The crystal chemistry of Mn3+ in the clino- and orthozoisite structure types, Ca2M3
 3+[OH|O|SiO4|Si2O7]: A structural and spectroscopic study of some natural piemontites and “thulites” and their synthetic equivalents

Langer, Klaus; Тиллманнс, Е.; Kersten, M.; Almen, Hartmut; Arni, R.K.

doi:10.1524/zkri.217.11.563.20780

Cited by 29 publications

(15 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Bonazzi and Menchetti [26] reviewed the studies about the ordering of these two transition elements between M(1) and M(3) in natural and synthetic piemontite and pointed out that Mössbauer spectroscopy [27] and neutron diffraction [28] data indicate that not all Mn 3+ is ordered at M(3) at the expense of Fe 3+ . As Langer et al [29] suggested, although the compression of the M(3) octahedron along the O(4)-M(3)-O(8) axis is directly related to the Mn 3+ content at this site, there is evidence that the distortion of M(3) in Mn 3+ -bearing epidote supergroup minerals is not related to the Jahn-Teller effect only, and that the distortion of the M sites is only partially affected by their composition. Moreover, a significant distortion of the M(1) octahedron along the O(4)-M(1)-O(4) axis seems to be also related with the increasing total Mn 3+ content in piemontites [29], thus indicating that part of Mn 3+ can be hosted at M (1).…”

Section: Crystal-chemistry Of Manganiakasakaite-(la) and Ferriakasakamentioning

confidence: 96%

“…As Langer et al [29] suggested, although the compression of the M(3) octahedron along the O(4)-M(3)-O(8) axis is directly related to the Mn 3+ content at this site, there is evidence that the distortion of M(3) in Mn 3+ -bearing epidote supergroup minerals is not related to the Jahn-Teller effect only, and that the distortion of the M sites is only partially affected by their composition. Moreover, a significant distortion of the M(1) octahedron along the O(4)-M(1)-O(4) axis seems to be also related with the increasing total Mn 3+ content in piemontites [29], thus indicating that part of Mn 3+ can be hosted at M (1). Nonetheless, because the derivation of a mineral name from chemical data should be possible also in the lack of non-conventional structural data (e.g., neutron diffraction), the octahedral cations are assigned to M(3) and M(1) following the procedures suggested by Armbruster et al [1], i.e., according to a sequence based on decreasing ionic radii, filling first M(3) and then M(1), and regarding Mn 3+ as larger than Fe 3+ owing to the Jahn-Teller distortion.…”

Section: Crystal-chemistry Of Manganiakasakaite-(la) and Ferriakasakamentioning

confidence: 96%

See 1 more Smart Citation

Manganiakasakaite-(La) and Ferriakasakaite-(Ce), Two New Epidote Supergroup Minerals from Piedmont, Italy

