Computers & Geosciences 63 (2014) 7087

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Computers & Geosciences

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A Windows program for calculation and classication of tourmaline-supergroup (IMA-2011)$

Fuat Yavuz a,n, Necati Karakaya b, Demet K. Yldrm a, Muazzez . Karakaya b, Mustafa Kumral a
a b

Department of Geological Engineering, Istanbul Technical University, 34469 Maslak, Istanbul, Turkey Seluk niversitesi, Mhendislik Fakltesi, Jeoloji Mhendislii Blm, 42079 Konya, Turkey

art ic l e i nf o
Article history: Received 11 June 2013 Received in revised form 17 October 2013 Accepted 18 October 2013 Available online 6 November 2013 Keywords: International Mineralogical Association (IMA) Tourmaline Classication Normalization Software

a b s t r a c t
A Microsoft Visual Basic program, WinTcac, has been developed to calculate structural formulae of tourmaline analyses based on the Subcommittee on Tourmaline Nomenclature (STN) of the International Mineralogical Association's Commission on New Minerals, Nomenclature and Classication (IMACNMCN) scheme. WinTcac calculates and classies tourmaline-supergroup minerals based on 31 O atoms for complete tourmaline analyses. For electron-microprobe-derived tourmaline analyses site occupancy can be estimated by using the stoichiometric H2O (wt%) and B2O3 (wt%) contents. This program also allows the user to process tourmaline analyses using 15 cations and 6 silicons normalization schemes. WinTcac provides the user to display tourmaline analyses in a various classication, environmental, substitution, and miscellaneous plots by using the Golden Software's Grapher program. The program is developed to predict cation site-allocations at the different structural positions, including the T, Z, Y, and X sites, as well as to estimate the OH1 , F1 , Cl1 , and O2 contents. WinTcac provides editing and loading Microsoft Excel les to calculate multiple tourmaline analyses. This software generates and stores all the calculated results in the output of Microsoft Excel le, which can be displayed and processed by any other software for verication, general data manipulation, and graphing purposes. The compiled program code is distributed as a self-extracting setup le, including a help le, test data les and graphic les, which are designed to produce a high-quality printout of the related plotting software. & 2013 Elsevier Ltd. All rights reserved.

1. Introduction Minerals of the tourmaline-supergroup are the most important and ubiquitous accessory borosilicate minerals in a great diversity of geological settings within the Earth's crust (Dutrow and Henry, 2011; van Hinsberg et al., 2011a, 2011b). Within these settings, tourmalines occur in a wide variety of rock compositions, including as authigenic overgrowths on detrial grains in sedimentary rocks (e.g., Henry et al., 1994; Henry and Dutrow, 1996; Van den Bleeken et al., 2007), as resistant and prograde minerals in different facies of metamorphic rocks (e.g., Henry and Dutrow, 1992, 2012; Kawakami, 2001; Torres-Ruiz et al., 2003; Abu El-Enen and Okrusch, 2007; Ertl et al., 2010; van Hinsberg and Schumacher, 2011), and as a primary phase in intrusive rocks and related pegmatites (e.g., London and Manning, 1995; Roda et al., 1995; Keller et al., 1999; Tindle et al., 2002; Trumbull et al.,
The executable code is available in the journal server or from corresponding author on request. n Corresponding author. E-mail address: yavuz@itu.edu.tr (F. Yavuz).

2008; Yavuz et al., 2008). Tourmaline is a common mineral in hydrothermal deposits that are formed by epigenetic and syngenetic processes (Slack and Trumbull, 2011). Tourmalines belong to the epigenetic style are composed of porphyry type Cu 7 Mo deposits (e.g., Lynch and Ortega, 1997; Yavuz et al., 1999), CuAu breccias pipes (e.g., Warnaars et al., 1985; Skewes et al., 2003), and SnW veins in or near granites (e.g., Manning, 1986; Mlynarczyk and Williams-Jones, 2006; Neiva et al., 2007; Esmaeily et al., 2009). Tourmaline-supergroup minerals in syngenetic category are mainly found in sedimentary-exhalative (SEDEX) ZnPbAg deposits (e.g., Bone, 1988; Slack et al., 1993; Jiang et al., 1995) and volcanogenic massive sulde (VMS) CuZnPbAgAu deposits (e.g., Taylor and Slack, 1984; Slack and Coad, 1989; Deb et al., 1997). The presence of tourmaline in such different geological environments made it important to understand the physical and chemical conditions of rock formation, ore-forming processes, and hydrothermal ore deposits. Since the tourmaline-supergroup minerals have an extensive temperature (T) and pressure (P) stability range, they have been used as a good petrogenetic indicator for PTfO2 conditions (Henry and Guidotti, 1985; van Hinsberg et al., 2011a, 2011b and references therein).

0098-3004/$ - see front matter & 2013 Elsevier Ltd. All rights reserved. http://dx.doi.org/10.1016/j.cageo.2013.10.012

F. Yavuz et al. / Computers & Geosciences 63 (2014) 70 87 Table 1 Relative site abundances of cations and anions in tourmaline-supergroup minerals (from Henry et al., 2011). Site X Y Relative abundance of ions with different valence states R1 4 R2 4 vacancy () R2 4 R3 4 R1 4 R4

71

Common cations and anions at each site in order of relative abundance R1 :Na1 4 4 K1 R2 :Ca2 R2 :Fe2 E Mg2 4 Mn2 4 4 4 Zn2 , Ni2 , Co2 , Cu2 R3 :Al3 4 4 Fe3 4 Cr3 4 4 V3 R1 :Li1 R4 :Ti4 R3 :Al3 4 4 Fe3 4 Cr3 4 V3 R2 :Mg2 4 Fe2 R4 :Si4 R3 :Al3 4 B3 R3 :B3

Z T B V W

R3 4 4 R2 R4 4 4 R3 R3 S 4 4S S1 E S2
1 2

S1:OH1 S2 :O2 S1:OH1 E F1 S2:O2

Notes: R cations; S anions; the bolded cations and anions represent the most common ions at these sites.

Table 2 IMA-accepted and prospective alkali-, calcic-, and vacant-group tourmaline species with their end-member compositions (revised from Henry et al., 2011). Row Alkali group 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 Calcic group 30 31 Calcic-subgroup 1 Fluor-uviten Feruviten Ca2 Ca Ca R32 Mg3 Fe32 R2 R53 MgAl5 MgAl5 R64 O18 Si6O18 Si6O18 (BO3)3 (BO3)3 (BO3)3 S31 (OH)3 (OH)3 S1 F (OH) General formula ( X) (Y3) (Z6) T6O18 (BO3)3 V3 W

Alkali-subgroup 1 Draviten Schorln Chromium-draviten Vanadium-draviten Fluor-draviten Fluor-schorn Potassium-dravite Tsilaisitea Alkali-subgroup 2 Elbaiten Fluor-elbaiteb Alkali-subgroup 3 Povondraiten Chromo-alumino-povondraiten Oxy-dravitec Oxy-schorld NaCrO root name (Oxy-chromium-dravite)e (Oxy-vanadium-dravite)f Vanadio-oxy-draviteg Vanadio-oxy-chromium-draviteh Potassium-povondraite Alkali-subgroup 4 NaLiO root name (Darrellhenryite)i Alkali-subgroup 5 Fluor-buergeriten Oleniten Buergerite Fluor-olenite Alkali-subgroup 6 NaAlAlAl root name NaAlAlB root name Fluor-NaAlAlAl root name Fluor-NaAlAlB root name

R1 Na Na Na Na Na Na K Na R1 Na Na R1 Na Na Na Na Na Na Na Na K R1 Na R1 Na Na Na Na R1 Na Na Na Na

R32 Mg3 Fe32 Mg3 Mg3 Mg3 Fe32 Mg3 Mn32 R1.51 R1.53 Li1.51 Al1.53 Li1.51 Al1.53 R33 Fe33 Cr3 Al3 Al3 Cr3 V3 V3 V3 Fe33 R11 R23 Li1 Al2 R33 Fe33 Al3 Fe33 Al3 R33 Al3 Al3 Al3 Al3

R63 Al6 Al6 Cr6 V6 Al6 Al6 Al6 Al6 R63 Al6 Al6 R43 R22 Fe34 Mg2 Al4 Mg2 Al4 Mg2 Al4 Fe22 Cr4 Mg2 V4Mg2 Al4 Mg2 Cr4 Mg2 Fe34 Mg2 R63 Al6 R63 Al6 Al6 Al6 Al6 R63 Al6 Al6 Al6 Al6

R64 O18 Si6O18 Si6O18 Si6O18 Si6O18 Si6O18 Si6O18 Si6O18 Si6O18 R64 O18 Si6O18 Si6O18 R64 O18 Si6O18 Si6O18 Si6O18 Si6O18 Si6O18 Si6O18 Si6O18 Si6O18 Si6O18 R64 O18 Si6O18 R63 O18 Si6O18 Si6O18 Si6O18 Si6O18 R33 R34 O18 Al3Si3O18 B3Si3O18 Al3Si3O18 B3Si3O18

(BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3

S31 (OH)3 (OH)3 (OH)3 (OH)3 (OH)3 (OH)3 (OH)3 (OH)3 S31 (OH)3 (OH)3 S31 (OH)3 (OH)3 (OH)3 (OH)3 (OH)3 (OH)3 (OH)3 (OH)3 (OH)3 S31 (OH)3 S32 (O)3 (O)3 (O)3 (O)3 S31 (OH)3 (OH)3 (OH)3 (OH)3

