The western Rhodope massif contains a significant number of ‘battery grade’ Mn-oxide deposits which are best developed in the area near Kato Nevrokopi, Drama district, N. Greece. Economic Mn-oxide ore concentrations are confined to fault zones and related karsts in marbles. The mineralisation has formed by weathering of hydrothermal veins that were genetically related to Oligocene magmatism.

At Kato Nevrokopi, progressive and continuous weathering of primary, hydrothermal veins of rhodochrosite, mixed sulphide, quartz and ‘black calcite’ (calcite and todorokite) has resulted in the formation of the assemblage MnO-gel-(amorphous Mn-oxide)-todorokite-azurite-goethite-cerussite in the veins and the assemblage MnO-gel-nsutite-chalcophanite-birnessite-cryptomelane-pyrolusite and malachite and amorphous Fe-oxides in karstic cavities.

The f s2 and f O2 of the hydrothermal fluids increased with time. The breakdown of the hypogene Mn-carbonate was aided by the production of an acidic fluid due to the oxidation of sulphides. Precipitation of the supergene ores was caused by neutralisation of the fluids due to reaction with the host marble and to mixing of relatively reduced fluids with oxygenated surface water in a fluctuation water table regime. Zinc was also mobile during weathering and became concentrated in the intermediate Mn-oxides, effectively stabilising their structures. The mineral paragenesis records the progressive oxidation of the ore and the appearance of less hydrated Mn-oxides, low in alkalis and alkaline earths.

The narrow belt of granophyre lying to the west of Blaven in the Isle of Skye showed so admirably the effects of chilling that a series of specimens was collected by one of us (L.R.W.) and found to contain, in the chilled marginal rock, phenoerysts of tridymite, now inverted to quartz. In the Thulean Tertiary igneous province former tridymite is known from certain acid lavas, for example, the Tardree rhyolite (von Lasaulx, 1877) and certain Icelandic liparites (Hawkes, 1916), and from metamorphosed arkoses adjacent to basic igneous intrusions (Harker, 1908, 1932), but it has not previously been noted in the intrusive acid rocks. In addition to phenocrysts of tridymite inverted to quartz, there is present in the groundmass of the unchilled granophyre a second generation of inverted tridymite crystals, surrounded by a final stage of quartz and felspar which has crystallized with normal microgranitic textures. Some of the textural features resemble those of the normal Skye granophyres, while others resemble certain metamorphosed arkoses.

Pyrochlore-group minerals are common accessory rare-metal bearing minerals in the calcite and ankerite carbonatites of the Amba Dongar complex (India). Pyrochlore from the Amba Dongar carbonatites differs from that in other Indian complexes in Ta, Zr, Ti, rare earth element (REE) and Pb contents, but is similar with respect to Ca, Ba and Sr abundances. The evolution of pyrochlore composition was studied to understand the alteration processes and the formation of late-stage pyrochlores enriched in REE and Pb. The early magmatic pyrochlore are calcio- and niobium-dominant types and were replaced by secondary cation-deficient varieties as a consequence of the action of hydrothermal fluids and supergene weathering. These processes produce changes mainly at the A site, rarely at the B site, and the original F is replaced by OH– groups. Calcium and Na can be extracted from the structure at the alteration stage and charge balance is achieved by the introduction of REE, Th, U, Ba or Sr. At the latest supergene stages, marginal and fractured zones of pyrochlore grains are altered to Pb-rich, Si-rich and cation-deficient hydrated varieties. The magmatic pyrochlore was crystallised in a highly alkaline environment at a high activity of Ca and at temperatures near 600°C, the alteration of pyrochlore began in a hydrothermal environment at temperatures below 350°C. The major compositional changes that are associated with the alteration are summarised by the following reactions: Ca2+ + Nb5+→ REE3+ + Ti4+; Nb5+ + Fe3+ → Ti4+ + Zr4+; and 2Nb5+ + Ca2+ → Ti4+ + Si4+ + U4+.

The compositions of more than eighty synthetic members of the apatite group with the general formula A 10(XO4)6 Z 2 have been used as a basis for classifying the apatites into three groups. The ratios of the mean sizes of the ‘A’ ions to those of the ‘X’ ions for all these compositions lie between the limits of 1·89 and 4·43. A discontinuity occurs between ratios of 2·50 and 2·60 and probably another between 3·25 and 3·35, and these discontinuities provide a structural basis for the division into the three groups. The groups are named after well-known mineral species occurring in each group, i.e. the vanadinite-svabites with an A : X ratio less than 2·5, the apatite-mimetites between 2·60 and 3·25, and the pyromorphites with A : X greater than 3·25.