et al. 2019

View full text Add to dashboard Cite

Two new monoclinic (P2 1 /m) epidote supergroup minerals manganiakasakaite-(La) and ferriakasakaite-(Ce) were found in the small Mn ore deposit of Monte Maniglia, Bellino, Varaita Valley, Cuneo Province, Piedmont, Italy. Manganiakasakaite-(La) occurs as subhedral grains embedded in pyroxmangite. Its empirical formula is A(1) (Ca 0.62 Mn 2+ 0.38 ) A(2) (La 0.52 Nd 0.08 Pr 0.07 Ce 0.07 Y 0.01 Ca 0.25 ) M(1) (Mn 3+ 0.52 Fe 3+ 0.28 Al 0.18 V 3+ 0.01 ) M(2) Al 1.00 M(3) (Mn 2+ 0.60 Mn 3+ 0.27 Mg 0.13 ) T(1−3) (Si 2.99 Al 0.01 ) O 12 (OH), corresponding to the end-member formula CaLaMn 3+ AlMn 2+ (Si 2 O 7 )(SiO 4 )O(OH). Unit-cell parameters are a = 8.9057(10), b = 5.7294(6), c = 10.1134(11) Å, β = 113.713(5) • , V = 472.46(9) Å 3 , Z = 2. The crystal structure of manganiakasakaite-(La) was refined to a final R 1 = 0.0262 for 2119 reflections with F o > 4σ(F o ) and 125 refined parameters. Ferriakasakaite-(Ce) occurs as small homogeneous domains within strongly inhomogeneous prismatic crystals, where other epidote supergroup minerals coexist [manganiandrosite-(Ce), "androsite-(Ce)", and epidote]. Associated minerals are calcite and hematite. Its empirical formula is A(1) (Ca 0.64 Mn 2+ 0.36 ) A(2) (Ce 0.37 La 0.17 Nd 0.06 Pr 0.03 Ca 0.35 0.02 ) M(1) (Fe 3+ 0.61 Al 0.39 ) M(2) Al 1.00 M(3) (Mn 2+ 0.64 Mn 3+ 0.33 Fe 3+ 0.02 Mg 0.01 ) T(1−3) Si 3.01 O 12 (OH), the end-member formula being CaCeFe 3+ AlMn 2+ (Si 2 O 7 )(SiO 4 )O(OH). Unit-cell parameters are a= 8.9033(3), b = 5.7066(2), c = 10.1363(3) Å, β = 114.222(2) • , V = 469.66(3) Å 3 , Z = 2. The crystal structure of ferriakasakaite-(Ce) was refined to a final R 1 = 0.0196 for 1960 unique reflections with F o > 4σ(F o ) and 124 refined parameters. Minerals 2019, 9, 353 2 of 15and 2 to the dollaseite group. Two additional minerals stand alone: zoisite, the unique example of epidote with orthorhombic symmetry, and åskagenite-(Nd), the unique example of epidote having a divalent anion dominant at the O(10) site. We herewith describe manganiakasakaite-(La) and ferriakasakaite-(Ce), two new minerals belonging to the allanite group. In this group, a trivalent cation, typically a REE, is dominant at the A(2) site, and a divalent cation is dominant at the M(3) site. According to the general guidelines for the nomenclature of epidotes [1], each distinct combination of dominant cations at the A(1) and M(3) sites deserves a proper root-name. In particular, the root-name "akasakaite" (after Masahide Akasaka, professor of mineralogy at the Shimane University) corresponds to the pair A(1) = Ca and M(3) = Mn 2+ [2]. Then, an adjectival prefix is appended to the root-name for the dominant cation at the M(1) (other than Al), and a Levinson suffix [3] is appended to the root-name for the dominant REE at the A(2) site. The names of the two new minerals are in keeping with the above guidelines, as they represent chemical variants of the mineral ferriakasakaite-(La), which was first described from Japan [2]. Both manganiakasakaite-(La) and ferriakasakaite-(Ce) were found in the Mn ore d...

show abstract

Section: Crystal-chemistry Of Manganiakasakaite-(la) and Ferriakasakamentioning

confidence: 96%

Section: Crystal-chemistry Of Manganiakasakaite-(la) and Ferriakasakamentioning

confidence: 96%

Manganiakasakaite-(La) and Ferriakasakaite-(Ce), Two New Epidote Supergroup Minerals from Piedmont, Italy

et al. 2019

View full text Add to dashboard Cite

show abstract

“…This structural arrangement gives rise to 9-coordinate A1 and 10-coordinate A2 sites. In epidote-group minerals (Mills et al, 2009) corresponding to the clinozoisite subgroup defined by Armbruster et al (2006), A1 and A2 are filled with Ca, and the octahedral M1, M2 and M3 sites are occupied by trivalent cations. Cations having large ionic radii, such as Sr and Ba, occupy A2, and those smaller than Ca, such as Mn 2+ , substitute for Ca at A1.…”

