Sperlingite, (H2O)K(Mn2+Fe3+)(Al2Ti)(PO4)4[O(OH)][(H2O)9(OH)]⋅4H2O, is a new monoclinic member of the paulkerrite group, from the Hagendorf-Süd pegmatite, Oberpfalz, Bavaria, Germany. It was found in corrosion pits of altered zwieselite, in association with columbite, hopeite, leucophosphite, mitridatite, scholzite, orange–brown zincoberaunite sprays and tiny green crystals of zincolibethenite. Sperlingite forms colourless prisms with pyramidal terminations, which are predominantly only 5 to 20 μm in size, rarely to 60 μm and frequently are multiply intergrown and are overgrown with smaller crystals. The crystals are flattened on {010} and slightly elongated along [100] with forms {010}, {001} and {111}. Twinning occurs by rotation about c. The calculated density is 2.40 g⋅cm–3. Optically, sperlingite crystals are biaxial (+), α = 1.600(est), β = 1.615(5), γ = 1.635(5) (white light) and 2V (calc.) = 82.7°. The optical orientation is X = b, Y = c and Z = a. Neither dispersion nor pleochroism were observed. The empirical formula from electron microprobe analyses and structure refinement is A1[(H2O)0.96K0.04]Σ1.00 A2(K0.52□0.48)Σ1.00 M1(Mn2+0.60Mg0.33Zn0.29Fe3+0.77)Σ1.99 M2+M3(Al1.05Ti4+1.33Fe3+0.62)Σ3.00(PO4)4 X[F0.19(OH)0.94O0.87]Σ2.00[(H2O)9.23(OH)0.77]Σ10.00⋅3.96H2O. Sperlingite has monoclinic symmetry with space group P21/c and unit-cell parameters a = 10.428(2) Å, b = 20.281(4) Å, c = 12.223(2) Å, β = 90.10(3)°, V = 2585.0(8) Å3 and Z = 4. The crystal structure was refined using synchrotron single-crystal data to wRobs = 0.058 for 5608 reflections with I > 3σ(I). Sperlingite is the first paulkerrite-group mineral to have co-dominant divalent and trivalent cations at the M1 sites; All other reported members have Mn2+ or Mg dominant at M1. Local charge balance for Fe3+ at M1 is achieved by H2O → OH– at H2O coordinated to M1.

Hydroxylbenyacarite, (H2O)2Mn2(Ti2Fe)(PO4)4[O(OH)](H2O)10⋅4H2O, is a new paulkerrite-group mineral from the El Criollo mine, Cordoba Province, Argentina (IMA2023–079). It was found in specimens of altered triplite, in association with bermanite, phosphosiderite, quartz, strengite and manganese oxides.

Hydroxylbenyacarite occurs as light greenish-yellow rhombic tablets with dimensions of typically 20 to 50 μm, occasionally to 400 μm. The crystals are flattened on {010}, slightly elongated on [001] and bounded by the {111} and {010} forms. The calculated density is 2.32 g cm–3. Optically, hydroxylbenyacarite crystals are biaxial (+), with α = 1.608(3), β = 1.624(3), γ = 1.642(3) (measured in white light) and 2V(meas.) = 88(2)°. The calculated 2V is 87.5°. The empirical formula is Ca0.06 A[K0.46(H2O)0.88□0.66]Σ2.00 M1(Mn1.52Mg0.02Fe2+0.35□0.11)Σ2.00 M2+M3(Fe3+1.21Al0.02Ti1.77)Σ3.00(PO4)4 X[F0.16(OH)0.70O1.14]Σ2.00(H2O)10⋅3.77H2O.

The average crystal structure for hydroxylbenyacarite has space group Pbca and unit cell parameters a = 10.5500(3) Å, b =20.7248(5) Å, c = 12.5023(3) Å, V = 2733.58(12) Å3 and Z = 4. It was refined using single-crystal data to wRobs = 0.074 for 2611 reflections with I > 3σ(I). The crystal structure contains corner-connected linear trimers of Ti-centred octahedra that share corners with PO4 tetrahedra to form 10-member rings parallel to (010). K+ cations and water molecules are located in interstitial sites within the rings. Additional corner-sharing of the PO4 tetrahedra with MnO2(H2O)4 octahedra occurs along [010] to complete the 3D framework structure. A new eight-coordinated interstitial site, previously unreported for paulkerrite-group minerals, is occupied by Ca2+ cations. Weak diffuse diffraction spots in reconstructed precession images for hydroxylbenyacarite violate the a and b glide plane extinctions for Pbca and are consistent with local, unit-cell-scale regions of monoclinic, P21/c structure, in which ordering of the interstitial K+ and Ca2+ cations occurs.

