.08 0.15 0.02 0.13 0.01 0.12 0.03 bd to 0.011 bd to 0.018 U 0.064 0.02 bd to 0.147 bd bd to 0.066 bd to 0.047 bd to 0.081 Cr 8.13 5.2 9.92 3.8 6.38 3.0 bd to 22.9 bd to 3.52 bd Co 0.073 0.05 0.079 0.01 bd to 0.05 bd 1.33 1.4 bd to 1.13 Rb bd to 2.24 bd to 0.054 bd to 0.060 bd to 0.093 0.062 0.03 bd to 0.064 Zr bd bd to 0.010 bd to 0.119 bd to 0.036 bd to 0.029 bd to 0.018 M o 0.185 0.07 0.473 0.22 0.387 0.25 bd to 0.567 0.301 0.08 bd to 0.272 Ag bd to 0.06 0.034 0.01 bd to 0.102 bd to 0.068 bd to 0.098 bd to 14.7 Cs bd to 0.068 bd to 0.054 bd to 0.071 0.013 0.00 bd to 9.05 bd to 0.056 Ba bd to 0.12 bd to 0.193 0.113 0.04 bd bd to 0.069 bd to 0.084 La bd to 0.082 bd to 0.047 0.022 0.01 bd to 0.232 bd to 0.004 bd to 0.004 Ce 0.066 0.02 0.044 0.02 bd to 0.029 0.111 0.11 bd to 0.241 bd ot 0.012 Pr bd to 0.011 bd to 0.010 bd to 0.011 0.018 0.02 bd to 0.008 bd to 0.007 Nd bd to 0.088 bd to 0.073 bd to 0.163 bd bd to 0.021 Sm bd to 0.086 bd to 0.053 bd bd to 0.049 bd to 0.040 bd to 0.023 Eu bd to 0.015 bd bd to 0.007 bd to 0.006 bd to 0.006 bd to 0.011 G d bd bd to 0.053 bd to 0.071 bd to 0.020 bd Tb bd bd to 0.004 bd to 0.007 bd to 0.006 bd to 0.006 Dy bd to 0.017 0.00 bd to 0.015 bd 0.028 0.02 bd to 0.011 bd to 0.013 Ho bd to 0.008 bd to 0.016 bd bd to 0.003 bd to 0.003 Tm bd to 0.01 bd to 0.003 bd bd to 0.003 bd to 0.003 bd to 0.006 Yb bd to 0.042 bd to 0.022 bd to 0.062 bd to 0.018

76 Lu bd to 0.004 bd to 0.007 bd to 0.008 bd to 0.003 bd to 0.003 Pt bd to 0.035 bd bd bd bd to 0.130 Au bd bd bd to 0.022 bd to 0.071 Table Par06: Chemical Compositions of Copper-Bearing Tourmalines from Nigeria LA-ICP-MS Analysis (in µg/g)

