From structure topology to chemical composition. XXVII. Revision of the crystal chemistry of the perraultite-type minerals of the seidozerite supergroup: Jinshajiangite, surkhobite, and bobshannonite

2020 ◽  
Vol 58 (1) ◽  
pp. 19-43
Author(s):  
Elena Sokolova ◽  
Frank C. Hawthorne ◽  
Fernando Cámara ◽  
Giancarlo Della Ventura ◽  
Yulia A. Uvarova
Keyword(s):  
Chemical Composition ◽  
Structure Type ◽  
Titanium Silicate ◽  
Ideal Formula ◽  
Structure Topology ◽  
Ideal Composition ◽  
Using Data ◽  
Cation Sites ◽  
Triclinic Unit Cell ◽  
The Ideal

ABSTRACT The crystal structures of the three perraultite-type minerals (bafertisite group, seidozerite supergroup)—jinshajiangite from Norra Kärr, Sweden, ideally NaBaFe2+4Ti2(Si2O7)2O2(OH)2F, Z = 4; surkhobite (holotype) from the Darai-Pioz massif, Tajikistan, ideally NaBaMn4Ti2(Si2O7)2O2(OH)2F, Z = 4; and bobshannonite (holotype) from Mont Saint-Hilaire, Canada, ideally Na2KBa(Mn7Na)Nb4(Si2O7)4O4(OH)4O2, Z = 2—were refined in space group C to R1 = 2.73, 2.85, and 2.02% on the basis of 2746, 2657, and 4963 unique reflections [Fo > 4σFo], respectively. Refinement was done using data from twinned crystals (jinshajiangite: three twin components; surkhobite and bobshannonite: two twin components). The parameters of a C-centered triclinic unit cell are as follows: jinshajiangite: a = 10.720(5), b = 13.823(7), c = 11.044(6) Å, α = 108.222(6), β = 99.28(1), γ = 89.989(6)°, V = 1532.0(2.2) Å3; surkhobite: a = 10.728(6), b = 13.845(8), c = 11.072(6) Å, α = 108.185(6), β = 99.219(5), γ = 90.001(8)°, V = 1540.0(2.5) Å3; and bobshannonite: a = 10.831(7), b = 13.903(9), c = 11.149(8) Å, α = 108.145(6), β = 99.215(9), γ = 90.007(7)°, V = 1572.6(3.2) Å3. New electron microprobe data are reported for the holotype surkhobite and new IR data for jinshajiangite. In the perraultite-type structure (structure type B1BG, B – basic, BG – bafertisite group), there is one type of TS (Titanium-Silicate) block and one type of I (Intermediate) block; they alternate along c. The TS block consists of HOH sheets (H-heteropolyhedral, O-octahedral). In the O sheet, the ideal composition of the five [6]MO sites is Fe2+4apfu (jinshajiangite), Mn4apfu (surkhobite), and (Mn7Na) (bobshannonite). There is no order of Fe2+ and Mn in the O sheet. In the H sheet, the ideal composition of the two [6]MH sites is Ti2apfu (jinshajiangite, surkhobite) and Nb4apfu (bobshannonite). The four [4]Si sites are occupied solely by Si. The MH octahedra and Si2O7 groups constitute the H sheet. The TS blocks link via common vertices of MH octahedra. The I block contains AP(1,2) and BP(1,2) cation sites. In the I block of jinshajiangite and surkhobite, the AP(1) site is occupied by Ba and the AP(2) site by K > Ba; the ideal composition of the two AP(1,2) sites is Ba apfu. In the I block of bobshannonite, Ba and K are ordered at the AP(1) and AP(2) sites, Ba:K ∼ 1:1 , ideally BaK apfu. The two BP(1,2) sites are each occupied by Na > Ca, ideally Na apfu (jinshajiangite, surkhobite) and solely by Na, ideally Na2apfu (bobshannonite). There is no order of Na and Ca at the BP(1,2) sites in jinshajiangite and surkhobite [currently defined as a Ca-ordered analogue of perraultite, ideally NaBaMn4Ti2(Si2O7)2O2(OH)2F, Z = 4]. The ideal formulae of surkhobite, KBa3Ca2Na2Mn16Ti8(Si2O7)8O8(OH)4(F,O,OH)8 (current IMA formula) and of bobshannonite, Na2KBa(Mn,Na)8(Nb,Ti)4(Si2O7)4O4(OH)4(O,F)2 (current IMA formula) have been revised as follows: NaBaMn4Ti2(Si2O7)2O2(OH)2F, Z = 4 (surkhobite) and Na2KBa(Mn7Na)Nb4(Si2O7)4O4(OH)4O2, Z = 2 (bobshannonite). The revised ideal formula of surkhobite is identical to the ideal formula of perraultite and hence surkhobite should be discredited.