Kerimasite, ideally is a new calcium zirconium silicate-ferrite member of the garnet group from the extinct nephelinitic volcano Kerimasi and surrounding explosion craters in northern Tanzania. The mineral occurs as subhedral crystals up to 100 μm in size in calcite carbonatites, and as euhedral to subhedral crystals up to 180 μm in size in carbonatite eluvium. Kerimasite is light to dark-brown in colour and transparent with a vitreous lustre. No cleavage or parting was observed and the mineral is brittle. The calculated density is 4.105(1) g/cm3. The micro-indentation, VHN25, ranges from 1168 to 1288 kg/mm2. Kerimasite is isotropic with n = 1.945(5). The average chemical formula of the mineral derived from electron microprobe analyses (sample K 94-25) and calculated for O = 12 and all Fe as Fe2O3 is (Ca3.00Mn0.01Ce0.01Nd0.01)Σ3.03(Zr1.72Nb0.14Ti0.08Mg0.02Y0.02)Σ1.98(Ti0.09)Σ3.00O12. The largest Fe content determined in kerimasite is 21.6 wt.% Fe2O3 and this value corresponds to 1.66 a.p.f.u. in the tetrahedral site. Kerimasite is cubic, space group with a = 12.549(1) Å, V = 1976.2(4) Å3 and Z = 8. The five strongest powder-diffraction lines [d in Å, (I/I o), hkl] are: 4.441 (49) (220), 3.140 (91) (400), 2.808 (70) (420), 2.564 (93) (422) and 1.677 (100) (642). Single-crystal structure refinement revealed the typical structure of the garnet-group minerals. The name is given after the locality, Kerimasi volcano, Tanzania.

Zircon from 14 representative granite samples of the late-Variscan Cornubian Batholith in SW England was analysed for W, P, As, Nb, Ta, Si, Ti, Zr, Hf, Th, U, Y, La, Ce, Pr, Nd, Sm, Gd, Dy, Er, Yb, Al, Sc, Bi, Mn, Fe, Ca, Pb, Cu, S and F using electron probe microanalyses. Zircons fromthe biotite and tourmaline granites are poor in minor and trace elements, usually containing 1.0–1.5 wt.% HfO2, <0.5 wt.% UO2 and P2O5, <0.25 wt.% Y2O3, <0.2 wt.% Sc2O3 and Bi2O3and <0.1 wt.% ThO2. Zircon from topaz granites from the St. Austell Pluton, Meldon Aplite and Megiliggar Rocks are slightly enriched in Hf (up to 4 wt.% HfO2), U (1– 3.5 wt.% UO2) and Sc (0.5–1 wt.% Sc2O3). Scarce metamictizedzircon grains are somewhat enriched in Al, Ca, Fe and Mn. The decrease of the zircon Zr/Hf ratio, a reliable magma fractionation index, from 110–60 in the biotite granites to 30–10 in the most evolved topaz granites (Meldon Aplite and Megiliggar Rocks), supports a comagmatic originof the biotite and topaz granites via long-lasting fractionation of common peraluminous crustal magma. In comparison with other European rare-metal provinces, the overall contents of trace elements in Cornubian zircons are low and the Zr/Hf and U/Th ratios show lower degrees of fractionationof the parental melt.

The high-pressure behaviour (up to 30 kbar) of dehydrated analcime, Na[AlSi2O6), has been studied in detail using polarized microscopy and Raman micro-spectroscopy. Samples were compressed using a diamond anvil cell in a quasi-hydrostatic medium (glycerol or water-ice). Two transitions at 3.7 and 11 kbar were observed.

At the first transition, phase II is observed under cross polarized light as a contrasting black zone, moving from the edge to the centre of the sample. At this transition the strong Raman doublet at ∼480 and 500 cm−1 transforms discontinuously to a singlet, which is similar to that of quasi-cubic natural analcime. This transition, with an increase of effective symmetry, seems unusual on increasing pressure.