S1 (OH) (OH) (OH) (OH) F F (OH) (OH) S1 (OH) F S2 O O O O O O O O O S2 O S1 F (OH) (OH) F S1 (OH) (OH) F F

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F. Yavuz et al. / Computers & Geosciences 63 (2014) 70 87

Table 2 (continued ) Row 32 33 34 35 36 37 38 Vacant group 39 40 41 42 43 44

a

General formula Uviten Fluor-feruvite Calcic-subgroup 2 Fluor-liddicoatiten Liddicoatite Calcic-subgroup 3 CaMgO root name CaFeO root name Calcic-subgroup 4 CaLiO root name Vacant-subgroup 1 Foititen Magnesio-foititen Vacant-subgroup 2 Rossmaniten Vacant-subgroup 3 MgO root name FeO root name Vacant-subgroup 4 LiO root name

( X) Ca Ca Ca2 Ca Ca Ca2 Ca Ca Ca2 Ca Vacancy () Vacancy () Vacancy () Vacancy () Vacancy () Vacancy () Vacancy () Vacancy () Vacancy () Vacancy ()

(Y3) Mg3 Fe32 R21 R13 Li21 Al3 Li21 Al3 R32 Mg3 Fe32 R1.51 R1.53 Li1.5 Al1.5 R22 R3 Fe22 Al Mg2Al R11 R23 Li1 Al23 R12 R23 MgAl2 Fe2 Al2 R0.51 R2.53 Li0.5 Al2.5

(Z6) MgAl5 MgAl5 R63 Al6 Al6 R63 Al6 Al6 R63 Al6 R63 Al6 Al6 R63 Al6 R63 Al6 Al6 R63 Al6

T6O18 Si6O18 Si6O18 R64 O18 Si6O18 Si6O18 R64 O18 Si6O18 Si6O18 R64 O18 Si6O18 R64 O18 Si6O18 Si6O18 R64 O18 Si6O18 R64 O18 Si6O18 Si6O18 R64 O18 Si6O18

(BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3 (BO3)3

V3 (OH)3 (OH)3 S31 (OH)3 (OH)3 S31 (OH)3 (OH)3 S31 (OH)3 S31 (OH)3 (OH)3 S31 (OH)3 S31 (OH)3 (OH)3 S31 (OH)3

W (OH) F S1 F (OH) S2 O O S2 O S1 (OH) (OH) S1 (OH) S2 O O S2 O

Tsilaisite recognized by the IMA-CNMNC (Bosi et al., 2012b). Fluor-elbaite recognized by the IMA-CNMNC (Bosi et al., 2013a). c Oxy-dravite recognized by the IMA-CNMNC (Bosi and Skogby, 2013). d Oxy-schorl recognized by the IMA-CNMNC (Bak et al., 2013). e Oxy-chromium-dravite recognized by the IMA-CNMNC (Bosi et al., 2012a). f Oxy-vanadium-dravite recognized by the IMA-CNMNC (Bosi et al., 2013b). g Vanadio-oxy-dravite recognized by the IMA-CNMNC (Bosi et al., in press-a). h Vanadio-oxy-chromium-dravite recognized by the IMA-CNMNC (Bosi et al., in press-b). i Darrellhenryite recognized by the IMA-CNMNC (Novk et al., 2013). n Tourmaline species recognized by the IMA-2011 tourmaline nomenclature scheme (Henry et al., 2011). Tourmaline species with compositions found in natural settings, but not currently recognized by the IMA-CNMNC. Tourmaline species produced experimentally or found in natural settings in which the tourmalines show a tendency for development of these compositions, and not recognized by the IMA-CNMNC.
b

Table 3 Description of column numbers in the Calculation Screen window of WinTcac program. Row Explanations Column numbers in the Calculation Screen of WinTcac program 131 3258 5995 9698 99102 103110 111 112 113142 143 144 145 146152 153175

1 2 3 4 5 6 7 8 9 10 11 12 13 14

Major oxide (wt%) tourmaline analyses Recalculated cations Recalculated cations in the T, Z, Y, and X sites Stoichiometric calculation of H2O, B2O3, and Li2O (wt%) contents Calculation of OH, F, and Cl (apfu) contents OH, O, F, and Cl (apfu) estimation at the W and V sites Determination of primary tourmaline groups (i.e., alkali-, calcic, and X-site vacant) based on the dominant occupancy of the X-site Determination of tourmaline species (i.e., hydroxyl-, oxy-, and uor-tourmaline) based on the anion occupancy of the W-site Estimation of various parameters used for the classication of tourmaline-supergroup minerals Determination of tourmaline subgroups (i.e., from subgroup 1 to subgroup 5) Determination of tourmaline species Normalization used for the calculation of tourmaline data Total cations at different sites and their allocations Calculated various useful ratios and parameters of tourmaline analyses

Table 4 Selected tourmaline analyses (wt%) with their structural formulae (apfu) and important parameters calculated by WinTcac program. Row 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 SiO2 TiO2 Al2O3 Fe2O3 FeO MnO MgO CaO Na2O K2O Li2O F H2O B2O3 O F Total (wt%) S1 36.670 1.130 29.690 0.130 7.500 0.003 7.580 1.550 1.700 0.040 0.000 0.060 3.190 10.250 0.025 99.468 6.047 0.000 6.047 5.770 0.016 0.214 0.000 6.000 0.000 0.140 1.034 o 0.001 1.649 0.000 2.824 0.274 0.543 0.008 0.175 1.000 8.824 14.871 15.696 0.047 49.000 0.817 2.914 5.956 0.003 1.100 2.684 5.973 2.758 S2 34.224 0.000 29.038 0.000 20.462 0.000 0.000 0.000 2.942 0.000 0.000 0.000 3.420 9.914 0.000 100.000 6.000 0.000 6.000 6.000 0.000 0.000 0.000 6.000 0.000 0.000 3.000 0.000 0.000 0.000 3.000 0.000 1.000 0.000 0.000 1.000 9.000 15.000 16.000 0.000 49.000 1.000 3.000 6.000 0.000 1.000 3.000 6.000 3.000 S3 38.486 0.000 40.819 0.000 0.000 0.000 0.000 0.000 3.308 0.000 2.393 0.000 3.846 11.148 0.000 100.000 6.000 0.000 6.000 6.000 0.000 0.000 0.000 6.000 1.500 0.000 0.000 0.000 0.000 1.500 3.000 0.000 1.000 0.000 0.000 1.000 7.500 13.500 14.500 0.000 49.000 1.000 0.000 7.500 1.500 1.000 0.000 6.000 3.001 S4 37.524 0.000 31.838 0.000 0.000 0.000 12.585 0.000 3.226 0.000 0.000 1.977 2.813 10.869 0.832 100.000 6.000 0.000 6.000 6.000 0.000 0.000 0.000 6.000 0.000 0.000 0.000 0.000 3.000 0.000 3.000 0.000 1.000 0.000 0.000 1.000 9.000 15.000 16.000 0.000 49.000 1.000 3.000 6.000 0.000 1.000 3.000 6.000 3.000 S5 34.159 0.000 28.984 0.000 20.423 0.000 0.000 0.000 2.936 0.000 0.000 1.800 2.561 9.895 0.758 100.000 6.000 0.000 6.000 6.000 0.000 0.000 0.000 6.000 0.000 0.000 3.000 0.000 0.000 0.000 3.000 0.000 1.000 0.000 0.000 1.000 9.000 15.000 16.000 0.000 49.000 1.000 3.000 6.000 0.000 1.000 3.000 6.000 3.000 S6 38.198 0.000 37.812 0.000 0.000 0.000 0.000 5.942 0.000 0.000 3.166 0.000 3.818 11.065 0.000 100.001 6.000 0.000 6.000 6.000 0.000 0.000 0.000 6.000 1.000 0.000 0.000 0.000 0.000 2.000 3.000 1.000 0.000 0.000 0.000 1.000 7.000 13.000 14.000 0.000 49.000 1.000 0.000 7.000 1.000 2.000 0.000 6.000 4.000 S7 33.762 0.000 23.872 0.000 20.186 0.000 3.775 5.252 0.000 0.000 0.000 0.000 3.374 9.780 0.000 100.001 6.000 0.000 6.000 5.000 0.000 1.000 0.000 6.000 0.000 0.000 3.000 0.000 0.000 0.000 3.000 1.000 0.000 0.000 0.000 1.000 9.000 15.000 16.000 0.000 49.000 1.000 4.000 5.000 1.000 2.000 3.000 5.000 4.000 S8 37.045 0.000 26.193 0.000 0.000 0.000 16.566 5.763 0.000 0.000 0.000 0.000 3.702 10.731 0.000 100.000 6.000 0.000 6.000 5.000 0.000 1.000 0.000 6.000 0.000 0.000 0.000 0.000 3.000 0.000 3.000 1.000 0.000 0.000 0.000 1.000 9.000 15.000 16.000 0.000 49.000 1.000 4.000 5.000 1.000 2.000 3.000 5.000 4.000 S9 38.117 0.000 37.732 0.000 0.000 0.000 0.000 5.926 0.000 0.000 3.159 2.009 2.862 11.041 0.846 100.000 6.000 0.000 6.000 6.000 0.000 0.000 0.000 6.000 1.000 0.000 0.000 0.000 0.000 2.000 3.000 0.999 0.000 0.000 0.001 1.000 7.000 13.000 14.000 0.000 49.000 0.999 0.000 7.000 1.000 1.999 0.000 6.000 4.000 S10 33.699 0.000 23.828 0.000 20.148 0.000 3.768 5.242 0.000 0.000 0.000 1.776 2.526 9.762 0.748 100.001 6.000 0.000 6.000 5.000 0.000 1.000 0.000 6.000 0.000 0.000 3.000 0.000 0.000 0.000 3.000 1.000 0.000 0.000 0.000 1.000 9.000 15.000 16.000 0.000 49.000 1.000 4.000 5.000 1.000 2.000 3.000 5.000 4.000 S11 36.969 0.000 26.140 0.000 0.000 0.000 16.533 5.751 0.000 0.000 0.000 1.948 2.771 10.709 0.820 100.001 6.000 0.000 6.000 5.000 0.000 1.000 0.000 6.000 0.000 0.000 0.000 0.000 3.000 0.000 3.000 1.000 0.000 0.000 0.000 1.000 9.000 15.000 16.000 0.000 49.000 1.000 4.000 5.000 1.000 2.000 3.000 5.000 4.000 S12 39.026 0.000 44.151 0.000 0.000 0.000 0.000 0.000 0.000 0.000 1.617 0.000 3.900 11.305 0.000 99.999 6.000 0.000 6.000 6.000 0.000 0.000 0.000 6.000 2.000 0.000 0.000 0.000 0.000 1.000 3.000 0.000 0.000 0.000 1.000 1.000 8.000 14.000 14.000 0.000 49.000 0.000 0.000 8.000 2.000 0.000 0.000 6.000 2.000 S13 35.996 0.000 35.632 0.000 14.347 0.000 0.000 0.000 0.000 0.000 0.000 0.000 3.598 10.427 0.000 100.000 6.000 0.000 6.000 6.000 0.000 0.000 0.000 6.000 1.000 0.000 2.000 0.000 0.000 0.000 3.000 0.000 0.000 0.000 1.000 1.000 9.000 15.000 15.000 0.000 49.000 0.000 2.000 7.000 1.000 0.000 2.000 6.000 2.000 S14 38.416 0.000 38.028 0.000 0.000 0.000 8.590 0.000 0.000 0.000 0.000 0.000 3.839 11.128 0.000 100.001 6.000 0.000 6.000 6.000 0.000 0.000 0.000 6.000 1.000 0.000 0.000 0.000 2.000 0.000 3.000 0.000 0.000 0.000 1.000 1.000 9.000 15.000 15.000 0.000 49.000 0.000 2.000 7.000 1.000 0.000 2.000 6.000 2.000 73