From Structure Topology to Chemical Composition. XXIX. Revision of the Crystal Structure of Perraultite, NaBaMn4Ti2(Si2O7)2O2(OH)2F, a Seidozerite-Supergroup TS-Block Mineral from the Oktyabr'skii Massif, Ukraine, and Discreditation of Surkhobite

2021 ◽  
Author(s):  
Elena Sokolova ◽  
Maxwell C. Day ◽  
Frank C. Hawthorne ◽  
Atali A. Agakhanov ◽  
Fernando Cámara ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Chemical Composition ◽  
Structure Type ◽  
Titanium Silicate ◽  
Space Group ◽  
Structure Topology ◽  
Ideal Composition ◽  
Using Data ◽  
Cation Sites ◽  
The Ideal

ABSTRACT The crystal structure of perraultite from the Oktyabr'skii massif, Donetsk region, Ukraine (bafertisite group, seidozerite supergroup), ideally NaBaMn4Ti2(Si2O7)2O2(OH)2F, Z = 4, was refined in space group C to R1 = 2.08% on the basis of 4839 unique reflections [Fo > 4σFo]; a = 10.741(6), b = 13.841(8), c = 11.079(6) Å, α = 108.174(6), β = 99.186(6), γ = 89.99(1)°, V = 1542.7(2.7) Å3. Refinement was done using data from a crystal with three twin domains which was part of a grain used for electron probe microanalysis. In the perraultite structure [structure type B1(BG), B – basic, BG – bafertisite group], there is one type of TS (Titanium-Silicate) block and one type of I (Intermediate) block; they alternate along c. The TS block consists of HOH sheets (H – heteropolyhedral, O – octahedral). In the O sheet, the ideal composition of the five [6]MO sites is Mn4 apfu. There is no order of Mn and Fe2+ in the O sheet. The MH octahedra and Si2O7 groups constitute the H sheet. The ideal composition of the two [6]MH sites is Ti2 apfu. The TS blocks link via common vertices of MH octahedra. The I block contains AP(1,2) and BP(1,2) cation sites. The AP(1) site is occupied by Ba and the AP(2) site by K > Ba; the ideal composition of the AP(1,2) sites is Ba apfu. The BP(1) and BP(2) sites are each occupied by Na > Ca; the ideal composition of the BP(1,2) sites is Na apfu. We compare perraultite and surkhobite based on the work of Sokolova et al. (2020) on the holotype sample of surkhobite: space group C , R1 = 2.85 %, a = 10.728(6), b = 13.845(8), c = 11.072(6) Å, α = 108.185(6), β = 99.219(5), γ = 90.001(8)°, V = 1540.0(2.5) Å3; new EPMA data. We show that (1) perraultite and surkhobite have identical chemical composition and ideal formula NaBaMn4Ti2(Si2O7)2O2(OH)2F; (2) perraultite and surkhobite are isostructural, with no order of Na and Ca at the BP(1,2) sites. Perraultite was described in 1991 and has precedence over surkhobite, which was redefined as “a Ca-ordered analogue of perraultite” in 2008. Surkhobite is not a valid mineral species and its discreditation was approved by CNMNC IMA (IMA 20-A).

From structure topology to chemical composition. XXVI. Crystal structure and chemical composition of a possible new mineral of the murmanite group (seidozerite supergroup), ideally Na2CaTi4(Si2O7)2O4(H2O)4, from the Lovozero alkaline massif, Kola Peninsula, Russia

2018 ◽  
Vol 83 (02) ◽  
pp. 199-207
Author(s):  
Elena Sokolova ◽  
Frank C. Hawthorne
Keyword(s):  
Crystal Structure ◽  
Chemical Composition ◽  
Kola Peninsula ◽  
Structure Refinement ◽  
Structural Formula ◽  
New Mineral ◽  
Titanium Silicate ◽  
Structure Topology ◽  
Alkaline Massif ◽  
The Ideal

