M?ssbauer spectroscopy of Pb-bearing minerals from the jarosite group

The minerals of the jarosite group, including the jarosite-beudantite-segnitite and jarosite-beaverite-osarizawaite isomorphic series, were studied with M?ssbauer spectroscopy. All the samples were collected from the oxidation zones of the South Urals sulfide deposits. In contrast to the jarosite containing one Fe³⁺ doublet in the M?ssbauer spectrum, the Pb-bearing members of the jarosite group—beudantite and beaverite—have two doublets in their spectra. Fe³⁺ is distributed at two sites with similar isomer shifts and different quadrupole splitting. The quantitative ratio of those doublets in the structure is roughly equal. The M?ssbauer spectra of the intermediate jarosite-beudantite and beaverite-osarizawaite members are superpositions of the jarosite and beudantite spectrum types with a prevalent jarosite doublet and larger quadrupole splitting. An admixture of antimony increases the Fe³⁺ content in the doublet with smaller quadrupole splitting. The unequal Fe³⁺ distribution in those two sites may be related to the ordering of cations in octahedrons. The appearance of two different Fe³⁺ sites probably resulted from the local coordinating role of Pb rather than from isomorphic replacement in anion groups.     

Fluorine and chlorine in mantle minerals and the halogen budget of the Earth’s mantle

The fluorine (F) and chlorine (Cl) contents of arc magmas have been used to track the composition of subducted components, and the F and Cl contents of MORB have been used to estimate the halogen content of depleted MORB mantle (DMM). Yet, the F and Cl budget of the Earth’s upper mantle and their distribution in peridotite minerals remain to be constrained. Here, we developed a method to measure low concentrations of halogens (≥0.4 µg/g F and ≥0.3 µg/g Cl) in minerals by secondary ion mass spectroscopy. We present a comprehensive study of F and Cl in co-existing natural olivine, orthopyroxene, clinopyroxene, and amphibole in seventeen samples from different tectonic settings. We support the hypothesis that F in olivine is controlled by melt polymerization, and that F in pyroxene is controlled by their Na and Al contents, with some effect of melt polymerization. We infer that Cl compatibility ranks as follows: amphibole > clinopyroxene > olivine ~ orthopyroxene, while F compatibility ranks as follows: amphibole > clinopyroxene > orthopyroxene ≥ olivine, depending on the tectonic context. In addition, we show that F, Cl, Be and B are correlated in pyroxenes and amphibole. F and Cl variations suggest that interaction with slab melts and fluids can significantly alter the halogen content of mantle minerals. In particular, F in oceanic peridotites is mostly hosted in pyroxenes, and proportionally increases in olivine in subduction-related peridotites. The mantle wedge is likely enriched in F compared to un-metasomatized mantle, while Cl is always low (<1 µg/g) in all tectonic settings studied here. The bulk anhydrous peridotite mantle contains 1.4–31 µg/g F and 0.14–0.38 µg/g Cl. The bulk F content of oceanic-like peridotites (2.1–9.4 µg/g) is lower than DMM estimates, consistent with F-rich eclogite in the source of MORB. Furthermore, the bulk Cl budget of all anhydrous peridotites studied here is lower than previous DMM estimates. Our results indicate that nearly all MORB may be somewhat contaminated by seawater-rich material and that the Cl content of DMM could be overestimated. With this study, we demonstrate that the halogen contents of natural peridotite minerals are a unique tool to understand the cycling of halogens, from ridge settings to subduction zones.     

Minerals in nature and “on Paper”: History of the commissions on new minerals in Russia and IMA and principles of classification and nomenclature of minerals

This paper reviews the history of the foundation of the Commission on New Minerals in Russia (1956) and the same Commission of the International Mineral Association (IMA). The terms mineral species, subspecies, and variety are considered. The nomenclature of mineral groups of lovozerite, eudialyte, and apatite is given as examples of using a root name and its suffixes.     

Newly formed minerals of the Fe–P–S system in Kolyma fulgurite

Newly obtained data from microscopic, geochemical, and thermomagnetic studies of the large Kolyma fulgurite are presented here: the fulgurite was formed in the Holocene as a result of lightning affected black shale alluvium. The composition is very close to that of glass formed from a melt. The glass has elevated concentrations of Y, Zr, Nb, and REEs. The newly formed mineral phases have been identified: those are Al–Si glass, α-cristobalite, moissanite, native iron with a phosphorus admixture, nickel-less shreibersite (?), troilite, and possibly cohenite. The formation of these minerals is related to the melt fractionation and the effects of element concentration and segregation of ore components under conditions of the rock melting caused by the effect of high-energy plasma (lightning strike).     