Section: Introductionmentioning

confidence: 99%

Ferriakasakaite-(La) and ferriandrosite-(La): new epidote-supergroup minerals from Ise, Mie Prefecture, Japan

et al. 2015

View full text Add to dashboard Cite

The new REE-rich, monoclinic, epidote-supergroup minerals ferriakasakaite-(La) and ferriandrosite-(La), found in tephroite Ô calcite veinlets cutting the stratiform ferromanganese deposit from the Shobu area, Ise City, Mie Prefecture, Japan, were studied using electron microprobe analysis and single-crystal X-ray diffraction methods. Ferriakasakaite-(La), ideally A1 Ca A2 La M1 Fe 3+M2 Al M3 Mn 2+ (SiO 4 )(Si 2 O 7 )O(OH) (Z = 2, space group P2 1 /m), has a new combination of dominant cations at A1(Ca) and M3(Mn 2+ ), which are the key sites to determine a root name for epidote-supergroup minerals. The unit-cell parameters are a = 8.8733 (2), b = 5.7415(1), c = 10.0805(3) Å , b = 113.845(2)º and V = 469.73(2) Å 3 . According to the structural refinement (R 1 = 3.13%), the determined structural formula is A1 (Ca 0.54 Mn 2+ 0.46 ) A 2 [(La 0.48 Ce 0.20 Pr 0.07 Nd 0.18 Gd 0.02 ) S 0.95 Ca 0.05 ] M 1 (Fe 3+ 0.42 V 3+ 0.34 Al 0.18 Ti 4+ 0.06 ) M 2 (Al 0.96 Fe 3+ 0.04 ) M 3 ( M n 2 + 0 . 5 0 F e 2 + 0 . 4 3 M g 0 . 0 7 ) ( S i O 4 ) ( S i 2 O 7 ) O ( O H ) . F e r r i a n d r o s i t e -( L a ) , i d e a l l y A1 Mn 2+A2 La M1 Fe 3+M2 Al M3 Mn 2+ (SiO 4 )(Si 2 O 7 )O(OH) (Z = 2, space group P2 1 /m), is the M1 Fe 3+ analogue of androsite. The unit-cell parameters are a = 8.8779(1), b = 5.73995(1), c = 10.0875(2) Å , b = 113.899(1)º and V = 469.97(2) Å 3 , and the structural formula is A1 (Mn 2+ 0.56 Ca 0.44 ) A2 [(La 0.49 Ce 0.20 Pr 0.08 Nd 0.19 Gd 0.02 ) S0.97 Ca 0.03 ] M1 (Fe 3+ 0.40 V 3+ 0.28 Al 0.20 Fe 2+ 0.05 Ti 4+ 0.07 ) M2 (Al 0.97 Fe 3+ 0.03 ) M3 (Mn 2+ 0.50 Fe 2+ 0.40 Mg 0.10 )(SiO 4 )(Si 2 O 7 )O(OH) (R 1 = 2.93%).The two new minerals, which are compositionally very similar overall, are distinguished by occupancy of A1, Ca vs. Mn 2+ . The structural properties of these minerals depend not only on the REE content at A2, but also on the Mn content at A1.

show abstract

“…A r t i c l e (OH)-Ca 2 Mn 3+ 3 Si 3 O 12 (OH) by Langer et al (2002) and Nagashima and Akasaka (2004), piemontites containing as much as 1.48 and 1.26 Mn 3+ apfu, respectively, were synthesized from the starting materials of Ca 2 Al 1.2 Mn 3+…”

Section: A D V a N C E P U B L I C A T I O Nmentioning

confidence: 99%

Crystal chemistry of Sr–rich piemontite from manganese ore deposit of the Tone mine, Nishisonogi Peninsula, Nagasaki, southwest Japan