AbstractThe crystal structure of a murmanite-related mineral (MRM) of the murmanite group (seidozerite supergroup), ideally Na2CaTi4(Si2O7)2O4(H2O)4, from Mt. Pyalkimpor, the Lovozero alkaline massif, Kola Peninsula, Russia, was refined in space group P$ {\bar 1} $ with a = 5.363(2), b = 7.071(2), c = 12.176(5) Å, α = 92.724(3), β = 107.542(7), γ = 90.13(2)°, V = 439.7(4) Å3 and R1 = 5.72%. On the basis of electron-microprobe analysis, the empirical formula calculated on 22 (O + F), with two constraints derived from structure refinement, OH = 0.11 per formula unit (pfu) and H2O = 3.89 pfu, is (Na2.12K0.07Sr0.01)Σ2.20Ca0.85(Ti3.01Nb0.39Mn0.20Fe2+0.19Mg0.17Zr0.01Al0.01)Σ3.98(Si4.20O14)[O3.90F0.10]Σ4[(H2O)3.89(OH)0.11]Σ4{P0.03}, with Z = 1. It seems unlikely that {P0.03} belongs to MRM itself. The crystal structure of MRM is an array of TS blocks (Titanium-Silicate) connected via hydrogen bonds. The TS block consists of HOH sheets (H = heteropolyhedral, O = octahedral) parallel to (001). In the O sheet, the Ti-dominant MO1 site and Ca-dominant MO2 site give ideally (Ca□)Ti2 pfu. In the H sheet, the Ti-dominant MH site and Na-dominant AP site give ideally Na2Ti2 pfu. The MH and AP polyhedra and Si2O7 groups constitute the H sheet. The ideal structural formula of MRM of the form AP2MH2MO4(Si2O7)2(XOM,A)4(XOA)2(XPM,A)4 is Na2Ti2(Ca□)Ti2(Si2O7)2O4(H2O)4. MRM is a Ca-rich and Na-poor analogue of murmanite, ideally Na2Ti2Na2Ti2(Si2O7)2O4(H2O)4 and a Na-rich and (OH)-poor analogue of calciomurmanite, ideally (Ca□)Ti2(Na□)Ti2(Si2O7)2O2[O(OH)](H2O)4. MRM and (murmanite and calciomurmanite) are related by the following substitutions: O(Ca2+□)MRM ↔ O(Na+2)mur and O(Ca2+□)MRM + H(Na+2)MRM + O(O2–)MRM ↔ O(Na+□)cal + H(Ca2+□)cal + O[(OH)–]cal. MRM is a possible new mineral of the murmanite group (seidozerite supergroup) where Ti + Mn + Mg = 4 apfu.

scholarly journals From structure topology to chemical composition. XXIII. Revision of the crystal structure and chemical formula of zvyaginite, Na2ZnTiNb2(Si2O7)2O2(OH)2(H2O)4, a seidozerite-supergroup mineral from the Lovozero alkaline massif, Kola peninsula, Russia

2017 ◽  
Vol 81 (6) ◽  
pp. 1533-1550 ◽  
Author(s):  
E. Sokolova ◽  
A. Genovese ◽  
A. Falqui ◽  
F.C. Hawthorne ◽  
F. Cámara
Keyword(s):  
Crystal Structure ◽  
Kola Peninsula ◽  
Microprobe Analysis ◽  
Structural Formula ◽  
Chemical Formula ◽  
Titanium Silicate ◽  
Structure Topology ◽  
Diffraction Patterns ◽  
Alkaline Massif ◽  
The Ideal

AbstractThe crystal structure and chemical formula of zvyaginite, ideally Na2ZnTiNb2(Si2O7)2O2(OH)2(H2O)4, a lamprophyllite-group mineral of the seidozerite supergroup from the type locality, Mt. Malyi Punkaruaiv, Lovozero alkaline massif, Kola Peninsula, Russia have been revised. The crystal structurewas refined with a new origin in space group C1, a = 10.769(2), b = 14.276(3), c = 12.101(2) Å, α = 105.45(3), β = 95.17(3), γ = 90.04(3)°, V = 1785.3(3.2) Å3, R1 = 9.23%. The electron-microprobe analysis gave the following empirical formula [calculated on 22 (O + F)]: (Na0.75Ca0.09K0.04□1.12)Σ2 (Na1.12Zn0.88Mn0.17Fe2+0.04□0.79)Σ3 (Nb1.68Ti1.25Al0.07)Σ3 (Si4.03O14)O2 [(OH)1.11F0.89]Σ2(H2O)4, Z = 4. Electron-diffraction patterns have prominent streaking along c* and HRTEM images show an intergrowth of crystalline zvyaginite with two distinct phases, both of which are partially amorphous. The crystal structure of zvyaginite is an array of TS (Titanium-Silicate) blocks connected via hydrogen bonds between H2O groups. The TS block consists of HOH sheets (H = heteropolyhedral, O = octahedral) parallel to (001). In the O sheet, the [6]MO(1,4,5) sites are occupied mainly by Ti, Zn and Na and the [6]MO(2,3) sites are occupied by Na at less than 50%. In the H sheet, the [6]MH(1,2) sites are occupied mainly by Nb and the [8]AP(1) and [8]AP(2) sites are occupied mainly by Na and □. The MH and AP polyhedra and Si2O7 groups constitute the H sheet. The ideal structural formula is Na□Nb2NaZn□Ti(Si2O7)2O2(OH)2(H2O)4. Zvyaginite is a Zn-bearing and Na-poor analogue of epistolite, ideally (Na□)Nb2Na3Ti(Si2O7)2O2(OH)2(H2O)4. Epistolite and zvyaginite are related by the following substitution in the O sheet of the TS-block: (Naþ 2 )epi↔Zn2+ zvy +□zvy. The doubling of the t1 and t2 translations of zvyaginite relative to those of epistolite is due to the order of Zn and Na along a (t1) and b (t2) in the O sheet of zvyaginite.