F. Yavuz et al. / Computers & Geosciences 63 (2014) 70 87

Cations based on 31 anions 17 T-site Si 18 Al 19 T-site total (apfu) 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 Z-site Al Fe3 Mg Fe2 Z-site total (apfu) Y-site Al Ti Fe2 Mn Mg Li Y-site total (apfu) X-site Ca Na K X-site vacancy X-site total (apfu) Z Y sites total (apfu) T Z Y sites total (apfu) T Z Y X sites total (apfu) Si excess (apfu) Cation charge R1 (apfu) R2 (apfu) R3 (apfu) X Al (Al-in-R2) (apfu) R (apfu) R2 (apfu) R3 (apfu) Mgn (apfu)

74

Table 4 (continued ) Row 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 Al (apfu) Nan (apfu) OHn (apfu) Fetot/(Fetot Mg) Na/(Na Ca) Al/(Al Mg) Al/(Al Si) Al/(Al Fetot Mg) Ca/(Ca Fetot Mg) OH (V W sites) OH (V-site) O (V-site) OH (W-site) F (W-site) O (W-site) V W sites Total (apfu) Dominant cation (X-site) Dominant divalent cation (Y-site) Total divalent cation (Y-site) (apfu) Dominant trivalent cation (Y-site) Total trivalent cation (Y-site) (apfu) Dominant divalent cation (Z-site) Total divalent cation (Z-site) (apfu) Dominant trivalent cation (Z-site) Total trivalent cation (Z-site) (apfu) Total divalent cation (Y Z sites) Dominant trivalent cation (Y Z sites) Total trivalent cation (Y Z sites) Dominant quadrivalent cation (Y Z sites) Total quadrivalent cation (Y Z sites) (apfu) Dominant cation (T-site) Dominant anion (V-site) Li-species test (Y-site) Mg/(Mg Fe2 ) (Y-site) R2 /(R2 2Li) (Y-site) Ca/(Ca Na K) (X-site) Vacancy/(Ca vacancy) (X-site) Vacancy/(Na K vacancy) (X-site) O/(O OH F) (W-site) OH/(OH F) (V-site) Al/(Al Fe3 Cr) (Z-site) Fe3 /(Al Fe3 Cr) (Z-site) Si/(Si B Al) (T-site) Species series (W-site) Group name (Henry, 2011) Subgroup name (Henry, 2011) Tourmalie species (Henry, 2011)
n

S1 6.066 0.552 0.540 0.360 0.665 0.756 0.488 0.664 0.086 3.509 3.000 0.000 0.509 0.031 0.460 4.000 Na Mg2 2.684 0.000 Mg2 0.214 Al3 5.786 2.898 Al3 5.786 Ti4 0.140 Si OH
4

S2 6.000 1.000 0.999 1.000 1.000 1.000 0.500 0.667 0.000 3.999 3.000 0.000 0.999 0.000 0.001 4.000 Na Fe2 3.000 0.000 0.000 Al3 6.000 3.000 Al3 6.000

S3 6.000 1.000 0.999 1.000 1.000 1.000 0.556 1.000 0.000 3.999 3.000 0.000 0.999 0.000 0.001 4.000 Na Fe2 0.000 Al3 1.500 0.000 Al3 6.000 0.000 Al3 7.500

S4 6.000 1.000 1.000 0.000 1.000 0.667 0.500 0.667 0.000 3.000 3.000 0.000 0.000 1.000 0.000 4.000 Na Mg2 3.000 0.000 Mg2 0.000 Al3 6.000 3.000 Al3 6.000

S5 6.000 1.000 1.000 1.000 1.000 1.000 0.500 0.667 0.000 3.001 3.000 0.000 0.000 1.000 0.000 4.000 Na Fe2 3.000 Al3 0.000 0.000 Al3 6.000 3.000 Al3 6.000

S6 5.000 0.000 1.000 1.000 0.000 1.000 0.538 1.000 1.000 4.000 3.000 0.000 1.000 0.000 0.000 4.000 Ca Fe2 0.000 Al3 1.000 0.000 Al3 6.000 0.000 Al3 7.000

S7 5.000 0.000 1.000 0.750 0.000 0.833 0.455 0.556 0.200 4.000 3.000 0.000 1.000 0.000 0.000 4.000 Ca Fe2 3.000 0.000 Mg2 1.000 Al3 5.000 4.000 Al3 5.000

S8 5.000 0.000 1.000 0.000 0.000 0.556 0.455 0.556 0.200 4.000 3.000 0.000 1.000 0.000 0.000 4.000 Ca Mg2 3.000 0.000 Mg2 1.000 Al3 5.000 4.000 Al3 5.000

S9 5.000 0.000 1.000 1.000 0.000 1.000 0.538 1.000 1.000 2.000 2.000 1.000 0.000 1.000 0.000 4.000 Ca Fe2 0.000 Al3 1.000 0.000 Al3 6.000 0.000 Al3 7.000

S10 5.000 0.000 1.000 0.750 0.000 0.833 0.455 0.556 0.200 3.000 3.000 0.000 0.000 1.000 0.000 4.000 Ca Fe2 3.000 0.000 Mg2 1.000 Al3 5.000 4.000 Al3 5.000

S11 5.000 0.000 1.000 0.000 0.000 0.556 0.455 0.556 0.200 3.000 3.000 0.000 0.000 1.000 0.000 4.000 Ca Mg2 3.000 0.000 Mg2 1.000 Al3 5.000 4.000 Al3 5.000

S12 7.000 0.000 1.000 1.000 1.000 1.000 0.571 1.000 0.000 4.000 3.000 0.000 1.000 0.000 0.000 4.000 X-site vacant Fe2 0.000 Al3 2.000 0.000 Al3 6.000 0.000 Al3 8.000

S13 7.000 0.000 1.000 1.000 1.000 1.000 0.538 0.778 0.000 4.000 3.000 0.000 1.000 0.000 0.000 4.000 X-site vacant Fe2 2.000 Al3 1.000 0.000 Al3 6.000 2.000 Al3 7.000

S14 7.000 0.000 1.000 0.000 1.000 0.778 0.538 0.778 0.000 4.000 3.000 0.000 1.000 0.000 0.000 4.000 X-site vacant Mg2 2.000 Al3 1.000 0.000 Al3 6.000 2.000 Al3 7.000

F. Yavuz et al. / Computers & Geosciences 63 (2014) 70 87

0.000 Si OH
4

0.000 Si OH
4

0.000 Si OH
4

0.000 Si OH
4

0.000 Si OH
4

0.000 Si OH
4

0.000 Si OH
4

0.000 Si OH
4

0.000 Si OH
4

0.000 Si OH
4

0.000 Si OH
4

0.000 Si OH
4

0.000 Si4 OH other 1.000 1.000 0.000 1.000 1.000 0.000 1.000 1.000 0.000 1.000 HydroxyX-vacant Subgroup 1

other 0.615 1.000 0.332 0.389 0.240 0.460 1.000 0.997 0.003 1.000 HydroxyAlkali Subgroup 1 Dravite

other 0.000 1.000 0.000 0.000 0.000 0.001 1.000 1.000 0.000 1.000 HydroxyAlkali Subgroup 1 Schorl