The analcime framework may be thought of as an array of four-, six-, or eight-membered interconnected rings. Phase transitions in the analcime group are considered in the literature in terms of deformations of the six-membered rings. However, the present work shows that these phase transitions should be associated with deformations of the four-membered rings (as the minimum size secondary building units) by rotation of rigid TO4 units. The strongest Raman band frequency is correlated with the mean T-O-T angle inside the four-membered ring: a rate of 4.5 cm−1/degree was found for analcimes and leucites. Using this correlation, one can estimate from Raman data the possible deformation of four-membered rings at the phase transitions.

Orbicules in diorite from the Grenville Front zone of eastern Labrador are defined by shell structures alternately enriched and depleted in biotite, epidote and magnetite. Hornblende occurs locally in orbicule cores and the matrix, but not in the shells. The shells enclose plagioclase-rich (An40–45), leucodioritic cores containing biotite, epidote, magnetite and/or hornblende-bearing mafic clots. The matrix of the orbicules is mineralogically-similar to the orbicule cores, but is mesocratic, and contains relatively sodic plagioclase and accessory quartz and K-feldspar. In places, hornblende contains quartz oikocrysts, implying the resorption of early-formed clinopyroxene, and is rimmed by biotite and epidote. The latter phases also occur as inclusions in quartz-free hornblende interpreted to have crystallized directly from the magma. Epidote has a pistacite content of 21 to 26 and occurs as (1) tiny, idiomorphic crystals (‘epidote I’) enclosed by plagioclase or hornblende, and (2) relatively large (to 1 mm) grains with vermicular textures (‘epidote II’), particularly where in mutual contact with biotite (or hornblende) and plagioclase. These microstructures suggest that epidote is a magmatic phase which formed by direct crystallization from the magma, and by reaction of previously-formed minerals with the magma.

The following approximate paragenetic sequence has been inferred for orbicule cores and the matrix: clinopyroxene (clinopyroxene resorbed [→ poikilitic hornblende]), epidote I, Ca-Na plagioclase, biotite, hornblende (biotite and/or hornblende ± plagioclase resorbed [→ epidote II]), quartz + K-feldspar. Biotite compositions became progressively more Fe-rich during crystallization (X Mg ⋍ 0.6 → 0.4), and the first-formed plagioclase (inclusions in quartz-free hornblende in orbicule cores) is more calcic (An51) than the last (matrix grains: An35).

The appearance of epidote early in the crystallization history of the diorite testifies to elevated P H2O and P Total (P T). The most aluminous hornblende indicates maximum P T of 5 to 6 kbar. Orbicule shell structures are interpreted to have crystallized from supercooled boundary layers enclosing water-saturated globules within the dioritic magma. Although sufficient to suppress the formation of hornblende in the shell structures, the extent of magma supercooling did not permit the development of comb layering in the orbicules. Supercooling is attributed to an influx into the magma of water from an unidentified source.

Analyses of tourmaline and coexisting muscovite in tourmaline-bearing rocks from SE Ireland indicate that the content of Si in tourmaline is not fixed but is dependent on bulk chemistry, varying inversely with Al. Zoning patterns within tourmaline reflect this and, despite theoretical objections, substitution of Si by Al in the tetrahedral site must occur in nature. Ti may also substitute for Si. Ca and Ti are generally involved in a coupled substitution. Estimates of the degree of alkali-defect and proton-loss substitution in SE Ireland tourmalines indicate that the former process is at least as important as the latter and that bulk chemistry is important in determining which substitution occurs. The general importance of alkali-defect substitution and Al⇌Si suggests that the most useful way to treat microprobe data for schorl-dravite tourmalines is to assume the presence of 3B and 4(OH) and calculate on the basis of 24.5 oxygen atoms.