From structure topology to chemical composition. XIV. Titanium silicates: refinement of the crystal structure and revision of the chemical formula of mosandrite, (Ca3REE)[(H2O)2Ca0.5□0.5]Ti(Si2O7)2(OH)2(H2O)2, a Group-I mineral from the Saga mine, Morje, Porsgrunn, Norway

2013 ◽  
Vol 77 (6) ◽  
pp. 2753-2771 ◽  
Author(s):  
E. Sokolova ◽  
F. C. Hawthorne
Keyword(s):  
Crystal Structure ◽  
Long Range ◽  
Structure Refinement ◽  
Alkali Cations ◽  
Oh Groups ◽  
Structure Topology ◽  
Titanium Silicates ◽  
Group I ◽  
Ideal Composition ◽  
Cation Sites

AbstractThe crystal structure of mosandrite, ideally (Ca3REE)[(H2O)2Ca0.5☐0.5]Ti(Si2O7)2(OH)2(H2O)2, from the Saga mine, Morje, Porsgrunn, Norway, has been refined as two components related by the TWIN matrix ( 0 0, 0 0, 1 0 1): a 7.4222(3), b 5.6178(2), c 18.7232(7) Å, β 101.4226(6)°, V = 765.23(9) Å3, space group P21/c, Dcalc. = 3.361 g.cm–3, R1 = 3.69% using 1347 observed (Fo > 4σF) reflections. The empirical formula of mosandrite (EMPA) was calculated on the basis of 4 Si a.p.f.u., with H2O determined from structure refinement: [(Ca2.89Ba0.01)Σ2.90(Ce0.39La0.18Nd0.14Sm0.02Gd0.03Y0.16Th0.03)Σ1.01Zr0.09]Σ4 [(H2O)2.00Ca0.32Na0.17Al0.10Mn0.04Fe2+0.02☐0.35]Σ3(Ti0.87Nb0.09Zr0.04)Σ1(Si2O7)2[(OH)1.54F0.46]Σ2[(H2O)1.50F0.50]Σ2, Z = 2. The crystal structure of mosandrite is a framework of TS (titanium silicate) blocks; each TS block consists of HOH sheets (H-heteropolyhedral, O-octahedral). In the TS block, there are five fully occupied cation sites, two [4]-coordinated Si sites with <Si–O> 1.623 Å , [7]-coordinated MH and AP sites occupied by Ca and REE in the ratio ∼3:1, and one [6]-coordinated Ti-dominant MO(1) site. There are two H2O-dominant H2O-alkali-cation sites. The partly occupied MO(2) site has composition [(H2O)0.5☐0.33Na0.17], ideally [(H2O)0.5☐0.5] p.f.u. The MO(3) site has ideal composition [(H2O)1.5Ca0.5] p.f.u. In the O sheet, the XOM and XOA anion sites have compositions [(OH)1.54F0.46] (XOM) and [(H2O)1.50F0.50] (XOA), ideally (OH)2 and (H2O)2 p.f.u. The MH and AP polyhedra and Si2O7 groups constitute the H sheet that is completely ordered. In the O sheet, MO(1) octahedra are long-range ordered whereas H2O and OH groups and alkali cations Na and Ca are long-range disordered. Two SRO (short-range ordered) arrangements have been proposed for the O sheet: (1) Na [MO(2)], Ca2 [MO(3)] and F4[XOM and XOA anion sites]; (2) 2 H2O [MO(2)] and MO(3)] and (OH)2 and (H2O)2 [XOM and XOA]. Linkage of H and O sheets occurs mainly via common vertices of MH polyhedra and Si2O7 groups and MO(1) octahedra. Two adjacent TS blocks are related by the glide plane cy. Mosandrite is an H2O- and OH-bearing Na- and Ca-depleted analogue of rinkite, ideally (Ca3REE)Na(NaCa) Ti(Si2O7)2(OF)F2. Mosandrite and rinkite are related by the following substitution at the MO(2,3) and XO(M,A) sites in the O sheet: M[(H2O)2 + ☐0.5] + X[(OH)–2 + (H2O)2] ↔ M[Na+2 + Ca2+0.5] + X[(OF)3– + (F2)2–].