Origin Nigeria Nigeria Nigeria Nigeria Nigeria Sample N 1533_lot 4.88 N 0671_kt 23.77 Ref. 2877 Ref. 2876 N 0441 Qty 5 5 5 5 5 Type Avg StDev Avg StDev Avg StDev Avg StDev Avg StDev Al 210000 210000 210000 210000 210000 Si 167860 2802 165280 2428 165480 1483 169120 1757 168380 1370 B 33560 646 32560 532 32560 181 32820 408 33420 465 Li 9810 188 10058 94 10060 89 9880 163 9952 47 Na 12820 383 11760 151 11500 18 12000 70 11580 109 Mn 6354 325 3066 73 659 35 3074 130 3292 41 Cu 3066 201 1634 59 1966 36 2534 65 1736 27 Be 33.0 4.8 30.2 7 29 4 36 3.2 35.2 6 Mg bd to 0.23 bd 2.0 1 bd to 4.72 6.7 1.1 K 109 2.7 100 2.2 102 2 103 1.1 113 1.1 Ca 5208 118 5726 118 4786 136 5120 86 5746 66 Sc bd to 0.48 bd to 0.47 bd to 0.43 bd to 0.47 0.3 0.1 Ti bd bd to 1.52 bd to 2.46 bd to 2.58 bd to 1.92 V 0.4 0.1 0.4 0.3 bd to 0.53 0.3 0.1 bd to 0.34 Fe 79.4 5.3 20.4 3.4 48.9 6 bd to 14.6 58.7 6 Zn 1360 86 10.1 0.8 9.3 2.1 36.6 2.3 17.1 1.2 Ga 105 3.6 103 2.5 133 3.8 98 1.5 105 3.2 Ge 24.3 0.7 22.6 1.2 33.8 1.5 26.3 1.1 24.2 0.4 Sr 20.6 0.7 119 2.6 138 3.7 21.8 0.4 117.4 0.9 Nb 2.8 0.1 3.8 0.1 1.0 0.1 2.6 0.1 4.0 0.2 Sn 0.9 0.1 1.3 0.1 1.9 0.4 1.8 0.4 1.3 0.1 Sb 9.8 0.6 12.2 0.5 55.4 1.6 13.9 0.5 12.8 0.6 Ta 20.0 1.0 13.7 1.2 8.9 0.5 15.8 0.3 15.1 0.2 Pb 1102 39 1102 37 487 17 1222 25 1156 1 Bi 273 6 348 12 323 12 379 6 368 3 Th 1.1 0.1 1.3 0.2 2.0 0.1 0.7 0.1 1.7 0.1 U bd bd bd to 0.004 bd to 0.004 bd to 0.003 Cr bd bd bd to 2.04 bd bd to 2.19 Co bd bd to 0.06 bd bd to 0.06 bd to 0.03 Rb bd to 0.97 bd to 0.14 bd bd bd to 0.10 Zr bd to 0.06 bd to 0.02 bd to 0.03 bd to 0.03 0.11 0.03 Mo bd to 0.05 bd bd bd to 0.10 bd Ag bd to 0.03 bd to 0.11 bd to 0.11 bd to 0.12 bd to 0.06 Cs bd to 0.89 bd to 0.13 bd bd to 0.02 bd to 0.01 Ba bd to 0.06 bd to 0.11 bd to 0.06 bd 0.17 0.10 La 0.08 0.02 bd to 0.01 0.03 0.01 bd to 0.10 bd to 0.02 Ce bd to 0.01 bd to 0.20 0.11 0.16 bd 0.02 0.01 Pr bd to 0.002 bd to 0.00 bd to 0.005 bd to 0.002 bd to 0.002 Nd bd to 0.01 bd to 0.02 bd to 0.03 bd to 0.01 bd to 0.02 Sm 0.01 0.01 bd to 0.17 bd to 0.02 bd bd to 0.03 Eu bd to 0.01 bd to 0.14 bd bd to 0.005 bd to 0.00 Gd bd to 0.04 bd bd to 0.04 bd to 0.02 bd to 0.04 Tb bd bd bd bd bd Dy bd to 0.01 bd to 0.01 bd to 0.01 bd to 0.01 bd to 0.01 Ho bd bd to 0.004 bd bd to 0.004 bd to 0.004 Tm bd to 0.004 bd to 0.01 bd to 0.003 bd to 0.01 bd to 0.003 Yb bd to 0.02 bd bd 0.01 0.01 bd Lu bd bd to 0.009 bd to 0.005 bd to 0.009 bd to 0.004 Pt bd to 0.03 bd to 0.03 bd to 0.03 bd bd Au 0.10 0.03 bd to 0.09 bd to 0.07 bd to 0.09 bd tp 0.29

77

Copper-bearing tourmaline with “Paraiba”-type color are considered the most valuable gems in the world of tourmalines. A documentation of recent and historical pictures of the mines in Brazil is presented in this report together with statistics on size and color of the most valuable tourmalines from different localities.

This study also derives a more simple and inexpensive chemical fingerprinting useful for origin and authenticity analysis of these tourmalines. For this purpose, color-zoned copper-bearing tourmalines from Brazil (such as from Paraiba) and from Mozambique have been analyzed by different chemical testing methods (EMPA, LA-ICP-MS, ED-XRF and LIBS).

Tourmalines from different origins can be separated, because they developed a different pattern of “Chemical Variations” during their growth.

Copyright by GRS Gemresearch Swisslab AG 6002 Lucerne, Switzerland. www.gemresearch.ch ISBN 978-3-9523359-9-4