Rewitzerite, K(H2O)Mn2(Al2Ti)(PO4)4[O(OH)](H2O)10⋅4H2O, is a new monoclinic member of the paulkerrite group, from the Hagendorf-Süd pegmatite, Oberpfalz, Bavaria, Germany. It was found in specimens of altered zwieselite, in association with rockbridgeite. Rewitzerite forms clusters of colourless elongated hexagonal-shaped prisms, up to 0.1 mm long. The crystals are flattened on {010} and elongated along [100], with forms {010}, {001}, {111} and {$\bar{1}$11}. The calculated density is 2.33 g⋅cm–3. Optically, rewitzerite crystals are biaxial (+), with α = 1.585(2), β = 1.586(2), γ = 1.615(2) (measured in white light) and 2V(meas) = 25(2)°. The empirical formula from electron microprobe analyses and structure refinement is A1[K0.77(H2O)0.23]A2[H2O] M1(Mn2+0.82Mg0.64Fe3+0.43□0.11)Σ2.00 M2+M3(Al1.51Ti4+1.06Fe3+0.43)Σ3.00(PO4)4 X[(OH)0.54F0.42O1.04]Σ2.00(H2O)10⋅4H2O, where □ = vacancy.

Rewitzerite has monoclinic symmetry with space group P21/c and unit-cell parameters a = 10.444(2) Å, b = 20.445(2) Å, c = 12.2690(10)Å, β = 90.17(3)°, V = 2619.8(6) Å3 and Z = 4. The crystal structure was refined using synchrotron single-crystal data to wRobs = 0.068 for 5894 reflections with I > 3σ(I). The crystal structure has the same topology as that for orthorhombic paulkerrite-group minerals but differs primarily in having an ordering of K+ and H2O molecules in different A sites, whereas they are disordered at a single A site in the orthorhombic members of the group.

Whiteite-(MnMnMn), Mn2+Mn2+Mn2+2Al2(PO4)4(OH)2⋅8H2O, is a new whiteite-subgroup member of the jahnsite group from the Foote Lithium Company mine, Kings Mountain district, Cleveland County, North Carolina, USA. It was found in small vugs of partially oxidised pegmatite minerals on the East dump of the mine, in association with eosphorite, hureaulite, fairfieldite, mangangordonite, whiteite-(CaMnMn) and jasonsmithite. It occurs as sugary aggregates of blade-like crystals up to 0.1 mm long and as epitaxial overgrowths on whiteite-(CaMnMn). The crystals are colourless to very pale brown, with a vitreous lustre and a white streak. The blades are flattened on {001} and elongated along [010], with poor cleavage on {001}. The calculated density is 2.82 g⋅cm–3. Optically it is biaxial (–) with α = 1.599(2), β = 1.605(2), γ = 1.609(2) (white light); 2V (calc.) = 78.2°, having no observable dispersion or pleochroism, and with orientation X = b. Electron microprobe analyses and structure refinement gave the empirical formula (Mn2+0.59Ca0.38Na0.03)Σ1.00Mn1.00(Mn2+1.04Fe3+0.58Fe2+0.23Zn0.16Mg0.08)Σ2.09Al2.04(PO4)3.89(OH)3.18(H2O)7.26. Whiteite-(MnMnMn) is monoclinic, P2/a, a = 15.024(3) Å, b = 6.9470(14) Å, c = 9.999(2) Å, β = 110.71(3)°, V = 976.2(4) Å3 and Z = 2. The crystal structure was refined using synchrotron single-crystal data to wRobs = 0.057 for 2014 reflections with I > 3σ(I). Site occupancy refinements confirm the ordering of dominant Mn in the X, M1 and M2 sites of the general jahnsite-group formula XM1(M2)2(M3)2(H2O)8(OH)2(PO4)4. A review of published crystallochemical data for jahnsite-group minerals shows a consistent chemical pressure effect in these minerals, manifested as a contraction of the unit-cell parameter, a, as the mean size of the X and M1 site cations increases. This is analogous to negative thermal expansion, but with increasing cation size, rather than heating, inducing octahedral rotations that result in an anisotropic contraction of the unit cell.