From structure topology to chemical composition. XXV: new insights into the close packing of cations in the structures of the seidozerite-supergroup TS-block minerals

2018 ◽  
Vol 233 (3-4) ◽  
pp. 205-221
Author(s):  
Elena Sokolova ◽  
Fernando Cámara
Keyword(s):  
Chemical Composition ◽  
Structural Unit ◽  
Direct Interaction ◽  
Close Packing ◽  
Titanium Silicate ◽  
Octahedral Sheet ◽  
Structure Topology ◽  
And Topology ◽  
Block Form ◽  
Block Structures

AbstractThe titanium-silicate (TS) block is the main structural unit in the 45 seidozerite-supergroup minerals; it consists of a central O (O=Octahedral) sheet and two adjacent H (H=Heteropolyhedral) sheets where Si2O7groups occur in the H sheets. The three HOH sheets of the TS block form a three-layered close packing of cations with an ABC repeat; mean cation–cation distances are 3.41 Å. Minerals of the seidozerite supergroup are divided into four groups based on the content of Ti and topology and stereochemistry of the TS block: in rinkite, bafertisite, lamprophyllite and murmanite groups, Ti (+Nb+Zr+Fe3++Mg+Mn)=1, 2, 3 and 4 apfu, respectively. All TS-block structures consist either solely of TS blocks or of two types of block: the TS block and anI(intermediate) block that comprises atoms between two TS blocks. The TS block propagates close packing of cations into theIblock. There are two types of close-packed layers of cations in theIblock: (I) a layer of Na+and P5+with mean cation–cation distances of 3.41 Å and (II) a layer of Ba2+(+K+, Sr2+and Na+) with mean cation–cation distances of 4.73 Å. The general topology of the TS block is independent of the topology and chemical composition of theIblock. However direct interaction between TS andIblocks takes place in the crystal structures of jinshajiangite, bobshannonite, bafertisite, hejtmanite, delindeite and cámaraite. Interaction of Ba atoms in theIblock and F (+O) atoms of the TS block results in doubling of the minimal translations, 2t1and 2t2, and a concomitant change in symmetry of the structure from primitive toC-centered.

From structure topology to chemical composition. XXIV. Revision of the crystal structure and chemical formula of vigrishinite, NaZnTi4(Si2O7)2O3(OH)(H2O)4, a seidozerite-supergroup mineral from the Lovozero alkaline massif, Kola peninsula, Russia

2018 ◽  
Vol 82 (4) ◽  
pp. 787-807 ◽  
Author(s):  
Elena Sokolova ◽  
Frank C. Hawthorne
Keyword(s):  
Crystal Structure ◽  
Kola Peninsula ◽  
Microprobe Analysis ◽  
Electron Microprobe Analysis ◽  
Structure Refinement ◽  
Structural Formula ◽  
Titanium Silicate ◽  
Structure Topology ◽  
Alkaline Massif ◽  
The Ideal