Nagashima

Sano

Kochi

et al. 2020

Journal of Mineralogical and Petrological Sciences

View full text Add to dashboard Cite

The crystal chemistry of Sr-rich piemontite from a layered manganese ore deposit of the Tone mine, Nishisonogi Peninsula, Japan, was studied using methods of electron microprobe analysis, single crystal X-ray structural refinement, 57 Fe Mössbauer spectroscopy, and X-ray and Time-of-Flight neutron Rietveld analyses to elucidate the intracrystalline distributions of Sr, Mn, and Fe and the general and individual features on the structural changes with Sr contents in piemontite and epidotes. Piemontite in the most piemontite-dominant layer of an ore is [Ca 1.73(15) Sr 0.22(13) ] Σ1.95 [Al 1.99(9) Mn 3+ 0.68(8) Fe 3+ 0.37(8) Mg 0.01(0) ] Σ3.05 Si 2.99(1) O 12 (OH) (Z = 2) in the average chemical formula. A single crystal X-ray structural refinement (R 1 = 2.51% for 2417 unique reflections) resulted in the unit-cell parameters of a = 8.8942(1), b = 5.6540(1), c = 10.1928(2) Å, and β = 115.100(1)°; and the occupancies of Ca 0.711(3) Sr 0.289 , Al 0.898(4) (Mn + Fe) 0.102 , and (Mn + Fe) 0.949(4) Al 0.051 at the X A2, VI M1, and VI M3 sites, respectively. All Fe in a powdered piemontite sample was Fe 3+ as indicated by the two Mössbauer doublets (isomer shift = 0.351 and 0.367 mm/s and quadrupole splitting = 2.189 and 1.93 mm/s, respectively) assigned to Fe 3+ at the M3 site. The neutron Rietveld refinement of the powder sample (R wp = 2.11%; R e = 0.88%) resulted in the occupancies of M1 [Al 0.902(5) Mn 0.098 ] and M3 [Mn 0.534(5) Fe 0.267 Al 0.20 ], where M3 Al was fixed to 0.20Al obtained by X-ray Rietveld refinement (R wp = 2.95%; R e = 2.13%). By applying the oxidation state of Fe and the distributions of Al, Fe, and Mn in the M1 and M3 sites in the powder sample, the site occupancies in the piemontite single crystal are constructed as A2 [Ca 0.711(3) Sr 0.289 ], M1 [Al 0.898(4) Mn 3+ 0.102 ] and M3 [Mn 3+ 0.633 Fe 3+ 0.316 Al 0.051 ]. The A2-O7,-O2', and-O10 distances, 2.303(2), 2.562(1), and 2.592(2) Å, respectively, are longer than those of Ca-piemontites. The mean < M3-O> and < M1-O> distances, 2.050 and 1.923 Å, respectively, are close to the published data of Ca-piemontites and Sr-rich and-bearing piemontites with Mn 3+ + Fe 3+ contents in the M3 and M1 sites similar to those of the Tone piemontite.

show abstract

The crystal chemistry of Mn³⁺ in the clino- and orthozoisite structure types, Ca₂M₃ ³⁺[OH|O|SiO₄|Si₂O₇]: A structural and spectroscopic study of some natural piemontites and “thulites” and their synthetic equivalents

Cited by 29 publications

References 14 publications

Manganiakasakaite-(La) and Ferriakasakaite-(Ce), Two New Epidote Supergroup Minerals from Piedmont, Italy

Manganiakasakaite-(La) and Ferriakasakaite-(Ce), Two New Epidote Supergroup Minerals from Piedmont, Italy

Ferriakasakaite-(La) and ferriandrosite-(La): new epidote-supergroup minerals from Ise, Mie Prefecture, Japan

Crystal chemistry of Sr–rich piemontite from manganese ore deposit of the Tone mine, Nishisonogi Peninsula, Nagasaki, southwest Japan

Contact Info

Product

Resources

About

The crystal chemistry of Mn3+ in the clino- and orthozoisite structure types, Ca2M3 3+[OH|O|SiO4|Si2O7]: A structural and spectroscopic study of some natural piemontites and “thulites” and their synthetic equivalents

Cited by 29 publications

References 14 publications

Manganiakasakaite-(La) and Ferriakasakaite-(Ce), Two New Epidote Supergroup Minerals from Piedmont, Italy

Manganiakasakaite-(La) and Ferriakasakaite-(Ce), Two New Epidote Supergroup Minerals from Piedmont, Italy

Ferriakasakaite-(La) and ferriandrosite-(La): new epidote-supergroup minerals from Ise, Mie Prefecture, Japan

Crystal chemistry of Sr–rich piemontite from manganese ore deposit of the Tone mine, Nishisonogi Peninsula, Nagasaki, southwest Japan

Contact Info

Product

Resources

About

The crystal chemistry of Mn³⁺ in the clino- and orthozoisite structure types, Ca₂M₃ ³⁺[OH|O|SiO₄|Si₂O₇]: A structural and spectroscopic study of some natural piemontites and “thulites” and their synthetic equivalents