The qualitative zoning record of minerals. A method for determining the duration of metamorphic events?

Summary The efficacy of ion exchange in petrological systems, for example the Fe-Mg exchange between garnet and biotite, is a function of grainsize, temperature, rates of temperature change and diffusion parameters. The combination of these variables determines the final zoning profile of minerals. Therefore, zoning profiles may be used to derive one of these variables if the others are known. For example, a mineral grain that experienced a short thermal event may still preserve a zoning profile characteristic of the heating path. In contrast, if that grain experienced a long thermal event it may develop a zoning profile typical of the cooling path. Conversely, for the same temperature-time cycle, large grains may not completely equilibrate at the metamorphic peak, and in smaller grains any previous record may have been erased. This is commonly observed in natural rocks where different grains within one thin section preserve often qualitatively different zoning profiles. Thus, a critical grainsize,l _crit, may exist that separates grains with qualitatively different zoning profiles so that grains of sizel > l _crit still retain zoning information about the heating path and grains of sizel <l _crit contain only information about the cooling path. If the critical grainsize can be measured and an independent estimate for the peak metamorphic temperature exists, the duration of the thermal event may, in principle, be estimated.The applicability of this method to natural garnets is hampered by a range of uncertainties. However, a parameterisation of the critical grain size may be used to illustrate the relative importance of grain size, temperature and event duration to the equilibration of minerals. In this paper, the critical grainsize is parameterized for various temperature-time cycles and its dependence on diffusion parameters is discussed. It is shown that, for Barrovian conditions,l _crit between 0.1 and 1 mm separates garnets retaining prograde information from garnets retaining cooling path information. For illustration, we compare the results with the critical grainsize of garnets from two metamorphic terranes, the Prydz Bay region (Antarctica) and the Koralm complex (Eastern Alps). Despite the large range of uncertainties attached to the method, it is shown that the critical grainsize of garnets in both terranes is consistent with a very short duration of the last thermal event that affected the two regions.

---

Die qualitative Form von Zonierungsprofilen in Mineralen. Information über die Dauer metamorpher Ereignisse?

Zusammenfassung Zonierungsprofile von Paragenesen im Ionenaustausch, zum Beispiel das Fe-Mg Austauschsgleichgewicht zwischen Granat und Biotit, sind eine Funktion von (i) Korngröße, (ii) Temperatur, (iii) Kühl- und Heizgeschwindigkeit sowie (iv) den Diffusionskonstanen. Es sollte daher möglich sein, Zonierungsprofile dazu zu verwenden, einen dieser Parameter zu bestimmen, wenn die anderen bekannt sind. Zonierungsprofile von Kristallen die ein kurzes thermisches Ereignis erfahren haben, mögen daher prograde Information beinhalten, wogegen derselbe Kristall ein retrogrades Profil aufweisen mag, wenn er einem langlebigen thermischen Ereignis unterlag (prograd und retrograd ist hier als: bei ansteigender Temperatur und bei abfallender Temperatur definiert). In Kristallen die dem gleichen Temperatur-Zeitpfad unterworfen waren, könnten kleine Körner nur die Kühlgeschichte dokumentieren, wogegen große noch Zonierungsinformation vom Heizpfad aufweisen. In natürlichen Gesteinen wird das oft dadurch beobachtet, daß verschiedene Körner auseinem Dünnschliff qualitativ verschiedene Zonierungsprofile aufweisen. Es ist daher möglich eine kritische Korngöße,l _crit, zu definieren, die Korngrößen mit qualitativ verschiedenen Zonierungsprofilen voneinander trennt. Körner mit einem Durchmesserl > l _crit haben, zumindest teilweise, noch prograde Profile, wogegen Körner mitl <l _crit nur retrograde Information dokumentieren. Wenn man diese kritische Korngröße messen kann, sollte sie dazu benutzt werden können, etwas über die Dauer des thermischen Ereignisses auszusagen.Die Anwendbarkeit dieser Methode ist durch eine Reihe von Fehlern limitiert. Nichtsdestotrotz, ist eine Parameterisierung der kritischen Korngröße nützlich um die relative Wichtigkeit von Korngröße, Temperatur und Zeit, für die Entwicklung von Zonierungsprofilen, zu illustrieren. Unser Modell kann dazu benutzt werden, um die Größenordnung von Granaten abzuschätzen, die noch prograde Information dokumentieren können. Die Abhängigkeit der kritischen Korngröße von Diffusionsparametern und der Form des Temperatur-Zeit Pfades wird ebenfalls diskutiert. Es wird gezeigt, daß für Metamorphose in der mittleren Grünschiefer und Amphibolit fazies,l _crit zwischen 0.1 and 1 mm prograd zonierte von retrograd zonierten Granaten trennt. Um das Modell zu illustrieren, werden die Ergebnisse auf die Prydz Bay Region (Antarktis) und den Koralm Komplex (Ostalpen) angewendet. Trotz der großen Fehlergrenzen der Methode glauben wir zeigen zu können, daß die kritische Korngröße beider Terrains andeutet, daß das letzte thermische Ereignis in beiden Gebieten kurzlebig war.