ABSTRACTThe crystal structure of vigrishinite, ideally NaZnTi4(Si2O7)2O3(OH)(H2O)4, a murmanite-group mineral of the seidozerite supergroup from the type locality, Mt. Malyi Punkaruaiv, Lovozero alkaline massif, Kola Peninsula, Russia, was refined in space group C$\bar 1$, a = 10.530(2), b = 13.833(3), c = 11.659(2) Å, α = 94.34(3), β = 98.30(3), γ = 89.80(3)°, V = 1675.5(2.1) Å3 and R1 = 12.52%. Based on electron-microprobe analysis, the empirical formula calculated on 22 (O + F), with two constraints derived from structure refinement, OH + F = 1.96 pfu and H2O = 3.44 pfu, is: (Na0.67Zn0.21Ca0.05□1.07)Σ2 (Zn0.86□1.14)Σ2(Zn0.14□0.36)Σ0.5(Ti2.60Nb0.62Mn0.30${\rm Fe}_{{\rm 0}{\rm. 23}}^{{\rm 2 +}} $Mg0.10Zr0.06Zn0.05Al0.03Ta0.01)Σ4(Si4.02O14) [O2.60(OH)1.21F0.19]Σ4[(H2O)3.44(OH)0.56]Σ4{Zn0.24P0.03K0.03Ba0.02} with Z = 4. It seems unlikely that constituents in the {} belong to vigrishinite itself. The crystal structure of vigrishinite is an array of TS blocks (Titanium Silicate) connected via hydrogen bonds. The TS block consists of HOH sheets (H = heteropolyhedral and O = octahedral) parallel to (001). In the O sheet, the Ti-dominant MO(1,2) sites, Na-dominant MO(3) and □-dominant MO(4) sites give ideally Na□Ti2 pfu. In the H sheet, the Ti-dominant MH(1,2) sites, Zn-dominant AP(1) and vacant AP(2) sites give ideally Zn□Ti2 pfu. The MH and AP(1) polyhedra and Si2O7 groups constitute the H sheet. The ideal structural formula of vigrishinite of the form ${\rm A}_{\rm 2}^{P} {\rm M}_{\rm 2}^{\rm H} {\rm M}_{\rm 4}^{\rm O} $(Si2O7)2(${\rm X}_{\rm M}^{\rm O} $)2(${\rm X}_{\rm A}^{\rm O} $)2(${\rm X}_{{\rm M,A}}^{P} $)4 is Zn□Ti2Na□Ti2(Si2O7)2O2O(OH)(H2O)4. Vigrishinite is a Zn-bearing, Na-poor and OH-rich analogue of murmanite, ideally Na2Ti2Na2Ti2(Si2O7)2O2O2(H2O)4. Murmanite and vigrishinite are related by the following substitution: H(${\rm Na}_{\rm 2}^{\rm +} $)mur + O(Na+)mur + O(O2–)mur ↔ H(Zn2+)vig + H(□)vig + O(□)vig + O[(OH)–]vig. The doubling of the t1 and t2 translations of vigrishinite compared to those of murmanite is due to the order of Zn and □ in the H sheet and Na and □ in the O sheet of vigrishinite.

scholarly journals Bobshannonite, Na2KBa(Mn,Na)8(Nb,Ti)4(Si2O7)4O4(OH)4(O,F)2, a new TS-block mineral from Mont Saint-Hilaire, Québec, Canada: Description and crystal structure

2015 ◽  
Vol 79 (7) ◽  
pp. 1791-1811 ◽  
Author(s):  
E. Sokolova ◽  
F. Cámara ◽  
Y.A. Abdu ◽  
F.C. Hawthorne ◽  
L. Horváth ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Polarized Light ◽  
Crystal Structure Analysis ◽  
X Ray Diffraction ◽  
Titanium Silicate ◽  
Ionic Radii ◽  
Mohs Hardness ◽  
Ideal Composition ◽  
Group Ii ◽  
The Ideal

AbstractBobshannonite, Na2KBa(Mn,Na)8(Nb,Ti)4(Si2O7)4O4(OH)4(O,F)2, is a new TS-block mineral from Mont Saint-Hilaire, Québec, Canada. It occurs as blocky crystals 0.5–1 mm across,perched on sérandite and albite. Other associated minerals are epididymite, catapleiite, aegirine, kupletskite, rhodochrosite and rhabdophane-(Ce). Bobshannonite occurs as vitreous to frosty, transparent to translucent very pale brown to orange brown crystals, has a very pale brown streak, hackly fracture and does not fluoresce under cathode or ultraviolet light. Cleavage is {001} very good, no parting was observed, Mohs hardness is ∼4, it is brittle and Dcalc. = 3.787 g/cm3. Crystals are twinned extensively and do not extinguish in cross-polarized light. Bobshannonite is triclinic, C1, a = 10.839(6), b = 13.912(8), c = 20.98(1) Å, α = 89.99(1), β = 95.05(2), γ = 89.998(9)°, V = 3152(5) Å3. The six strongest reflections in the powder X-ray diffraction data [d (Å),I, (hkl)] are: 2.873, 100, (241, 241, 044, 044, 241, 241); 3.477, 60, (006); 3.193, 59, (224, 224); 2.648, 40, (402, 243, 243); 2.608, 35, (008, 226, 226); 1.776, 30, (249). Chemical analysis by electron microprobe gave Ta2O5 0.52, Nb2O5 19.69,TiO2 5.50, SiO2 26.31, Al2O3 0.06, BaO 7.92, ZnO 1.02, FeO 0.89, MnO 26.34, MgO 0.06, Rb2O 0.42, K2O 2.38, Na2O 4.05, F 0.70, H2Ocalc. 1.96, O = –0.29, total 97.53 wt.%, where the H2O content was calculated from the crystal-structure analysis. The empirical formula on the basis of 38 anions is Na1.89(K0.93Rb0.08)Σ1.01Ba0.95(Mn6.85Na0.52Zn0.23Fe0.232+Mg0.03Al0.02)Σ7.88(Nb2.73Ti1.27Ta0.04)Σ4.04(Si8.07O28)O9.32H4.01F0.68,Z = 4. The crystal structure was refined to R1 = 2.55% on the basis of 7277 unique reflections [F > 4σ(F)] and can be described as a combination of a TS (Titanium Silicate) block and an I (Intermediate) block. The TS block consists ofHOH sheets (H – heteropolyhedral, O – octahedral). The topology of the TS block is as in Group II of the Ti disilicates: Ti + Nb = 2 a.p.f.u. per (Si2O7)2 [as defined by Sokolova (2006)]. In the O sheet, ten[6]MO sitesare occupied mainly by Mn, less Na and minor Zn, Fe2+, Mg and Al, with <MO–ϕ> = 2.223 Å. In the H sheet, four [6]MH sites are occupied by Nb and Ti (Nb > Ti), with <MH–ϕ> = 1.975 Å,and eight [4]Si sites are occupied by Si, with <Si–O> = 1.625 Å. The MH octahedra and Si2O7 groups constitute the H sheet. The TS blocks link via common vertices of MH octahedra. In the I block, Ba and Kare ordered at the AP(1) and AP(2) sites with Ba:K = 1:1 and the two BP sites are occupied by Na. The ideal composition of the I block is Na2KBa a.p.f.u. Bobshannonite, perraultite, surkhobite and jinshajiangite are topologically identical Group-II TS-block minerals. Bobshannonite is the Nb-analogue of perraultite. The mineral is named bobshannonite after Dr. Robert (Bob) D. Shannon (b. 1935), in recognition of his major contributions to the field of crystal chemistry in particular and mineralogy in general through his development of accurate and comprehensive ionic radii and his work on dielectric properties of minerals.