Aldermanite from Tom's quarry in the Kapunda–Angaston area of the Mount Lofty Ranges, South Australia has been characterised by electron microprobe analyses and single-crystal structure analysis. The empirical formula is Na0.72K0.13Ca0.06Mg1.15Al2.92(PO4)2.05[(OH)2.92F2.96]Σ5.88⋅8.91H2O, based on 23 anions. Analysis of a specimen from the type locality, the nearby Klemm's quarry, Moculta, gave a similar formula, Na0.59K0.06Ca0.36Mg0.92Al3.16(PO4)1.97[(OH)4.08F2.70]Σ6.78⋅8.36H2O. Na and F were not analysed in the original description of the mineral. The ideal end-member formula is [Mg(H2O)6][Na(H2O)2Al3(PO4)2(OH)6]⋅H2O, compared to the original formula of Mg5Al12(PO4)8(OH)22⋅nH2O with n ≈ 32. Aldermanite is monoclinic, P21/c with a = 13.524(3), b = 9.958(2), c = 7.013(1) Å and β = 97.40(3)°. The crystal structure of aldermanite is built from sawtooth layers of cis- and trans-corner-connected, Al-centred octahedra, decorated with corner-connected PO4 tetrahedra to give (100) layers of composition Al3(PO4)2(OH,F)6. Interlayer Mg(H2O)6 octahedra and H2O molecules hold the layers together through H bonding. The corner-connected octahedra form 6-membered rings that are centred by 8-coordinated Na and have a topology identical to a 3-octahedra-wide {110} slice of the pyrochlore structure. This pyrochlore element contains intersecting kagomé nets of Al atoms, parallel to (111) and (11$\bar{1}$) of cubic pyrochlore. Minerals of the walentaite group, as well as zirconolite-3O polytypes have the same type of intersecting kagomé nets of small cations.

Galeaclolusite, [Al6(AsO4)3(OH)9(H2O)4]⋅8H2O, is a new secondary hydrated aluminium arsenate mineral from Cap Garonne, Var, France. It forms crusts and spheroids of white fibres up to 50 μm long by 0.4 μm wide and only 0.1 μm thick. The fibres are elongated along [001] and flattened on (100). The calculated density is 2.27 g⋅cm–3. Optically, galeaclolusite is biaxial with α = 1.550(5), β not determined, γ = 1.570(5) (white light) and partial orientation: Z = c (fibre axis). Electron microprobe analyses coupled with crystal structure refinement results gives an empirical formula based on 33 O atoms of Al5.72Si0.08As2.88O33H34.12. Galeaclolusite is orthorhombic, Pnma, with a = 19.855(4), b = 17.6933(11), c = 7.7799(5) Å, V = 2733.0(7) Å3 and Z = 4. The crystal structure of galeaclolusite was established from its close relationship to bulachite and refined using synchrotron powder X-ray diffraction data. It is based on heteropolyhedral layers, parallel to (100), of composition Al6(AsO4)3(OH)9(H2O)4 and with H-bonded H2O between the layers. The layers contain [001] spiral chains of edge-shared octahedra, decorated with corner-connected AsO4 tetrahedra, that are the same as in the mineral liskeardite.

Kagomé nets of corner-connected triangles of atoms occur in diverse minerals, from the {111} anion arrays in perovskite-group minerals to natural metallic alloys like auricupride, AuCu3, to the cation layers in atacamite-group minerals. We review here two- and three-dimensional kagomé networks in minerals where the kagomé node atoms are octahedrally coordinated in hexagonal tungsten bronze (HTB) arrays. Octahedral tilting, coupled with capping of the apical anions of the triangular groupings of octahedra in the HTB layers, gives rise to several important mineral groups, including pyrochlores, alunite-supergroup minerals, zirconolite and weberite polytypes and spinel-group minerals, as a function of the magnitude and type of the octahedral tilting.

Bulachite specimens from Cap Garonne, France, comprise two intimately mixed hydrated aluminium arsenate minerals with the same Al:As ratio of 2:1 and with different water contents. The crystal structures of both minerals have been solved using data from low-dose electron diffraction tomography combined with synchrotron powder X-ray diffraction. One of the minerals has the same powder X-ray diffraction pattern (PXRD) as for published bulachite. It has orthorhombic symmetry, space group Pnma with unit-cell parameters a = 15.3994(3), b = 17.6598(3), c = 7.8083(1) Å and Z = 4, with the formula [Al6(AsO4)3(OH)9(H2O)4]⋅2H2O. The second mineral is a higher hydrate with composition [Al6(AsO4)3(OH)9(H2O)4]⋅8H2O. It has the same Pnma space group and unit-cell parameters a = 19.855(4), b = 17.6933(11) and c = 7.7799(5) Å i.e. almost the same b and c parameters but a much larger a parameter. The structures are based on polyhedral layers, parallel to (100), of composition [Al6(AsO4)3(OH)9(H2O)4] and with H-bonded H2O between the layers. The layers contain [001] spiral chains of edge-shared octahedra, decorated with corner connected AsO4 tetrahedra that are the same as in the mineral liskeardite. The spiral chains are joined together by octahedral edge-sharing to form layers parallel to (100). Synchrotron PXRD patterns collected at different temperatures during heating of the specimen show that the higher-hydrate mineral starts transforming to bulachite when heated to 50°C, and the transformation is complete between 75 and 100°C.