Li species 0.000 0.000 0.000 1.000 0.000 0.001 1.000 1.000 0.000 1.000 HydroxyAlkali Subgroup 2 Elbaite

other 1.000 1.000 0.000 0.000 0.000 0.000 1.000 1.000 0.000 1.000 FluorAlkali Subgroup 1

other 0.000 1.000 0.000 1.000 0.000 0.000 1.000 1.000 0.000 1.000 FluorAlkali Subgroup 1

Li species 0.000 0.000 1.000 0.000 0.000 0.000 1.000 1.000 0.000 1.000 HydroxyCalcic Subgroup 2 Liddicoatite

other 0.000 1.000 1.000 0.000 0.000 0.000 1.000 1.000 0.000 1.000 HydroxyCalcic Subgroup 1 Feruvite

other 1.000 1.000 1.000 0.000 0.000 0.000 1.000 1.000 0.000 1.000 HydroxyCalcic Subgroup 1 Uvite

Li species 0.000 0.000 1.000 0.001 0.944 0.000 0.667 1.000 0.000 1.000 FluorCalcic Subgroup 2

other 0.000 1.000 1.000 0.000 0.018 0.000 1.000 1.000 0.000 1.000

other 1.000 1.000 1.000 0.000 0.000 0.000 1.000 1.000 0.000 1.000

Li species 0.000 0.000 0.000 1.000 1.000 0.000 1.000 1.000 0.000 1.000 HydroxyX-vacant Subgroup 2 Rossmanite

other 0.000 1.000 0.000 1.000 1.000 0.000 1.000 1.000 0.000 1.000 HydroxyX-vacant Subgroup 1 Foitite

FluorFluorCalcic Calcic Subgroup 1 Subgroup 1

F. Yavuz et al. / Computers & Geosciences 63 (2014) 70 87 Notes: Tourmaline analyses are taken from Henry (2011); apfu atomic per formula unit; () Calculated by WinTcac; R1 Na Ca (row 42), R2 Fetot Mg Mn(row 43), R3 Al 1.33Ti (row 44), X Al (Al-in-R2) Al 1.33Ti Si-12 (row 45) (London and Manning, 1995); R Na K 2Ca2 (row 46), R2 Fe2 Mg2 Mn2 (row 47), R3 Al3 Fe3 1.3Ti4 (row 48) (Foit Jr. et al., 1989); Mgn Mg Fe2 Mn 2LiTi (row 49), Aln Al Fe3 2Ti Li (row 50), Nan Na K (row 51), OHn OH F (row 52) (Henry and Dutrow, 1990).

75

Hydroxy-

Calcic subgroup 2

Calcic subgroup 1 Liddicoatite Feruvite

Hydroxy-

The Subcommittee on Tourmaline Nomenclature (STN) of the International Mineralogical Association's Commission on New Minerals, Nomenclature and Classication (CNMCN) has classied tourmalines with the tourmaline-supergroup terminology as they consist of two or more mineral groups (Henry et al., 2011). The general formula of tourmaline-supergroup can be expressed as XY3Z6(T6O18)(BO3)V3W, where the most common ions (or vacancy) at each site are X Na1 , Ca2 , K1 , Pb2 , and vacancy (); Y Fe2 , Mg2 , Mn2 , Al3 , Li1 , Fe3 , Ti4 , and Cr3 ; Z Al3 , Fe3 , Mg2 , and Cr3 ; T Si4 , Al3 , and B3 ; B B3 ; V OH1 and O2 ; and W OH1 , F1 , and O2 . This formula show that tourmaline incorporates a wide variety of elements as mono-, di-, tri-, and tetravalent cations and mono- and divalent anions as well as extensive solid solution at Z and Y sites (Table 1). According to the IMA-2011 (Henry et al., 2011), the tourmaline-supergroup consist of 18 species (Table 2), but the best known minerals are dravite, schorl, and elbaite (Dutrow and Henry, 2011). Consequently, there are essentially two main types of common tourmaline: Li-dominated tourmaline (elbaite-rich), and MgFe dominated tourmaline (dravite-schorl). In this study, we developed a Microsoft Visual Basic program, WinTcac, to calculate structural formulae of tourmaline analyses based on the current International Mineralogical Association (IMA-2011) nomenclature scheme. This software calculates tourmaline analyses both based on 31 O atoms normalization as default and 15 cations and 6 silicons as optional, shares out the recalculated cations at different sites (T, Z, Y, and X), estimates the OH 1 and O2 contents at the V-site and OH1 , F1 , Cl1 , and O2 contents at the W-site, and allows the user to display tourmalinesupergroup minerals in various binary and ternary diagrams by using the Golden Software's Grapher program.

X-vacant subgroup 1 Calcic subgroup 2

Hydroxy-

Hydroxy-

Fluor-

Fluor-

Fluor-

Hydroxy-

Calcic subgroup 1 Uvite

Fluorliddicoatite

Fluorliddicoatite

Calcic subgroup 1 Fluorferuvite

Fluorferuvite

Calcic subgroup 1 Fluoruvite

Fluoruvite

X-vacant X-vacant subgroup 2 subgroup 1 Rossmanite Foitite

Hydroxy-

Magnesiofoitite

Magnesiofoitite

2. Program description Compared to the software on amphibole group minerals (e.g., Yavuz, 2007 and references therein), programs as well as spreadsheets to calculate and classify the structural formulae of tourmalines are limited (Yavuz, 1997; Yavuz et al., 2002, 2006). Pesquera et al. (2008) presented a Visual Basic program (TOURCOMP) based on a linear algebraic model to calculate the end-member proportions of tourmaline analyses from their structural formulae. Henry (2011) developed an Excel spreadsheet, which is designed to use already-calculated cations for determining the tourmaline species based on an ordered distribution of elements in the tourmaline formula taking into account the current tourmaline nomenclature scheme. WinTcac, a Windows program for tourmaline calculation and classication, is the compiled software developed for running on the Microsoft Windows platform. The program described here is a comprehensive implementation of the chemistry-based nomenclature of the tourmaline-supergroup minerals (Henry et al., 2011) and it is intended for use with major oxide (wt%) tourmaline chemical data. WinTcac consists of a self-extracting setup le, which is compiled by using the Inno Setup software (http://www. jrsoftware.org/isdl.php). On successful installation of the WinTcac program, the start-up screen form with various pull-down menus and equivalent shortcuts appears on the screen. 2.1. Data entry The users of this program can edit tourmaline analyses by clicking the New icon on the toolbar, by selecting New File from the pull-down menu of File option or pressing the Ctrl N keys. The program dened standard 29 variables for calculation and classication of tourmaline analysis in the following order:

FluorFluorHydroxyHydroxyHydroxy-

Species series (W-site) (by WinTcac) Group name (by WinTcac) Subgroup name (by WinTcac) 97 98 99

100

Tourmaline species (by WinTcac)

Alkali subgroup 1 Dravite

Alkali subgroup 1 Schorl

Alkali subgroup 2 Elbaite

Alkali subgroup 1 Fluordravite

Fluordravite

Alkali subgroup 1 Fluorschorl

Fluorschorl

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F. Yavuz et al. / Computers & Geosciences 63 (2014) 70 87

Sample No, SiO2, TiO2, SnO2, Al2O3, V2O3, Bi2O3, Cr2O3, Mn2O3, Fe2O3, FeO, MnO, NiO, CoO, ZnO, CuO, MgO, CaO, PbO, BaO, Na2O, K2O, Rb2O, Cs2O, Li2O, F, Cl, H2O, and B2O3. Tourmaline analyses typed in Excel les with the extension of . xls or .xlsx, as in the above order, can be loaded into the program's data entry section by clicking the Open Excel File option from the pull-down menu of File and then selecting the 1997 2003 Files or 2007Later Files alternatives. For example, two representative tourmaline Excel data les (WinTcac_Henry and WinTcac_Test) in the folder (i.e., C:\Program Files\WinTcac\Open Excel Files) can be used for this purpose by the user. Once the tourmaline analyses in an Excel le is displayed on the screen by using the Open Excel File option, it can be stored with the extension of .tou by clicking the Save As option from the pull-down menu of File. By selecting the Edit Excel File option from the pull-down menu of File and subsequently selecting the 19972003 Files or 2007Later Files, tourmaline analyses can be typed in a blank Excel le (i.e., WinTcac) in the (C:\Program Files\WinTcac\Edit Excel File) folder, stored in a different le name with the extension of .xls or .xlsx, and then loaded into the program's data entry section by clicking the Open Excel File option from the pull-down menu of File for the next calculation. Additional knowledge on data entry or similar topics can be reached by pressing the F1 function key to display the WinTcac help le on the screen. 2.2. Normalization Normalization based on anions and cations can be used for tourmaline recalculation scheme. The best approach for determination of the structural formula of tourmaline-supergroup minerals is to use all possible analytical techniques (e.g., electronmicroprobe, secondary-ion mass spectrometry (SIMS), magicangle-spinning nuclear magnetic resonance (MAS NMR), and 57 Mssbauer spectroscopy) for a tourmaline sample. With the complete tourmaline analyses, including light elements (H, Li, and B), normalization can be properly carried out on a 31 anion basis that would give an accurate formula (Henry and Dutrow, 1996; Clark, 2007; Henry et al., 2011). However, without accurate analyses of H, Li, B, and oxidation states of some transition elements (e.g., Fe, Mn, V, Cr, and Ti), the question is that what is the most convenient normalization scheme for a tourmaline analysis? There are various cation normalization schemes that come with implicit assumptions. For example 19 cations assumes that the X-site is fully occupied, which is uncommon, and requires a known B-content; Y Z T 15 assumes a