Nanodiamonds can be synthesized hydrothermally in the laboratory by using a C-O-H fluid in the graphite stability field, in which the graphite/nanodiamond transition depends on the crystal size as a function of temperature. In nature, the hydrothermal circulation of seawater in serpentinitesplays an important role in the carbon speciation in the oceanic crust and exposed mantle, in which hydrocarbons (mainly CH4) of abiogenic origin (via Fischer-Tropsch-type reaction) and occasionally graphite particles are detected. Can nanodiamonds nucleate and grow in serpentinite-hostedhydrothermal systems? To answer this question, a theoretical modelling study which compares the physico-chemical conditions in hydrothermal synthesis with those observed in modern and fossil serpentinite-hosted hydrothermal systems is proposed. Nanodiamonds are predicted to precipitate froma C-O-H fluid, consisting of CH4-CO2-H2O at 350 – 400°C and P<0.2 GPa near the FMQ buffer (Fayalite-Magnetite-Quartz), which are conditions compatible with those existing in serpentinite-hosted hydrothermal systems. In these environments,carbon-supersaturated fluids can be derived from water consumption (serpentine formation) under low water/rock ratios, which may promote the growth of nanodiamonds. This theoretical approach sheds light on the intriguing problem of carbon speciation in abyssal-type hydrothermal systems, suggestingthat serpentinites may host nanodiamond deposits, even though none have been found yet.

Work which has been in progress during the last few years on the low-grade regionally metamorphosed rocks of western Otago, New Zealand, has shown that members of the stilpnomelane group, hydrous iron- (or manganese-) rich silicates, are exceedingly widespread in rocks with the most varied mineral assemblages. In many cases the mineral in question is in sufficient quantity to rank as an essential constituent and may even be the most abundant one present. Hence in view of the importance of this mineral in the rocks of this region, it was considered that exact analytical data were necessary, and preliminary work in this connexion was carried out by Dr. F. J. Turner and the writer in 1934, but at that time, owing to the difficulties of separation, the pure minerals could not be obtained for analysis.

A rapid fusion technique is described in which the Li2B4O7 bead is polished, not crushed. The reliability of the technique is illustrated by a series of precision tests and analyses of standard rocks, using a 2:1 Li2B4O7 : rock-powder dilution. It is also pointed out that such a low-dilution fusion method may be used for Na2O and trace element analyses with only a small loss in sensitivity relative to the unfused-powder method. Any fusion method has the advantages of greatly reducing absorption effects and eliminating particle-size effects.

An investigation of the system Cu-Fe-O has established the existence of a phase near 3Cu2O.Fe3O4 and the non-existence of Cu2O.Fe2O3 a in the system over the range of oxygen pressures investigated.

The X-ray diffraction patterns obtained from four samples of natural delafossite have been found to be similar to that obtained from a synthetic sample of the 3Cu2O.Fe3O4 phase. It has also been shown that, when heated under equilibrium conditions in the thermobalance in air, a sample of natural delafossite and the synthetic 3Cu2O.Fe3O4 behaved similarly.

The new mineral species oxycalcioroméite, Ca2Sb5+ 2O6O, has been discovered at the Buca della Vena mine, Stazzema, Apuan Alps, Tuscany, Italy. It occurs as euhedral octahedra, up to 0.1 mm in size, embedded in dolostone lenses in thebaryte + pyrite + iron oxides ore. Associated minerals are calcite, cinnabar, derbylite, dolomite, hematite, 'mica', pyrite, sphalerite and 'tourmaline'. Oxycalcioroméite is reddish-brown in colour and transparent. It is isotropic, with ncalc = 1.950.

Electron microprobeanalysis gave (wt.%; n = 6) Sb2O5 63.73, TiO2 3.53, SnO2 0.28, Sb2O3 10.93, V2O3 0.68, Al2O3 0.28, PbO 0.68, FeO 5.52, MnO 0.13, CaO 13.68, Na2O 0.83, F 1.20, O =F – 0.51, total 100.96. No H2O, above the detection limit, was indicated by either infrared or micro-Raman spectroscopies. The empirical formula, based on 2 cations at the B site, is (Ca1.073Fe2+ 0.338Sb3+ 0.330Na0.118Pb0.013Mn0.008)Σ=1.880(Sb5+ 1.734Ti0.194V0.040Al0.024Sn0.008)Σ=2.000(O6.682F0.278)Σ6.960.The crystal structure study gives a cubic unit cell, space group Fd m, with a 10.3042(7) Å, V 1094.06(13) Å3, Z = 8. The five strongest X-ray powder diffraction lines are [d(Å)I(visually estimated)(hkl)]:3.105(m)(311); 2.977(s)(222); 2.576(m)(400); 1.824(ms)(440); and 1.556(ms)(622). The crystal structure of oxycalcioroméite has been solved by X-ray single-crystal study on the basis of 114 observed reflections, with a final R 1 = 0.0114. It agrees with the general featuresof the members of the pyrochlore supergroup.