---

---

With 5 Figures     

Adsorption of radioelements on mixtures of minerals — experimental study

An experimental study has been undertaken concerning the adsorption of radioelements on mixtures of minerals. The question is whether the adsorption of trace elements by rocks and soils can be easily predicted from the properties of the constituent minerals. The goal of these experiments was the comparison between the measurements of distribution coefficients of some radioelements for pure minerals and for binary mixtures according to the Doehlert’s uniform shell designs and to test an additive law of combination of Kd. The results showed that when one of the constituents acts as a dilutant in the mixture, i.e. it presents a very low adsorption capacity with respect to some trace element, then the relations of additivity of Kd are fulfilled. Otherwise, these relations are not satisfied and this is probably caused, in the present cases, by interactions from solubilized species.     

First report of platinum-group minerals from a hornblende gabbro dyke in the vicinity of the Southeast Extension Zone of the Voisey’s Bay Ni-Cu-Co deposit, Labrador

Summary This study reports the first documented occurrence of platinum group-minerals (PGM) in the vicinity of the Voisey’s Bay magmatic sulfide ore deposit. The PGM are present in a sulfide poor, hornblende gabbro dyke in the Southeast Extension Zone of the massive sulfide Ovoid deposit. The dyke has somewhat elevated concentrations of platinum-group elements (PGE) and gold (up to 1.95 g/t Pt, 1.41 g/t Pd, and 6.59 g/t Au), as well as Cu, Pb, Ag, Sn, Te, Bi and Sb. The PGM formed by magmatic processes and were little disturbed by subsequent infiltration of an externally-supplied hydrothermal fluid. To date, no similar PGM occurrences have been discovered in the Ovoid deposit itself. Whole rock REE patterns indicate that the dyke is geochemically related to the main conduit troctolites, which carry the bulk of the massive sulfide mineralization at Voisey’s Bay. The PGE mineralization is Pt- and Pd-rich, where the Pt and Pd occur predominantly as discrete PGM with minor Pd in solid solution in galena (average=1.8 ppm) and pentlandite (average=2 ppm). The discrete PGM are predominantly hosted by disseminated base-metal sulfides (bornite, chalcopyrite, and galena) (56 vol%) and are associated with other precious metal minerals (13 vol%) with only ∼3 vol% of the PGM hosted by silicate minerals. In whole rock samples, the PPGE (Pt, Pd, and Rh) correlate with abundances of chalcopyrite, bornite, galena, and other precious metal minerals (PMM), whereas the IPGE (Ir, Ru, and Rh) correlate with pyrrhotite and pentlandite. There are no correlations of the PGE with chlorine. Lead isotope compositions of galena associated with the PGE mineralization in the Southeast Extension Zone are broadly similar to those for galena in the Ovoid. The lead isotope compositions are much different from those in the Voisey’s Bay Syenite, which is a potential external hydrothermal fluid source. The observed Cu-rich, Pb-rich sulfide compositions and associated Pt-Pd-Au-Ag-Sn-Te-Bi-Sb assemblage in the dyke can be produced magmatically as late ISS differentiates (e.g., Prichard et al., 2004). Melting temperatures of the PGM are also consistent with a magmatic origin. Following crystallization of PGM from magmatic sulfide, an external REE-enriched hydrothermal fluid was introduced to the system, producing secondary amphibole and locally remobilizing the Pb and Sn from the sulfides hosting the PGM. Author’s address: M. A. E. Huminicki, Department of Earth Sciences, Memorial University of Newfoundland, St. John’s, NL, Canada A1B 3X5     