Jahnsite-(CaMnZn), CaMn2+Zn2Fe3+2(PO4)4(OH)2⋅8H2O, is a new jahnsite-group mineral associated with alteration of phosphophyllite at the Hagendorf-Süd pegmatite, Bavaria. It forms as thin yellow crusts and brown epitactic growths on altered phosphophyllite, both of which comprise lath-like crystals in orthogonal orientation, up to 100 μm long. The crystals contain intergrowths of jahnsite-(CaMnZn) and jahnsite-(CaMnMn) on a scale of ~50 μm. The calculated density is 2.87 g cm−3 based on the empirical formula. Optically it is biaxial (–), with α = 1.675(2), β = 1.686(2) and γ = 1.691(2) (white light). The calculated 2V is 68°. Dispersion could not be observed, and the optical orientation is Z = b. Pleochroism was imperceptible. Electron microprobe analyses together with results from Mössbauer spectroscopy gives the formula (Ca0.59Mn0.24)Σ0.83Mn(Zn0.74Mn2+0.48Mg0.18Fe2+0.13Fe3+0.47)Σ2Fe3+2(P0.995O4)4(OH)2.03(H2O)7.97.

Jahnsite-(CaMnZn) is monoclinic, P2/a, with a = 15.059(1), b = 7.1885(6), c = 10.031(2) Å, β = 111.239(8)° and V = 1012.1(2) Å3. The recent International Mineralogical Association approved nomenclature system for jahnsite-group minerals was applied to establish jahnsite-(CaMnZn) from the empirical formula. The structural flexibility of jahnsite-group minerals to accommodate cations of quite different sizes in the X and M1 sites is discussed in terms of rotations about the 7 Å axis of two independent octahedra centred at the M3 sites.

The general structural formula for the walentaite group is [((A1yA1’1–y), A2)(H2O)n][Bx(As2)2–x(As3)M1(M2)2(TO4)2(O,OH)7], based on heteropolyhedral layers of configuration [M1(M2)2(TO4)2(O,OH)6], with surface-coordinated species at the B, As2 and As3 sites, and with interlayer hydrated cation groups centred at the A sites. The group is divided into walentaite and halilsarpite subgroups based on T = P5+ and As5+, respectively. Alcantarillaite, (IMA2019-072), [Fe3+0.5□0.5(H2O)4][CaAs3+2(Fe3+2.5W6+0.5)(AsO4)2O7], is a new member of the walentaite group from the Alcantarilla wolframite mine, Belalcázar, Córdoba, Andalusia, Spain. It occurs most commonly as lemon-yellow fillings together with massive scorodite in fissures and cracks in quartz adjacent to löllingite. It is also found as tiny yellow rosettes lining vugs and as spheroids of ultrathin blades. It is associated with scorodite, pharmacosiderite, ferberite and schneiderhöhnite. Optically it is biaxial (–), with α = 1.703(calc), β = 1.800(5), γ = 1.850(5) and 2V = 68(1)° (white light). Dispersion is r > v, moderate. The optical orientation is X = a, Y = c and Z = b. The calculated density is 3.06 g cm–3. Electron microprobe analyses together with crystal structure refinement results gives the empirical formula [Fe3+0.52□0.48(H2O)4][(Ca0.44K0.11Na0.05Fe2+0.24□0.42)As3+1.83][Fe3+2.54Al0.03W6+0.43)((As0.65P0.35)O4)2O5.86(OH)1.14]. Alcantarillaite is orthorhombic, with an average structure described in Imma, and with a = 24.038(8) Å, b = 7.444(3) Å, c = 10.387(3) Å, V = 1858.6(11) Å3 and Z = 4. The structure (wRobs = 0.078 for 651 reflections to a resolution of 0.91 Å) differs most significantly from other walentaite-group members in having an interlayer A2 site occupied. Square-pyramidal polyhedra centred at the A2 sites form edge-shared dimers, (Fe3+)2O4(H2O)4. The dimers share vertices with TO4 anions in the layers on either side to form 8-sided channels along [010] occupied by H2O molecules.