stoichiometric amount of B, and fully occupied Y, Z and T sites. These are, in fact, not just different options in the normalization, but are based on assumptions about the site occupancy. For an incomplete tourmaline analysis, normalization approach based on 24.5 anions may provide a good rst approximation, but as it leaves out the W-site (O(1)) this scheme is prone to errors especially for F-bearing tourmaline species. Normalized to 15 total cations (i.e., Y Z T) is the recommended approach for tourmaline with low Li contents and minor B in the tetrahedral site (Henry et al., 2011). The 15 total cations normalization procedure will be appropriate for tourmalines in almost all metamorphic and most igneous rocks (Henry et al., 2011). Normalization approach based on the Si 6 (apfu) is useful for tourmaline analyses with signicant amounts of unanalyzed elements especially for Li contents (Henry et al., 2011). This method assumes that T-site is fully occupied by Si and there is no signicant amount of tetrahedral Al or B contents. Normalization on 6 (apfu) of Si seems to be an appropriate procedure for many Li-rich tourmalines. Where there is a complete tourmaline analysis, including H2O, B2O3, and Li2O (wt%) contents, WinTcac estimates site occupancy for normalization based on 31 anions. The program allows the user to select the normalization option for the calculation of structural formulae based on 31 anions, 15 total cations (i.e., Y Z T), and

Fig. 2. Plot of tourmalines in the ternary V3 Cr3 Al3 subsytem (low F3 ) used for explaining the dominant occupancy of the Z-site (from Henry et al., 2011). Data used in this gure are taken from Henry (2011).

Fig. 1. (a). Classication of primary tourmaline groups in the ternary Ca2 X-site vacancyNa1 (K1 ) system based on the dominant occupancy at the X-site (from Henry et al., 2011). (b) Plot of tourmaline species in the ternary O2 F1 OH1 system based on the anion occupancy of the W-site (from Henry et al., 2011). Data used in these gures are taken from Henry (2011).

Table 5 Examples of recently recognized tourmaline species with their calculation and classication parameters by WinTcac program. Row 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 SiO2 TiO2 Al2O3 V2O3 Cr2O3 Fe2O3 FeO MnO ZnO MgO CaO Na2O K2O Li2O F Cl H2O B2O3 O F O Cl Total (wt%) R1a 36.10 0.32 37.10 0.00 0.00 0.00 0.00 9.60 0.00 0.00 0.09 2.11 0.03 0.81 0.79 0.00 3.09 10.24 0.333 0.000 99.947 5.889 0.039 7.133 0.000 0.000 0.000 0.000 1.326 0.000 0.000 0.016 0.667 0.006 0.531 0.408 0.000 3.000 3.362 3.000 0.000 0.362 0.408 0.000 0.230 4.000 Na Mn2 Al3 Al3 Mn2 Al3 R2b 37.48 0.00 37.81 0.00 0.00 0.00 3.39 2.09 0.27 0.00 0.34 2.51 0.06 1.58 1.49 0.00 3.03 10.83 0.627 0.000 100.253 6.017 0.000 7.153 0.000 0.000 0.000 0.455 0.284 0.032 0.000 0.058 0.781 0.012 1.020 0.756 0.000 3.001 3.245 3.000 0.000 0.244 0.756 0.000 0.000 4.000 Na Fe2 Al3 Al3 Fe2 Al3 R3c 37.01 0.14 33.11 0.00 0.00 5.00 0.19 0.00 0.00 8.56 0.00 2.65 0.10 0.00 0.00 0.00 2.65 10.76 0.000 0.000 100.170 5.889 0.017 6.210 0.000 0.000 0.599 0.025 0.000 0.000 2.031 0.000 0.818 0.020 0.000 0.000 0.000 3.000 2.813 2.813 0.187 0.000 0.000 0.000 1.000 4.000 Na Mg2 Fe3 Al3 Mg2 Al3 R4d 33.10 0.02 39.81 0.00 0.00 0.00 7.97 0.03 0.00 2.31 0.58 1.83 0.00 0.00 0.26 0.01 2.92 10.45 0.109 0.002 99.178 5.438 0.002 7.708 0.000 0.000 0.000 1.095 0.004 0.000 0.566 0.102 0.583 0.000 0.000 0.135 0.003 3.000 3.200 3.000 0.000 0.200 0.135 0.003 0.662 4.000 Na Fe2 Al3 Al3 Fe2 Al3 R5e 31.73 0.32 3.61 5.81 36.25 0.00 0.00 0.00 0.00 7.49 0.00 2.78 0.08 0.00 0.78 0.00 2.18 9.35 0.328 0.000 100.052 5.792 0.044 0.777 0.850 5.232 0.000 0.000 0.000 0.000 2.038 0.000 0.984 0.019 0.000 0.450 0.000 3.000 2.654 2.654 0.346 0.000 0.450 0.000 0.550 4.000 Na Mg2 V3 Cr3 Mg2 Cr3 R6f 33.05 0.41 4.30 38.56 1.48 0.00 0.00 0.00 0.00 8.21 0.00 2.50 0.32 0.00 0.13 0.00 2.60 9.59 0.055 0.000 101.095 5.897 0.055 0.904 5.516 0.209 0.000 0.000 0.000 0.000 2.184 0.000 0.865 0.073 0.000 0.073 0.000 3.000 3.094 3.000 0.000 0.094 0.073 0.000 0.832 4.000 Na Mg2 V3 V3 Mg2 V3 R7g 35.34 0.29 20.36 15.97 1.48 0.34 0.15 0.00 0.00 9.65 1.24 2.11 0.09 0.00 0.00 0.00 2.86 10.23 0.000 0.000 100.110 5.914 0.036 4.016 2.143 0.196 0.043 0.021 0.000 0.000 2.408 0.222 0.685 0.019 0.000 0.000 0.000 3.000 3.193 3.000 0.000 0.193 0.000 0.000 0.807 4.000 Na Mg2 V3 Al3 Mg2 Al3 R8h 37.94 0.00 42.77 0.00 0.00 0.00 0.17 0.02 0.00 0.00 0.07 1.81 0.12 1.88 0.64 0.00 2.86 11.01 0.269 0.000 99.021 5.908 0.000 7.849 0.000 0.000 0.000 0.022 0.003 0.000 0.000 0.012 0.546 0.024 1.177 0.315 0.000 3.000 2.971 2.971 0.029 0.000 0.315 0.000 0.685 4.000 Na Fe2 Al3 Al3 Fe2 Al3 R9i 32.75 0.00 7.64 24.36 12.87 0.42 0.00 0.00 0.00 7.19 0.00 2.52 0.24 0.00 0.25 0.00 2.40 9.56 0.105 0.000 100.095 5.842 0.000 1.606 3.484 1.815 0.056 0.000 0.000 0.000 1.912 0.000 0.872 0.055 0.000 0.141 0.000 3.000 2.856 2.856 0.144 0.000 0.141 0.000 0.859 4.000 Na Mg2 V3 V3 Mg2 V3

F. Yavuz et al. / Computers & Geosciences 63 (2014) 70 87

Cations based on 31 anions 22 Si (apfu) 23 Ti 24 Al 25 V 26 Cr 27 Fe3 28 Fe2 29 Mn 30 Zn 31 Mg 32 Ca 33 Na 34 K 35 Li 36 F 37 Cl 39 B 40 41 42 43 44 45 46 47 48 49 50 51 52 53 OH (V W sites) OH (V-site) O (V-site) OH (W-site) F (W-site) Cl (W-site) O (W-site) V W sites total (apfu) Dominant Dominant Dominant Dominant Dominant Dominant cation (X-site) divalent cation (Y-site) trivalent cation (Y-site) trivalent cation (Z-site) divalent cation (Y Z sites) trivalent cation (Y Z sites)

77

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F. Yavuz et al. / Computers & Geosciences 63 (2014) 70 87

OxyAlkali subgroup 3 Vanadio-oxy-chromium-dravite

6 silicons from the pull-down menu of Normalization ) Structural formulae. WinTcac, thus provides the user the opportunity to calculate tourmaline analyses from a variety of modes of occurrence. Clicking the (OH F Cl) 4 option under the pull-down menu of Normalization ) Structural formulae allows the user to normalize the sum of OH, F, and Cl to 4 for microprobe-derived tourmaline analyses.