scholarly journals From structure topology to chemical composition. XX. Titanium silicates: the crystal structure of hejtmanite, Ba2Mn4Ti2(Si2O7)2O2(OH)2F2, a Group-II TS-block mineral

2016 ◽  
Vol 80 (5) ◽  
pp. 841-853 ◽  
Author(s):  
E. Sokolova ◽  
F. Cámara ◽  
F. C. Hawthorne ◽  
L. A. Pautov
Keyword(s):  
Crystal Structure ◽  
Chemical Composition ◽  
Structure Refinement ◽  
Central Province ◽  
Crystal Structure Refinement ◽  
Titanium Silicate ◽  
Oh Groups ◽  
Structure Topology ◽  
Titanium Silicates ◽  
Group Ii

AbstractThe crystal structure of hejtmanite, Ba2Mn4Ti2(Si2O7)2O2(OH)2F2, from Mbolve Hill, Mkushi River area, Central Province, Zambia (holotype material) has been refined on a twinned crystal toR1= 1.88% on the basis of 4539 [|F| > 4|F|] reflections. Hejtmanite is triclinic,C1̅,a= 10.716(2),b= 13.795(3),c= 11.778 (2) , = 90.07(3), = 112.24(3), = 90.03(3),V= 1612(2)3. Chemical analysis (electron microprobe) gives: Ta2O50.09, Nb2O51.27, ZrO20.65, TiO214.35, SiO223.13, BaO 26.68, SrO 0.19, FeO 11.28, MnO 15.12, Cs2O 0.05, K2O 0.33, F 3.82, H2Ocalc. 1.63, O = F 1.61, total 97.10 wt.%, where the H2O content was calculated from the crystal-structure refinement, with (OH F) = 4 apfu. The empirical formula, calculated on the basis of 20 (O F) anions, is of the form(Si2O7)2(XO)4(XP)2, Z=4: (Ba1.82K0.07Sr0.02)Σ1.91(Mn2.33Zr0.04Mg0.03)Σ3.95(Ti1.88Nb0.10Zr0.02)Σ2(Si2.02O7)2O2[(OH)1.89F0.11]Σ2F2. The crystal structure is a combination of a TS (Titanium Silicate) block and an I (intermediate) block. The TS block consists of HOH sheets (H heteropolyhedral, O octahedral). The topology of the TS block is as in Group-II TS-block minerals: Ti ( Nb) = 2 apfu per (Si2O7)2[as defined by Sokolova (2006)]. In the O sheet, five[6]MOsites are occupied mainly by Mn, less Fe2and minor Zr and Mg, with <MOφ> = 2.198 (φ = O,OH), ideally giving Mn4apfu. In the H sheet, two[6]MHsites are occupied mainly by Ti, with <MHφ> = 1.962 (φ = O,F), ideally giving Ti2apfu; four[4]Sisites are occupied by Si, with < SiO> = 1.625 . The MHoctahedra and Si2O7groups constitute the H sheet. The two[12]Ba-dominant AP(1,2) sites, with <APφ> = 2.984 (φ = O, F), ideally give Ba2apfu. Two(1,2) and two(1,2) sites are occupied by O atoms and OH groups with minor F, respectively, ideally giving (XO)4= ()2()2=O2(OH)2pfu. Two(1,2) sites are occupied by F, giving F2apfu. TS blocks link via a layer of Ba atoms which constitute the I block. Simplified and end-member formulae of hejtmanite are Ba2(Mn,Fe2)4Ti2(Si2O7)2O2(OH,F)2F2and Ba2Mn4Ti2(Si2O7)2O2(OH)2F2,Z= 4. Hejtmanite is a Mn-analogue of bafertisite, Ba24 Ti2(Si2O7)2O2(OH)2F2.