Evolution of borate minerals from contact metamorphic to hydrothermal stages: Ludwigite-group minerals and szaibélyite from the Vysoká – Zlatno skarn,Slovakia

Mineralogy and Petrology - Borate minerals of the ludwigite group (LGM) and szaibélyite in association with hydroxylclinohumite, clinochlore, a serpentine mineral, magnesian magnetite, spinel,...     

Significance of graphite inclusion occurrence in the minerals of the San Miguel skarn for the Palaeoproterozoic basement of Tandilia Belt (Argentina) and for the Río de la Plata Craton

Graphite in Archaean-Palaeoproterozoic rocks has been a subject of interest since it could represent an evidence of early life on Earth. In the Palaeoproterozoic basement of the Tandilia Belt, graphite was found both in fluid inclusions (FI) hosted in the San Miguel skarn calc-silicate minerals, and as solid inclusions in calcite crystals from the protolithic marble (a¹³C enriched carbonate from the “Lomagundi-Jatuli event”). FI microthermometry and oxygen stable isotope ratios indicated the skarn minerals formation within the range of 630–650 °C (at ∼5 kbars) and ∼642–654 °C, respectively. Also, the characterisation of the metasomatic fluid (of a low salinity <7 wt% NaCl eq. NaClH₂O/NaClKClH₂O aqueous system) pointed out that the zonal crystallisation pattern shown by the skarn minerals (wollastonite-vesuvianite, grossular-diopside-calcite and diopside-calcite zones in the exoskarn, and grossular-diopside and diopside-calcic plagioclase zones in the endoskarn) responds to the increase of the involved cation activity gradients (Ca²⁺-Si⁴⁺-Mg²⁺-Fe^2+/3+-Al³⁺) and not to significant changes in the temperature or concentration of CO₂ in the system. Variation in the crystallinity degree of the graphite hosted in the skarn minerals and in marble calcite, shown by Raman spectroscopy, would indicate that the graphite could have been formed from the ripening of organic matter present in the sedimentary rocks during the metamorphic-metasomatic event (Transamazonian Orogeny). In this sense, the increase of the organic carbon productivity in the oceans during the Palaeoproterozoic, represented by the “Lomagundi-Jatuli event”, would support this graphite origin and also the possible existence of a marine sedimentary basin in the previous stages of the Río de la Plata amalgamation (Siderian-Rhyacian), in the San Miguel area of the Tandilia Belt.     

Accessory minerals of the Cínovec (Zinnwald) granite cupola, Czech Republic: indicators of petrogenetic evolution