Li 1.000 1.000 0.000 1.000 0.074 0.859 0.952

R9i

OxyAlkali subgroup 4 Darrellhenryite

2.3. Li, B2O3, and H2O estimation Tourmalines in Li-bearing pegmatites may contain a signicant amount of lithium at the Y-site. In such cases, the Li content of tourmaline can be calculated stoichiometrically by initially normalizing to 29 oxygens basis or 24.5 oxygens basis, and then estimating Li (apfu) content (i.e., Li (apfu) 3 (Y-site)) as proposed by Henry and Dutrow (1996). By clicking the Yes option from the pull-down menu of Li calculation ) Calculate Li content, WinTcac calculates the stoichiometric amounts of Li2O (wt%) except for the 15 cations (i.e., Y Z T) normalization method. WinTcac also automatically assumes B2O3 (wt%) (i.e., stoichiometric amounts of B 3 apfu) and calculates H2O (wt%) contents if Yes option is selected from the pull-down menu of H2O Calculation ) Calculate H2O content.

other 0.000 0.010 0.020 0.973 0.423 0.685 0.990 other 0.991 1.000 0.240 0.249 0.095 0.807 1.000 other 1.000 1.000 0.000 1.000 0.062 0.832 1.000 Ti4 Ti4

R8h

OxyAlkali subgroup 3 Oxy-vanadium-dravite

R6f

OxyAlkali subgroup 3 Vanadio-oxy-dravite

R7g

2.4. Ferric iron estimation Although the Fe3 contents calculated from electron-microprobe measurements do not correlate with measured Fe3 values (McGuire et al., 1989), an empirical ferric iron estimation procedure can be used for some of the rock-forming mineral (e.g., amphibole and pyroxene) analyses derived from electronmicroprobe technique (e.g., Papike et al., 1974; Droop, 1987). Lynch and Ortega (1997) proposed that ferric iron state of tourmaline analysis at the Y-site may be calculated from the simple equation (i.e., Fe3 (apfu) Fetot (3 Mg) Ca) based on the 24.5 oxygens normalization scheme. Users must be aware, however, that Fe3 values calculated from this equation makes direct assumptions about the exchange vector for Fe3 , which are not universally accepted. Using this approach to allocate ferric iron content at Y and Z sites is also impossible without taking into account the Mssbauer effect spectroscopy (Fuchs et al., 1995). WinTcac calculates the ferric iron content of microprobe-derived tourmaline analysis based on criteria given by Lynch and Ortega (1997) by clicking the Fe3 estimation for 24.5 oxygens normalization option from the pull-down menu of Normalization ) Structural formulae in the Start-up Screen.

FluorFluorAlkali Alkali subgroup 1 subgroup 2 Tsilaisite Fluor-elbaite

Li 0.000 0.274 0.069 0.717 0.157 0.000 1.000

R2b

OxyAlkali subgroup 3 Oxy-dravite

species 0.988 1.000 0.000 1.000 0.162 1.000 0.938

Ti4

R3c

OxyAlkali subgroup 3 Oxy-schorl

other 0.341 1.000 0.149 0.755 0.351 0.664 1.000

Ti4

R4d

OxyAlkali subgroup 3 Oxy-chromium-dravite

other 1.000 1.000 0.000 0.000 0.000 0.550 0.885

Ti4

R5e

Tsilaisite (from Bosi et al., 2012b). Fluor-elbaite (Bosi et al., 2013a). Oxy-dravite (Bosi and Skogby, 2013). d Oxy-schorl (Bak et al., 2013). e Oxy-chromium-dravite (Bosi et al., 2012a). f Oxy-vanadium-dravite (Bosi et al., 2013b). g Vanadio-oxy-dravite (Bosi et al., in press-a). h Darrellhenryite (Novk et al., 2013). i Vanadio-oxy-chromium-dravite (Bosi et al., in press-b).
b c

Dominant quadrivalent cation (Y Z sites) Ti4

other 0.000 0.555 0.023 0.952 0.316 0.230 1.000

R1a

3. Worked examples The following examples show how WinTcac can be used for a variety of calculations and classications of tourmalinesupergroup analyses. A list of the specic calculation steps in the Calculation Screen of the program is given in Table 3. Validity of program outputs has been tested for numerous tourmaline data sets, and results are given in Table 4. Once the tourmaline analyses are processed by clicking the Calculate icon (i.e., ) in the Data Entry Section of the program, all the estimation output is displayed in columns 1179 (see Table 3) of the Calculation Screen. Pressing the Ctrl F keys or clicking the Open File to Calculate option from the Calculate menu also executes to calculate these selected data le with the extension of .tou.

Li-species test (Y-site) Mg/(Mg Fe2 ) (Y-site) R2 /(R2 2Li) (Y-site) Ca/(Ca Na K) (X-site) Vacancy/(Ca vacancy) (X-site) Vacancy/(Na K vacancy) (X-site) O/(O OH F) (W-site) OH/(OH F) (V-site)

Notes : apfu atomic per formula unit. Tourmaline analyses:

Table 5 (continued )

Row

Species series (W-site) Group name (X-site) Subgroup name Tourmaline species

55 56 57 58 59 60 61 62

54

63 64 65 66

F. Yavuz et al. / Computers & Geosciences 63 (2014) 70 87

79

3.1. Calculation of tourmaline data and the IMA-2011 classication diagrams Representative tourmaline-supergroup mineral analyses with their estimations based on 31 anions by the program are given in Table 4. WinTcac rst calculates cations of tourmaline analyses and

then distributes the recalculated values into the T, Z, Y, and X sites (see rows 1736 in Table 4). Stoichiometric estimation of H2O (wt%), B2O3 (wt%), and Li2O (wt%) contents of electron-microprobe tourmaline data are listed in columns 9698 in the Calculation Screen. Calculation of OH, F, and Cl (apfu) as well as OH and O contents (apfu) at V-site and OH, F, Cl, and O contents (apfu) at W-site (see

Fig. 3. Diagrams for establishing tourmaline subgroups within the alkali-, calcic-, and X-vacant groups (from Henry et al., 2011). (a) Determination of subgroups 14 for alkali- and calcic groups. (b) Determination of subgroups 14 for alkali- and X-vacant groups. Data used in these gures are taken from Henry (2011).

Fig. 4. Classication of alkali-group tourmaline species in the ternary 2Li1 YFe2 YMg2 subsystem (from Henry et al., 2011). (a) Dominance of OH1 at the W-site. (b) Dominance of F1 at the W-site. (c) Dominance of O2 at the W-site. Data used in these gures are taken from Henry (2011).

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F. Yavuz et al. / Computers & Geosciences 63 (2014) 70 87

rows 5965 in Table 4) are displayed in columns from 99 to 110 in the Calculation Screen. WinTcac denes primary tourmaline groups (row 98 in Table 4) and general tourmaline species (row 100 in Table 4) based on the dominant occupancy at the X-site (see Fig. 1a) and anion occupancy at the W-site (see Fig. 1b). Estimation of

various parameters (see rows 6692 in Table 4) used in classication of tourmaline-supergroup minerals are listed in columns from 113 to 142 in the Calculation Screen. These parameters include dominant cation at the X-site (e.g., Na1 , K1 ,Ca2 , Pb2 ; see row 66 in Table 4), dominant divalent cation at the Y-site (e.g., Mg2 ,

Fig. 5. Classication of calcic-group tourmaline species on the ternary 2Li1 YFe2 YMg2 subsystem (from Henry et al., 2011). (a) Dominance of OH1 at the W-site. (b) Dominance of F1 at the W-site. (c) Dominance of O2 at the W-site. Data used in these gures are taken from Henry (2011).

Fig. 6. Classication of vacant-group tourmaline species in the ternary 2Li1 YFe2 YMg2 subsystem (from Henry et al., 2011). (a) Dominance of OH1 at the W-site. (b) Dominance of O2 at the W-site. Data used in these gures are taken from Henry (2011).

F. Yavuz et al. / Computers & Geosciences 63 (2014) 70 87

81

Mn2 , Fe2 ; see row 67 in Table 4), dominant trivalent cation at the Y-site (e.g., Al3 , V3 , Fe3 , Cr3 ; see row 69 in Table 4), dominant divalent cation at the Z-site (e.g., Mg2 , Fe2 ; see row 71 in Table 4), dominant trivalent cation at the Z-site (e.g., Al3 , Cr3 , V3 , Fe3 ; see row 73 in Table 4 and Fig. 2), dominant cation at the T-site (e.g., Si4 , Al3 , B3 ; see row 80 in Table 4), and dominant anion at the V-site (e.g., OH1 , O2 ; see row 81 in Table 4). Following the group name (see row 98 in Table 4), WinTcac identies tourmaline-subgroups (see row 99 in Table 4) and corresponding tourmaline species (see row 100 in Table 4) using the estimated parameters in columns from 113 to 142 in the Calculation Screen. Although the IMA-CNMNC recognized 18 tourmaline minerals for alkali, calcic, and vacant groups (Henry et al., 2011), recently recognized species [e.g., Tsilaisite (Bosi et al., 2012b), Fluor-elbaite (Bosi et al., 2013a), Oxy-vanadium-dravite (Bosi et al., 2013b), Oxy-dravite (Bosi and Skogby, 2013), Oxyschorl (Bak et al., 2013), Oxy-chromium-dravite (Bosi et al., 2012a), Vanadio-oxy-darvite (Bosi et al., in press-a, in press-b), Vanadio-oxy-chromium-darvite (Bosi et al., in press-a, in press-b), and Darrellhenryite (Novk et al., 2013)] based on the full characterization of physical, chemical, and structural properties are determined by WinTcac program with their estimated calculation and classication parameters (Table 5). This program automatically uses 31 anions normalization scheme for the complete tourmaline data. Various calculation parameters such as allocations of sites, Si excess, cation charge, compositional variations [e. g., R1 Na Ca (apfu), R2 Fetot Mg Mn (apfu), R3 Al 1.33Ti (apfu), Al-in-R2 Al 1.33Ti Si-12 (apfu) (London and Manning, 1995), Mgn Mg Fe2 Mn 2Li-Ti (apfu), Aln Al Fe3 2TiLi (apfu), Nan Na K (apfu), OHn OH F (apfu) (Henry and Dutrow, 1990)], and some important ratios [e.g., Fetot/(Fetot Mg), Al/ (Al Fetot Mg), Ca/(Ca Fetot Mg)] are listed in columns from 146 to 175 in the Calculation Screen. WinTcac provides the user a visual representation of useful diagrams for establishing the appropriate tourmaline-subgroups minerals within the alkali, calcic and vacant groups (see Fig. 3a and b). A visual classication of alkali (see Fig. 4ac), calcic (see Fig. 5ac), and vacant group (see Fig. 6a and b) tourmaline analyses are displayed in various ternary diagrams. The program allows the user to display some specic diagrams, which are useful for establishing the appropriate tourmaline subgroups and generalized tourmaline species in binary plots (see Figs. 7 and 8).