Several silicate-minerals, such as ardennite – Mn2+ 4MgAl5[Si5(As5+,V5+)O22](OH)6, Z = 2, tiragalloite – Mn2+ 4[Si3As5+O12(OH)], Z = 4 and medaite – Mn2+ 6[Si5(V5+,As5+)O18(OH)], Z = 4 possess (V5+,As5+,P5+)O4 tetrahedra. Using electron-microprobe analysis (EMPA) and single-crystal X-ray diffraction methods, the crystal chemistry of ardennite from Salam-Château, Belgium and the Vernetto mine, Italy, tiragalloite from the Gambatesa mine, Italy, and medaite from the Molinello mine, Italy and the Fianel mine, Switzerland, were studied. Structure refinements converged to R 1 values of 2.10–5.67%. According to chemical analysis, the Σ(As+V+P) content increases with decreasing Si content. Thus, Si replaces pentavalent cations in tetrahedral coordination. The (As5+,V5+,P5+,Si4+)O4 tetrahedra are categorized by their connections to SiO4 tetrahedra. The (As5+,V5+,P5+,Si4+)O4 tetrahedron of ardennite is isolated, and those of tiragalloite and medaite terminate a tetrahedral chain. The <T–O> of the isolated (As5+,V5+,P5+,Si4+)O4 tetrahedron shows a positive correlation with the mean ionic radius. For (As5+,V5+,P5+,Si4+)O4 tetrahedra with one T–O–T link, <T–O> and mean ionic radius are also correlated. In addition, the longest bridging T–O bond occurs between (As,V,P,Si)O4 and the adjacent SiO4 tetrahedron. The bridging O atom is over-bonded to satisfy the charge requirement of Σ(As+V+Si).

The Ceylonese gemstone sinhalite, AlMgBO4, is isomorphous with olivine and chrysoberyl. Aluminium and magnesium are oetahedrally coordinated and boron occupies slightly distorted tetrahedra. Because of size differences, the smaller Al ion can be assigned to the inversion symmetry sites, with Mg in mirror plane positions. Least-squares refinement based on single crystal X-ray data gave an accurate set of atomic coordinates with mean interatomic distances: Al-O 1·90, Mg-O 2·10, B-O 1·49 Å.

Argentotetrahedrite-(Zn), Ag6(Cu4Zn2)Sb4S13, has been approved as a new mineral species by the International Mineralogical Association Commission on New Minerals, Nomenclature and Classification (IMA-CNMNC) using samples from Kremnica, Slovak Republic (hereafter KR), and Lengenbach, Switzerland (LE). Additionally, it was also identified at the small deposit of Zvěstov (Stříbrnice), Czech Republic (ZV). At the Slovak locality, it occurs as anhedral grains up to 0.1 mm in size, steel-grey in colour, with a metallic lustre, in association with ‘argentotennantite-(Fe)’ and tiny chalcopyrite grains in quartz gangue. At Lengenbach, it was found as domains of tristetrahedral crystal of tetrahedrite-(Zn), up to 1 mm in size, associated with dolomite. At Zvěstov, it occurs as irregular aggregates, up to 0.2 mm in size, partly rimmed by kenoargentotetrahedrite-(Fe). Argentotetrahedrite-(Zn) is isotropic, grey in colour, with blue-greenish tints. Reflectance data for COM wavelengths in air (KR sample) are [λ (nm), R (%)]: 470, 30.1; 546, 29.8; 589, 29.8; and 650, 28.3. Chemical formulae of the samples studied, recalculated on the basis of ΣMe = 16 apfu (atoms per formula unit), are: (Ag3.27Cu2.69)Σ5.96[Cu4.00(Zn1.69Fe0.23Cu0.05Cd0.02Hg0.01)Σ2.00](Sb3.86As0.17)Σ4.03S12.73 (KR), (Ag3.17Cu2.79)Σ5.96[Cu4.00(Zn1.55Cd0.23Fe0.16Cu0.05Hg0.01)Σ2.00](Sb3.71As0.32)Σ4.03S12.77 (LE) and (Ag3.27Cu2.67)Σ5.94[Cu4.00(Zn1.39Fe0.50Cu0.07Cd0.03Hg0.01)Σ2.00](Sb4.03As0.04)Σ4.07S13.08 (ZV). Argentotetrahedrite-(Zn) is cubic, I$\overline 4$3m, with a = 10.5505(10) Å, V = 1174.4(3) Å3 and Z = 2 (KR); a = 10.5155(13) Å and V = 1162.8(4) Å3 (LE); and a = 10.5663(12) Å and V = 1179.7 Å3 (ZV). The crystal structure of argentotetrahedrite-(Zn) has been refined by single-crystal X-ray diffraction data to a final R1 = 0.035 on the basis of 327 unique reflections with Fo > 4σ(Fo) and 22 refined parameters (sample KR). Argentotetrahedrite-(Zn) is isotypic with other members of the tetrahedrite group. The structural relationship between argentotetrahedrite-(Zn) and other members of the freibergite series are discussed and previous findings of this species are briefly reviewed.