Pseudorutile, , has recently been revalidated as a mineral species, and the neotype locality is now South Neptune Island, South Australia. Powder X-ray diffraction data are given on a hexagonal primitive unit cell with a = 2.8667(5) and c = 4.5985(9) Å. Leucoxene, arizonite and proarizonite are considered to be mixtures. Kleberite is considered to be a hydroxylian pseudorutile, .

Schmidite, Zn(Fe3+0.5Mn2+0.5)2ZnFe3+(PO4)3(OH)3(H2O)8 and wildenauerite, Zn(Fe3+0.5Mn2+0.5)2Mn2+Fe3+(PO4)3(OH)3(H2O)8 are two new oxidised schoonerite-group minerals from the Hagendorf-Süd pegmatite, Hagendorf, Oberpfalz, Bavaria, Germany. Schmidite occurs as radiating sprays of orange–brown to copper-red laths on and near to altered phosphophyllite in a corroded triphylite nodule, whereas wildenauerite forms dense compacts of red laths, terminating Zn-bearing rockbridgeite. The minerals are biaxial (+) with α = 1.642(2), β = 1.680(1), γ = 1.735(2) and 2Vmeas = 81.4(8)° for schmidite, and with α = 1.659(3), β = 1.687(3), γ = 1.742(3) and 2Vmeas = 73(1)° for wildenauerite. Electron microprobe analyses, with H2O from thermal analysis and FeO/Fe2O3 from Mössbauer spectroscopy, gave FeO 0.4, MgO 0.3, Fe2O3 23.5, MnO 9.0, ZnO 15.5, P2O5 27.6, H2O 23.3, total 99.6 wt.% for schmidite, and FeO 0.7, MgO 0.3, Fe2O3 25.2, MnO 10.7, ZnO 11.5, P2O5 27.2, H2O 24.5, total 100.1 wt.% for wildenauerite. The empirical formulae, scaled to 3 P and with OH– adjusted for charge balance are Zn1.47Mn2+0.98Mg0.05Fe2+0.04Fe3+2.27(PO4)3(OH)2.89(H2O)8.54 for schmidite and Zn1.11Mn2+1.18Mg0.05Fe2+0.08Fe3+2.47(PO4)3(OH)3.25(H2O)9.03 for wildenauerite. The two minerals have orthorhombic symmetry, space group Pmab and Z = 4. The unit-cell parameters from refinement of powder X-ray diffraction data are a = 11.059(1), b = 25.452(1) and c = 6.427(1) Å for schmidite, and a = 11.082(1), b = 25.498(2) and c = 6.436(1) Å for wildenauerite. The crystal structures of schmidite and wildenauerite differ from that of schoonerite in having minor partitioning of Zn from the [5]Zn site to an adjacent vacant tetrahedral site [4]Zn, separated by ~1.0 Å from [5]Zn. The two minerals are distinguished by the cation occupancies in the octahedral M1 to M3 sites. Schmidite has M1 = M2 = (Fe3+0.5Mn2+0.5) and M3 = Zn and wildenauerite has M1 = M2 = (Fe3+0.5Mn2+0.5) and M3 = Mn2+.

The crystal structures have been refined for the first time for the strunzite-group minerals ferristrunzite and ferrostrunzite. Structure refinements are also presented for strunzite from three different localities. A common feature of all refined structural models is the presence of zeolitic water in the interlayer region, displaced by 0.4–0.5 Å from an inversion centre at (½ 0 ½). The refined occupancy of the site ranged from 44% to 100% in the samples studied. H-bonding associated with the zeolitic water causes large displacements, up to 0.7 Å, of neighbouring coordinated water molecules, relative to the structure with no zeolitic water. A new formula is proposed for strunzite-group minerals with divalent interlayer cations as M2+ Fe23+(PO4)2(OH)2·(6.5–x)H2O where M = Mn, Fe or Zn, and 0 < x < 0.5 accounts for varying degrees of dehydration. For ferristrunzite and other potential strunzite-group members with trivalent cations in the interlayer octahedron, the formula is M3+ Fe23+ (PO4)2(OH)3·(5.5–x)H2O.