Further developments in the structure topology of the astrophyllite-group minerals

2012 ◽  
Vol 76 (4) ◽  
pp. 863-882 ◽  
Author(s):  
E. Sokolova
Keyword(s):  
Crystal Chemistry ◽  
Structure Topology ◽  
Ideal Composition ◽  
The Ideal

AbstractThe structure topology and crystal chemistry have been considered for ten astrophyllite-group minerals that contain the HOH layer, a central trioctahedral (O) sheet and two adjacent (H) sheets of [5]- and [6]-coordinated D polyhedra and the astrophyllite (T4O12) ribbons. The HOH layer is characterized by a planar cell with a ∼5.4, b ∼11.9 A ˚ and a^b ∼103°. The ideal composition of the O sheet is Fe72+ (astrophyllite) or Mn72+(kupletskite). All structures consist of an HOH layer and an I (intermediate) block that consists of atoms between two HOH layers. In the astrophyllite group, there are two types of structures based on the type of linkage of HOH layers: (1) HOH layers link directly where they share common vertices of D octahedra, and (2) HOH layers do not link directly via polyhedra of the H sheets. The type-1 structure occurs in astrophyllite, niobophyllite, nalivkinite, tarbagataite, kupletskite, niobokupletskite and kupletskite-(Cs); the type-2 structure occurs in magnesioastrophyllite, sveinbergeite and devitoite. The general formulae for the eight astrophyllite-group minerals (astrophyllite, niobophyllite, nalivkinite, tarbagataite, kupletskite, niobokupletskite, kupletskite-(Cs), magnesioastrophyllite) and for the extended astrophyllite group including devitoite and sveinbergeite are A2BC7D2T8O26(OH)4X0–1 and A2pBrC7D2(T4O12)2IXD2OXA4OXDnP, respectively, where C and D are cations of the O and H sheets, C =[6](Fe2+, Mn, Fe3+, Na, Mg, Zn) at the M(1–4) sites; D = [6,5](Ti, Nb, Zr, Fe3+); T = Si, minor Al; A2pBrI is the composition of the I block where p = 1,2; r = 1,2; A = K, Cs, Li, Ba, H2O, ☐; B = Na, Ca, Ba, H2O, ☐; I represents the composition of the central part of the I block, excluding peripheral layers of the form A2B; X = O, OH, F and H2O; n = 0, 1, 2. Two topological issues have been considered: (1) the pattern of sizes of the M octahedra in the O sheet, M(1) > M(2) > M(3) > M(4) and (2) different topologies of the HOH layer in magnesioastrophyllite and all other structures of the astrophyllite group.

Determination of the composition of natural nephelines by an X-ray method

1954 ◽  
Vol 30 (226) ◽  
pp. 439-449 ◽  
Author(s):  
J. V. Smith ◽  
Th. G. Sahama
Keyword(s):  
Chemical Composition ◽  
Ray Method ◽  
X Ray ◽  
Ideal Composition ◽  
The Ideal

In the course of the investigation of the nepheline-kalsilite system by Tuttle and Smith an X-ray method for determining the KAlSiO4 content of synthetic nephelines of composition (Na,K)AlSiO4 has been developed. This method is rapid and sensitive to about 1 % in composition ; details will be given in a later publication.Natural nephelines usually do not have the ideal composition (K,Na)AlSiO4, for they often contain excess silica and certain substituted atoms like Ca and Fe. We have, however, used this X-ray method on natural nephelines to see whether it is also applicable to them. If the method proved satisfactory, information on the chemical composition of natural nephelines could be rapidly obtained.

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