Fig. 8. Plot of generalized tourmaline species in the Mg/(Mg Fe) vs. X/ (X Na1 K1 ) diagram (from Henry et al., 2011). Data used in this gure are taken from Henry (2011).

Calculation of all tourmaline analyses by WinTcac is carried out in two windows called Data Entry Screen (see Fig. 9a) and Calculation Screen (see Fig. 9b).

3.2. Compositions of tourmaline data on classication, environmental, miscellaneous, and substitution diagrams WinTcac displays total 88 plots for classication, environmental, miscellaneous, and substitution diagrams. These plots are viewed by the Golden Software's Grapher program by selecting diagram types from the pull-down menu of Graph in the Calculation Screen of WinTcac. Fifteen tourmaline classication diagrams (see Figs. 18) proposed by the IMA-2011 nomenclature scheme can be displayed by WinTcac from the pull-down menu of Graph ) Classication Diagrams of IMA (2011) Nomenclature Scheme options in the Calculation Screen. Since tourmaline-supergroup minerals have a large compositional range of major and trace elements, they are used as an indicator of the host environment. For example, tourmaline from granitic pegmatitites show high Li contents (e.g., Neiva and Gomes, 2012; Ertl et al., 2012), whereas Ni-, Cr-, and V-bearing tourmalines are associated with basic, ultramac, and metamorphic rocks, (e.g., Henry and Dutrow, 2001; Baksheev and Kudryavtseva, 2004; Bak et al., 2011). Because tourmaline is resistant to chemical weathering and mechanical abrasion, Henry and Guidotti (1985) proposed to use the composition of detrial tourmaline grains in provenance studies to correlate with tourmaline composition and host-rock type (e.g., Henry and Dutrow, 1992; Morton et al., 2005; Nascimento et al., 2007). These diagrams (see Fig. 10a and b), also called as the environmental diagrams (e.g., van Hinsberg et al., 2011a), are displayed by selecting diagram types from the pulldown menu of Graph ) Environmental Diagrams options in the Calculation Screen. Pirajno and Smithies (1992) proposed that the FeO/(FeO MgO) ratio (i.e., proximity index Fe#) of tourmaline can be used as a discriminatory tool for granitegreisenendocontact systems in granite-related SnW deposits based on their compilation of tourmaline analyses. The proximity index may be used as a rst approximation to identify the relative distance of the granite-related SnW deposits to the source of their hydrothermal uids. WinTcac allows the user to display the modied form of proximity index diagram (see Fig. 11) by selecting the third

Fig. 7. Alternative diagram useful for tourmaline subgroups within the alkali-, calcic-, and vacationing groups (from Henry et al., 2011). Data used in this gure are taken from Henry (2011).

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Fig. 9. (a) Screenshot of the WinTcac Data Entry Screen showing data edits of tourmaline-supergroup analyses. (b) Screenshot of the WinTcac Calculation Screen displaying the results of estimated tourmaline analyses.

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Fig. 10. Compositional diagram of tourmalines used for illustrating the host rock type. (a) The ternary AlFetotMg plot (from Henry and Guidotti, 1985). (b) The ternary CaFetotMg plot (from Henry and Guidotti, 1985). Data used in these gures are taken from Yavuz et al. (2008).

substitutions (e.g., Foit Jr. and Rosenberg, 1977; Gallagher, 1988; Burt, 1989; Henry and Dutrow, 1990, 1996, 2001; Kazachenko et al., 1993; London and Manning, 1995; Jiang et al., 2004; Baksheev and Kudryavtseva, 2004; Burinek and Novk, 2007; Arif et al., 2010; Yavuz et al., 2011; Ertl et al., 2013). These substitution mechanisms that make the tourmaline crystal chemistry difcult to characterize are used in different binary plots to reveal the specic features of tourmaline composition. WinTcac allows the user to display 55 different substitution diagrams from the pull-down menu of Graph ) Substitution Diagrams options in the Calculation Screen. Fig. 13 shows some of selected substitution diagrams with their exchange vectors.

4. Summary and availability of WinTcac WinTcac is a user-friendly software package for tourmalinesupergroup minerals developed for personal computers running the Windows operating system. The program calculates structural formulae of tourmaline analyses according to the IMA-2011 nomenclature scheme for different normalization options. WinTcac generates mainly two windows: the rst (i.e., Data Entry Screen) appears on the screen with several pull-down menus and equivalent shortcuts, and the second (i.e., Calculation Screen) allows the user to display the structural formulae at the T, Z, Y, and X sites with tourmaline classication parameters, groups, subgroups, names, and dominant cations at each site. By selecting options or clicking buttons on the start-up screen, the user can enter and load tourmaline analyses in the Data Entry Screen and make necessary arrangements for a desired calculation scheme. All the estimated tourmaline data in the Calculation Screen are sent to the Microsoft Excel le (i.e., output.xlsx). WinTcac display recalculated tourmaline data in a variety of binary and ternary classications, environmental, substitution, and miscellaneous diagrams in the Calculation Screen by using the Golden Software's Grapher program. WinTcac is a compiled program that consists of a self-extracting setup le, including support les, help le, data les (i.e., tou, xls,

Fig. 11. Plot of tourmaline composition from granite-related hydrothermal deposits in the MgO (wt%) vs. FeO/(FeO MgO) diagram (from Pirajno and Smithies, 1992). Data used in this gure are taken from Yavuz et al. (2008).

diagram type from the pull-down menu of Graph ) Environmental Diagrams options in the Calculation Screen. WinTcac allows to display recalculated tourmaline analyses in different classication diagrams used by several authors (e.g., Jiang et al., 1996; Hawthorne and Henry, 1999; Selway et al., 1999; Dutrow and Henry, 2000; Novk and Taylor, 2000; Henry and Dutrow, 2001; Tindle et al., 2005; Arif et al., 2010; Bosi et al., 2012a, 2012b, 2013b; Bak et al., 2013). These diagrams (see Fig. 12) can be displayed by selecting diagram types from the pull-down menu of Graph ) Miscellaneous Diagrams options in the Calculation Screen of WinTcac. The crystallography of tourmaline-supergroup minerals enables to accommodate a wide range of major, minor, and trace elements in the structure and causes isovalent and coupled

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Fig. 12. (a) Plot of tourmaline composition in the Fe/(Fe Mg) at the Y-site vs. Ca/(Na Ca) at the X-site diagram (from Jiang et al., 1996). (b) Variation of tourmaline in the Fe/ (Fe Li) vs. X-vacancy/(Na X-vacancy) diagram (from Dutrow and Henry, 2000). (c) Variation of tourmaline in the Al/(Al Fe) at the Y-site vs. Na/(Na X-vacancy) at the X-site (from Selway et al., 1999). (d) Variation of tourmaline in the Al/(Al Fe2 ) at the Y-site vs. Ca/(Ca Na) at the X-site (from Tindle et al., 2005). (e) Ternary diagram for the VCrAl subsystem used for showing the dominant occupancy at the Y-site for oxy-tourmaline species (revised from Bosi et al., 2012a). (f) Ternary elbaite-schorl (oxyschorl)-dravite (oxy-dravite) subsystem used for determination of dominant occupancy at the Y-site (from Bak et al., 2013). Data used in these gures are taken from Henry (2011).

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Fig. 13. (a) Variation of tourmaline composition. (a) Mg vs. Fetot (apfu) diagram (revised from London and Manning, 1995). (b) R3 vs. (R1 R2 ) (apfu) diagram (revised from Manning, 1982). (c) Ca (apfu) vs. X-site vacancy diagram (from Henry and Dutrow, 1990). (d) Ca vs. Na (apfu) diagram (from Henry and Dutrow, 1990). (e) Altot vs. Fetot (apfu) diagram (from Williamson et al., 2000). (f) Y ZR2 vs. R3 (apfu) diagram (from Novk et al., 2011). Data used in these gures are taken from Yavuz et al. (2008).

and xlsx), and Grapher plot document les (i.e., grf les). The program and its associated les are installed into the directory of C:\Program Files\WinTcac during an installation. The selfextracting setup le is approximately 25 MB and can be obtained in the journal server or from corresponding author on request.