Bettertonite, [Al6(AsO4)3(OH)9(H2O)5]•11H2O and penberthycroftite, [Al6(AsO4)3(OH)9(H2O)5].8H2O, two new minerals from the Penberthy Croft mine, Cornwall, have flexible layer structures based on corner-connected heteropolyhedral columns. Their response to dehydration on heating was studied using in situ synchrotron powder X-ray diffraction at temperatures in the range -53 to 157°C. The bettertonite sample transforms to penberthycroftite in a narrow temperature range of 67 to 97°C with a large (8%) contraction of the layer separation and a 6 Å sliding of adjacent layers relative to each other. Above 100°C a second phase transition occurs to a DL (displaced layer) phase, involving another 8% inter-layer contraction combined with a rotation of the columns. On heating the penberthycroftite sample the phase transition to the DL phase occurs at a lower temperature of ∼80°C. The DL phase is stable to a temperature of ∼120°C. At higher temperatures, increased rotation of the columns is accompanied by a progressive amorphization of the sample. Bettertonite, penberthycroftite and the DL phase exhibit negative thermal expansion (NTE) along all three axes with large NTE coefficients, of the order of-100 x 10 -6 °C-1.

In North America, terrestrial records of biodiversity and climate change that span Marine Oxygen Isotope Stage (MIS) 5 are rare. Where found, they provide insight into how the coupling of the ocean–atmosphere system is manifested in biotic and environmental records and how the biosphere responds to climate change. In 2010–2011, construction at Ziegler Reservoir near Snowmass Village, Colorado (USA) revealed a nearly continuous, lacustrine/wetland sedimentary sequence that preserved evidence of past plant communities between ~140 and 55 ka, including all of MIS 5. At an elevation of 2705 m, the Ziegler Reservoir fossil site also contained thousands of well-preserved bones of late Pleistocene megafauna, including mastodons, mammoths, ground sloths, horses, camels, deer, bison, black bear, coyotes, and bighorn sheep. In addition, the site contained more than 26,000 bones from at least 30 species of small animals including salamanders, otters, muskrats, minks, rabbits, beavers, frogs, lizards, snakes, fish, and birds. The combination of macro- and micro-vertebrates, invertebrates, terrestrial and aquatic plant macrofossils, a detailed pollen record, and a robust, directly dated stratigraphic framework shows that high-elevation ecosystems in the Rocky Mountains of Colorado are climatically sensitive and varied dramatically throughout MIS 5.

The literature on the λ Boo stars has grown to become somewhat heterogenous, as different authors have applied different criteria across the UV, optical, and infrared regions to determine the membership status of λ Boo candidates. We aim to clear up the confusion by consulting the literature on 212 objects that have been considered as λ Boo candidates, and subsequently evaluating the evidence in favour of their admission to the λ Boo class. We obtained new spectra of ~ 90 of these candidates and classified them on the MK system to aid in the membership evaluations. The re-evaluation of the 212 objects resulted in 64 members and 103 non-members of the λ Boo class, with a further 45 stars for which membership status is unclear. We suggest observations for each of the stars in the latter category that will allow them to be confidently included or rejected from the class. Our reclassification facilitates homogenous analysis on group members, and represents the largest collection of confirmed λ Boo stars known.

Doping of calcium tantalate, Ca2Ta2O7, with small amounts (<5 mole%) of Ca2Nb2O7 results in a 50% increase in the dielectric constant, K (from 23 to 35 at 1 MHz), and a zero temperature coefficient of K is achieved at about 18 mole% of Ca2Nb2O7. This opens up the possibility of applications in microwave communication devices. Crystallographic information needed to understand the structure/property relationships in this system is lacking. We have prepared samples of calcium tantalates doped with different elements including Nb, Sm, Ti, Nd and Zr, and have structurally characterised them using X-ray diffraction and transmission electron microscopy. The diffraction patterns of the tantalates all display strong subcell reflections characteristic of the trigonal weberite structure together with complex distributions of superlattice reflections that depend on the nature and concentration of the dopant and on the reaction temperature. The diffraction patterns were indexed using related trigonal or pseudo-trigonal unit cells with a ~7.3 Å, c ~ n × 6 Å. Polytypes with n = 3, 4, 5, 6 and 7 were prepared as single crystals by the flux method. Single crystal X-ray data was used in conjunction with high resolution electron microscope images to solve the structures. Details are given for a 6M polytype (M=monoclinic). A characteristic structural feature of the polytypes is a fluorite-type cation array which is periodically twinned on (111)f to give mixed cubic-hexagonal stacking of the cation layers. The structure relations with the pyrochlore and weberite structures are discussed.