Summary A fully cored drillhole was drilled to 1596m by the Czech Geological Survey in 1961–1963 in the central part of the Cínovec (Zinnwald) granite cupola. Two types of granite were intersected: zinnwaldite granite (ZG), observed down to a depth of 730m, and protolithionite granite (PG), occurring to the end of the hole. The core was used to study the distribution and chemistry of: zircon, thorite, xenotime, monazite, bastnäsite, synchysite, REE oxyfluorides and hydroxyfluorides. Zircon occurs throughout the drillcore; it is strongly hydrated and fluorinated with about 18.5wt.% H₂O content in the apical part of the cupola. Its F-content reaches 2.41wt.%. Within the PG, the F concentration in zircon is low. Zircon is poor in Th and U and its HfO₂ contents vary from 1.01 to 5.24wt.%. Thorite is common in the PG, becoming rare in the ZG. It is strongly hydrated (up to 14wt.% H₂O) and fluorinated (up to 2.04wt.% F). Extensive solid solution between ThSiO₄ and YPO₄ was observed. Xenotime is strongly hydrated (up to 16wt.% H₂O), but its F content is low (<0.31wt.%). Two types of monazite were identified: Th-rich (up to 9.3wt.% ThO₂) in the ZG, and Th-poor (<2.5wt.% ThO₂) in the PG. Monazite remained stable during the hydration and fluorination process. Its REE chondrite-normalized distribution patterns show negative anomalies for La and Nd and a pronounced negative anomaly for Eu. Chemical compositions of several REE oxyfluorides and hydroxyfluorides were studied. REE fluorocarbonates are represented by bastnäsite and synchysite. Bastnäsite is abundant in the ZG. Its chondrite-normalized REE patterns are characterized by an important negative Eu anomaly and downward kinks at La and Nd. Synchysite-(Ce) and synchysite-(Y) are particularly well developed in the deeper parts of the cupola, and exhibit REE distribution patterns characterized by a weak negative Eu anomaly (synchysite-(Ce)), or a weak positive Eu anomaly (synchysite-(Y)).The distribution of accessory minerals reveals five major evolution stages: (1) Early magmatic crystallization of albite and orthoclase. (2) A late magmatic stage comprising protolithionite, quartz, accessory zircon, thorite, xenotime and monazite. (3) Interaction of this magmatic association with a fluid phase rich in F, CO₂ and H₂O, leading to the transformation protolithionite zinnwaldite and to the remobilisation of Nb, Ta, Ti, W, Sn. Accessory minerals formed during stage (2) were hydrated and fluorinated, except monazite. (4) The transfer of volatiles into the apical part of the cupola followed by the opening of the magmatic system generated microgranites and hydrolysis-type reactions leading to the appearance of REE oxyfluorides and hydroxyfluorides. (5) A late CO₂- and F-rich fluid phase was responsible for the deposition of REE fluorocarbonates. Monazite and xenotime became unstable in the apical part of the cupola. An influx of fluids with high Ca-activity occurred late during stage (5) and led to the formation of synchysite, and finally to the extensive precipitation of fluorite.     

Alteration of platinum-group minerals and dispersion of platinum-group elements during progressive weathering of the Aguablanca Ni–Cu deposit, SW Spain

The distribution, mineralogy and mobility of the platinum-group elements (PGE) in the surface environment are poorly understood. This study of the lower, less altered and upper, more altered gossan, overlying the Aguablanca Ni–Cu-(PGE) magmatic deposit (Spain), has shown that the platinum-group minerals (PGM) are progressively oxidised and dispersed into iron oxides that form the gossan. A combination of the characterization of PGE in host PGM, using a scanning electron microscope, and measurement of PGE at lower concentrations in host iron oxides, using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), has for the first time allowed the total distribution of the PGE within a gossan to be documented. This study has revealed a complete in situ alteration and dispersion sequence of the PGM including (1) breakdown of both the more stable Pt-arsenides, Pt/Pd-tellurides and the less stable bismuthotellurides, (2) formation of partially oxidised PGM, (3) development of a wide range of oxidised Pt- and Pd-bearing phases, (4) subsequent formation of Fe–PGE-oxides and PGE-hydroxides, (5) incorporation of PGE into ferruginous supergene products and lastly (6) concentration of PGE at the edges of veins and iron oxides. Dispersion of Pd is greater than for the other PGE with Pd being widely distributed throughout the iron oxides. This oxidising environment produced PGE-oxides rather than PGE-alloys, also commonly found in the surface environment, especially in placers. These results provide critical evidence for the stages of mineralogical change from PGE host mineralogy in magmatic ores to surface weathering producing PGE-oxides.     

Zincobotryogen and zincocopiapite–two new varieties of sulfate minerals

Two new varieties of sulfate minerals, zincobotryogen and zincocopiapite, belonging to the botryogen group and the copiapite group, respectively, were found in the oxidation zone of a lead-zinc deposit, situated on the northern border of the extremely arid Tsadam basin. – Authors.     