An unusual form of sector zoning has been recorded in some Lewisian zircons. The sectors lie in a plane cut perpendicular to the c-axis and are observed as variations in the intensity of cathodoluminescence, and in trace-element concentrations. Sectors radiating from the centre of growth out to the {100} faces exhibit low-intensity cathodoluminescence and are enriched in Y and depleted in Hf and Zr. Those radiating to the {110} faces are brightly luminescent, slightly enriched in Hf and depleted in Y. X-ray diffraction data, and comparison with previous studies of zircons, suggest that the sectors vary slightly in crystallographic orientation, such that the boundaries between sectors form discontinuities in the structure.

Thermal aspects of the conflicting hypotheses that the acid magmas of the British Tertiary Igneous Province were generated by either fractional crystallization of basic magmas or partial fusion of country rocks around basic intrusions are investigated by combining petrological and experimental data. Sparse large xenoliths (up to 12 m2 outcrops) of Lewisian gneiss occur in the ferrodiorite member of the Marscoite Suite in the Western Redhills Eocene intrusive complex of Skye. Most of the blocks are of granodioritic-tonalitic gneiss which is very similar to the grey gneisses of the northern and southern regions of the mainland Lewisian. One is a two-pyroxene basic granulite, closely resembling in petrography and composition the granulite-facies basic gneisses of the central region of the Scottish mainland Lewisian. During Tertiary thermal metamorphism the xenoliths recrystallized patchily to pyroxene hornfelses and up to 50% of melting occurred in any parts of blocks that were rich in alkali feldspar and quartz. Microprobe analyses of intergrown Ca-rich and Ca-poor pyroxenes in a hornfelsed ultramafic mica pyroxenite lens within a leucogneiss block give a calculated temperature of 950 °C for the Tertiary metamorphism. Melting experiments at 1 kb P H2O were carried out on leucocratic and mesocratic Lewisian gneisses (from the xenoliths), Torridonian arkose and shale. Extensive melting of the leucogneiss and arkose, to peraluminous liquids, occurs within a few degrees above their solidus (715 °C). The silicate liquidus of the leucogneiss is at 930 °C. Microprobe analyses of the glass products of melting experiments (mostly of leucogneiss) show that liquid composition trends during progressive melting are consistent with theoretical equilibria in the synthetic system Ab-Or-An-Qz-H2O. Partial fusion in the Skye Lewisian gneiss xenoliths took place at a water vapour pressure of a few hundred bars, probably under water-undersaturated conditions.

The crystal structure of H3O+-exchanged pharmacosiderite (pharmacosiderite is KFe4(AsO4)3(OH)4·nH2O, sensu stricto) has been determined by single-crystal X-ray diffraction and refined to R 1 = 0.0418. H3O+-exchanged pharmacosiderite, (H3O+)Fe4(AsO4)3(OH)4·4.5H2O, is cubic, space group P m, with a = 7.982(9) Å, V = 508.5(9) Å3 and Z = 1. The structure broadly conforms to that of the general pharmacosiderite structure type, with the hydronium ion generated by partial protonation of a site corresponding to a molecule of water of crystallization and its symmetry-related equivalents. In addition, the structure of a “pharmacosiderite” from Cornwall, United Kingdom, in which no alkali metals could be detected, has been re-evaluated and found to be consistent with that of the H3O+- exchanged structure. Its composition is (H3O+)Fe4(AsO4)3(OH)4·4H2O, with the partially occupied water found for the exchanged structure at (½, ½, ½) being absent in this case.