Acknowledgments We thank Darrell J. Henry for providing us representative tourmaline analyses, which are used to test during the development of WinTcac program. The authors are grateful to Vincent

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F. Yavuz et al. / Computers & Geosciences 63 (2014) 70 87 Fuchs, Y., Lagache, M., Linares, J., Maury, R., Varret, F., 1995. Mssbauer and optical spectrometry of selected schorl-dravite tourmalines. Hyperne Interact. 96, 245258. Gallagher, V., 1988. Coupled substitutions in schorl-dravite tourmaline: new evidence from SE Ireland. Mineral. Mag. 52, 637650. Hawthorne, F.C., Henry, D.J., 1999. Classication of the minerals of the tourmaline group. Eur. J. Mineral. 11, 201215. Henry, D.J., 2011. Spreadsheet for determining the tourmaline species based on an ordered distribution of elements in the tourmaline formula. http:// www.minsocam.org/msa/ammin/toc/2011/MJ11_Data/Henry_p895_11_Tourma lineSpecies.xls. (accessed 21.10.12). Henry, D.J., Dutrow, B.L., 1990. Ca substitution in Li-poor aluminous tourmaline. Can. Mineral. 28, 111124. Henry, D.J., Dutrow, B.L., 1992. Tourmaline in a low grade clastic metasedimentary rock: an example of the petrogenetic potential of tourmaline. Contrib. Mineral. Petrol. 112, 203218. Henry, D.J., Dutrow, B.L., 1996. Metamorphic tourmaline and its petrologic applications. In: Grew, E.S., Anovitz, L.M. (Eds.), Boron: Mineralogy, Petrology, and Geochemistry, Reviews in Mineralogy, vol. 33. Mineralogical Society of America, Chantilly, Virginia, pp. 503557. Henry, D.J., Dutrow, B.L., 2001. Compositional zoning and element partitioning in nickeloan tourmaline from a metamorphosed karstbauxite from Samos, Greece. Am. Mineral. 86, 11301142. Henry, D.J., Dutrow, B.L., 2012. Tourmaline at diagenetic to low-grade metamorphic conditions: its petrologic applicability. Lithos 154, 1632. Henry, D.J., Guidotti, C.V., 1985. Tourmaline as a petrogenetic indicator mineral: an example from the staurolite-grade metapelites of NW Maine. Am. Mineral. 70, 115. Henry, D.J., Lu, G., McCabe, C., 1994. Epigenetic tourmaline in sedimentary redbeds: an example from the Silurian Rose Hill Formation, Virginia. Can. Mineral. 32, 599605. Henry, D.J., Novk, M., Hawthorne, F.C., Ertl, A., Dutrow, B.L., Uher, P., Pezozotta, F., 2011. Nomenclature of the tourmaline-supergroup minerals. Am. Mineral. 96, 895913. Jiang, S.Y., Palmer, M.R., Li, Y.-H., Xue, C.-J., 1995. Chemical compositions of tourmaline in the YindongziTongmugou PbZn deposits, Qinling, China: implications for hydrothermal ore-forming processes. Miner. Depos. 30, 225234. Jiang, S.Y., Palmer, M.R., McDonald, A.M., Slack, J.F., Leitch, C.H.B., 1996. Feruvite from the Sullivan PbZnAg deposit, British Columbia. Can. Mineral. 34, 733740. Jiang, S.Y., Yu, J.M., Lu, J.J., 2004. Trace and rare-earth element geochemistry in tourmaline and cassiterite from the Yunlong tin deposit, Yunnan, China: implication for migmatitic-hydrothermal uid evolution and ore genesis. Chem. Geol. 209, 193213. Kazachenko, V.T., Butsik, L.A., Sapin, V.I., Kitaev, I.V., Barinov, N.N., Narnov, G.A., 1993. Vanadian-chromian tourmaline and vanadian muscovite in contactmetamorphosed carbonaceous rocks, Primorye, Russia. Can. Mineral. 31, 347356. Kawakami, T., 2001. Tourmaline breakdown in the migmatite zone of the Ryoke metamorphic belt, SW Japan. J. Metamorph. Geol. 19, 6175. Keller, P., Robles, E.R., Prez, A.P., Fontan, F., 1999. Chemistry, paragenesis and signicance of tourmaline in pegmatites of the Southern Tin Belt, central Namibia. Chem. Geol. 158, 203225. London, D., Manning, D.A.C., 1995. Chemical variation and signicance of tourmaline from southwest England. Econ. Geol. 90, 495519. Lynch, G., Ortega, J., 1997. Hydrothermal alteration and tourmaline-albite equilibria at the Coxheat porphyry CuMoAu deposit, Nova Scotia. Can. Mineral. 35, 7994. Manning, D.A.C., 1982. Chemical and morphological variation in tourmalines from the Hub Kapong batholith of peninsular Thailand. Mineral. Mag. 45, 139147. Manning, D.A.C., 1986. Contrasting styles of SnW mineralization in peninsular Thailand and SW England. Miner. Depos. 21, 4452. Morton, A.C., Whitham, A.G., Fanning, C.M., 2005. Provenance of Late Cretaceous to Paleocene submarine fan sandstones in the Norwegian Sea: integration of heavy mineral, mineral chemical and zircon age data. Sediment. Geol. 182, 328. McGuire, A.V., Dyar, M.D., Ward, K.A., 1989. Neglected Fe3 /Fe2 ratiosa study of Fe3 content of megacrysts from alkali basalts. Geology 17, 687690. Mlynarczyk, M.S.J., Williams-Jones, A.E., 2006. Zoned tourmaline associated with cassiterite: implications for uid evolution and tin mineralization in the San Rafael SnCu deposit, southeastern Peru. Can. Mineral. 44, 347365. Nascimento, M.S., Ges, A.M., Macambira, M.J.B., Brod, J.A., 2007. Provenance of Albian sandstones in the So Lus-Graja Basin (northern Brasil) from evidence of PbPb zircon ages, mineral chemistry of tourmaline and palaeocurrent data. Sediment. Geol. 201, 2142. Neiva, A.M.R., Silva, M.M.V.G., Gomes, M.E.P., 2007. Crystal chemistry of tourmaline from Variscan granites, associated tin-tungsten- and gold deposits, and associated metamorphic and metasomatic rocks from northern Portugal. Neues Jahrb. Mineral. Abh. 184, 4576. Neiva, A.M.R., Gomes, C.A.A.L., 2012. Tourmaline-group minerals in the Naipa Li CsTa granitic pegmatite group, Mozambique: tracers of magmatic to postmagmatic evolution trends. Neues Jahrb. Mineral. Abh. 189, 120. Novk, M., Ertl, A., Povondra, P., Galiov, M.V., Rossman, G.R., Pristacz, H., Prem, M., Giester, R., Gadas, P., koda, R., 2013. Darrellhenryite, Na(LiAl2)

J. van Hinsberg and Ekkehart Tillmanns for their constructive comments and critiques.

Appendix A. Supplementary material Supplementary data associated with this article can be found in the online version at http://dx.doi.org/10.1016/j.cageo.2013.10.012. References
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Torres-Ruiz, J., Pesquera, A., Gil-Crespo, P.P., Velilla, N., 2003. Origin and petrogenetic implications of tourmaline-rich rocks in the Sierra Nevada (Beltic Cordillera, southeastern Spain). Chem. Geol. 197, 5586. Trumbull, R.B., Krientiz, M.-S., Gottesmann, B., Wieddenbeck, M., 2008. Chemical and boron-isotope variations in tourmalines from an S-type granite and its source rock: the Erongo granite and tourmalinites in the Damara Belt, Namibia. Contrib. Mineral. Petrol. 155, 118. van den Bleeken, G., Corteel, C., Van den Haute, P., 2007. Epigenetic to low-grade tourmaline in the Gdoumont metaconglomerates (Belgium): a sensitive probe of its chemical environment of formation. Lithos 95, 165176. van Hinsberg, V.J., Henry, D.J., Dutrow, B.L., 2011a. Tourmaline as petrologic forensic mineral: a unique recorder of its geologic past. Elements 7, 327332. van Hinsberg, V.J., Henry, D.J., Marschall, H.R., 2011b. Tourmaline: an ideal indicator of its host environment. Can. Mineral. 49, 116. van Hinsberg, V.J., Schumacher, J.C., 2011. Tourmaline as a petrogenetic indicator mineral in the Haut-Allier metamorphic suite, Massif Central, France. Can. Mineral. 49, 177194. Warnaars, F.W., Holmgren, C., Barassi, F., 1985. Porphyry copper and tourmaline breccias at Los Bronces-Rio Blanco, Chile. Econ. Geol. 80, 15441565. Williamson, B.J., Spratt, J., Adams, J.T., Tindle, A.G., Stanley, C.J., 2000. Geochemical constraints from zoned hydrothermal tourmalines on uid evolution and Sn mineralization: an example from fault breccias at Roche, SW England. J. Petrol. 41, 11391453. Yavuz, F., 1997. TOURMAL: software package for tourmaline, tourmaline-rich rocks and related ore deposits. Comput. Geosci. 23, 947959. Yavuz, F., 2007. WinAmphcal: a windows program for the IMA-04 amphibole classication. Geochem. Geophys. Geosyst. 8, 112, http://dx.doi.org/10.1029/ 2006GC001391. Yavuz, F., Fuchs, Y., Karakaya, N., Karakaya, M.., 2008. Chemical composition of tourmaline from the Asarck PbZnCu 7 U deposit, ebinkarahisar, Turkey. Mineral. Petrol. 94, 195208. Yavuz, F., Gltekin, A.H., Karakaya, M.., 2002. CLASTOUR: a computer program for classication of the minerals of the tourmaline group. Comput. Geosci. 28, 10171036. Yavuz, F., Jiang, S.Y., Karakaya, N., Karakaya, M.., Yavuz, R., 2011. Trace-element, rare-earth element and boron isotopic compositions of tourmaline from a veintype PbZnCu 7 U deposit, NE Turkey. Int. Geol. Rev. 53, 124. Yavuz, F., skenderolu, A., Jiang, S.Y., 1999. Tourmaline compositions from the Salikvan porphyry CuMo deposit and vicinity, northeastern Turkey. Can. Mineral. 37, 10071023. Yavuz, F., Yavuz, V., Sasmaz, A., 2006. WinClastoura Visual Basic program for tourmaline formula calculation and classication. Comput. Geosci. 32, 11561168.