Thermally induced alterations of minerals during measurements of the temperature dependence of magnetic susceptibility: a case study from the hydrothermally altered Soultz-sous-Forêts granite,France

Identification of magnetic minerals using the temperature dependence of magnetic susceptibility in low field (κ–T) combined with optical microscopy, microprobe, X-ray diffraction, and chemical analysis provided new constraints on the alteration of Fe-bearing minerals of the magnetite-bearing Soultz-sous-Forêts granite from the EPS-1 borehole (upper Rhine Graben, France). While relatively fresh granite shows largely reversible κ–T curves typical of magnetite, the altered granite revealed a wide variety of irreversible heating and cooling curves, which allowed an assignment to different alteration stages under specific geochemical conditions. Though paramagnetic minerals like Fe-bearing carbonates, pyrite, or antiferromagnetic hematite could not be detected according to their Curie or Neél temperature, they were identified due to reactions to new ferrimagnetic phases during the heating/cooling experiments at specific temperatures. Mineral reactions were proved by measurements of the single mineral phases hematite, Fe-carbonates, and illite. Our mineralogical results combined with the thermomagnetic measurements imply that first faulting of the granite occurred already during cooling of the magma, which caused a first magnetite oxidation event. During uplift of the granitic body and exposure to a paleo-erosion surface, strongly acidic fluids, emerged from pyrite oxidation, caused a decomposition of Fe-bearing minerals like martite (hematite derived from magnetite oxidation) and Fe-carbonates and an ongoing transformation of magnetite to martite. Subsequently, precipitation of fine-grained hematite was restricted only to the upper part of the pluton. In the deeper part of the borehole, pyrite was preserved from oxidation. In an active fault, zone martite was reduced back to magnetite, which can be explained with the occurrence of organic matter transported by fluids.     

Geological significance of nickeliferous minerals in the Fule Pb–Zn deposit,Yunnan Province,China

The Fule Pb–Zn deposit is located in the Sichuan–Yunnan–Guizhou Province, and it is an important and giant low temperature metallogenic domain in China. In our research area, the Pb–Zn deposits are mainly hosted in the Permian Yangxin Formation and are composed of dolostone and limestone. The distance between the ore bodies and the Permian Emeishan basalt ranged from 50 to 160 m. In this study, the nickel rich minerals, including vaesite, polydymite and millerite, were reported for the first time in the Fule deposit. These minerals occurred as xenomorphic mineral aggregate and were sporadically distributed in the sphalerite–galena–calcite vein, which is the main ore type in the deposit. Our study indicated that the paragenetic sequence of minerals in the Fule deposit is the following order: polydymite?→?vaesite?→?millerite?→?sphalerite?→?galena?→?tetrahedrite (tennantite). The geological occurrence characteristics of those nickeliferous minerals suggested that the Permian Emeishan basalt is a possible barrier layer of Pb–Zn ore-forming fluid, and it is an important source for the Ni and part of the Cu in the deposit. The Sichuan–Yunnan–Guizhou Pb–Zn mineralization province is a world-class production base of Pb and Zn, in which the Permian Emeishan basalt and Pb–Zn deposits have uniformly spatial distribution, but the relationship of mineralization between them is still under debate. This report provides new evidence for understanding the relationship between Pb–Zn mineralization and Permian Emeishan basalt in the Sichuan–Yunnan–Guizhou Pb–Zn mineralization province.     

Optical absorption investigation of Cr3+ ion-bearing minerals in the temperature range 77–797 K

The effect of raising temperature on spin-allowed dd-transitions of octahedral Cr³⁺ was studied for various point symmetries of the Cr³⁺-bearing structural sites, i.e. 3 m and 3 with inversion center in spinel and garnets, respectively, or 32, 3, 2 and 1, lacking the inversion centre, in beryl, corundum, diopside and topaz, respectively. For this purpose, crystals of Cr³⁺-bearing spinel, pyrope, andradite, grossular, uvarovite, emerald, ruby, diopside and topaz were analyzed by microprobe, oriented, and measured in polarized radiation (except for the cubic minerals) in the spectral range 30 000 to 11 100 cm^-1 and at temperatures between 77 and 797 K. The evaluation of the intensities, half widths, and energy positions of bands due to Cr³⁺-transitions derived from ⁴ A _2g ⁴ T _2g (F) and ⁴ T _1g (F) as well as of Dq- and B-values derived, had the following results:In all cases, red shift of the above bands and, hence, independent on the site symmetry of Cr³⁺, decreases in the Dq-values were obtained. The dependcies of Dq on T are nearly linear above room temperature and amount between -1.6% in topaz and -5.1% in pyrope in the temperature range studied. From this, values for the local thermal expansion of the Cr³⁺-centered octahedra, _loc, were derived on the basis of the R _M-0 ^-5 -proportionality of 10Dq. Such values are consistently higher than those obtained from X-ray refinements, a method averaging r_m-o for all the respective octahedral positions.