The triplite–triploidite supergroup: structural modulation in wagnerite, discreditation of magniotriplite, and the new mineral hydroxylwagnerite

Electron-microprobe analysis, single-crystal X-ray diffraction with an area detector, and high-resolution transmission electron microscopy show that minerals related to wagnerite, triplite and triploidite, which are monoclinic Mg, Fe and Mn phosphates with the formula Me2+ 2PO4(F,OH), constitute a modulated series based on the average triplite structure. Modulation occurs along b and may be commensurate with (2b periodicity) or incommensurate but generally close to integer values (∼3b, ∼5b, ∼7b, ∼9b), i.e. close to polytypic behaviour. As a result, the Mg- and F-dominant minerals magniotriplite and wagnerite can no longer be considered polymorphs of Mg2PO4F, i.e., there is no basis for recognizing them as distinct species. Given that wagnerite has priority (1821 vs. 1951), the name magniotriplite should be discarded in favour of wagnerite. Hydroxylwagnerite, end-member Mg2PO4OH, occurs in pyrope megablasts along with talc, clinochlore, kyanite, rutile and secondary apatite in two samples from lenses of pyrope–kyanite–phengite–quartz-schist within metagranite in the coesite-bearing ultrahigh-pressure metamorphic unit of the Dora-Maira Massif, western Alps, Vallone di Gilba, Val Varaita, Piemonte, Italy. Electron microprobe analyses of holotype hydroxylwagnerite and of the crystal with the lowest F content gave in wt%: P2O5 44.14, 43.99; SiO2 0.28, 0.02; SO3 –, 0.01; TiO2 0.20, 0.16; Al2O3 0.06, 0.03; MgO 48.82, 49.12; FeO 0.33, 0.48; MnO 0.01, 0.02; CaO 0.12, 0.10; Na2O 0.01, –; F 5.58, 4.67; H2O (calc) 2.94, 3.36; –O = F 2.35, 1.97; Sum 100.14, 99.98, corresponding to (Mg1.954Fe0.007Ca0.003Ti0.004Al0.002Na0.001)Σ=1.971(P1.003Si0.008)Σ=1.011O4(OH0.526F0.474)Σ=1 and (Mg1.971Fe0.011Ca0.003Ti0.003Al0.001)Σ=1.989(P1.002Si0.001)Σ=1.003O4(OH0.603F0.397)Σ=1, respectively. Due to the paucity of material, H2O could not be measured, so OH was calculated from the deficit in F assuming stoichiometry, i.e., by assuming F + OH = 1 per formula unit. Holotype hydroxylwagnerite is optically biaxial (+), α 1.584(1), β 1.586(1), γ 1.587(1) (589 nm); 2V Z(meas.) = 43(2)°; orientation Y = b. Single-crystal X-ray diffraction gives monoclinic symmetry, space group P21/c, a = 9.646(3) Å, b = 12.7314(16) Å, c = 11.980(4) Å, β = 108.38(4) , V = 1396.2(8) Å3, Z = 16, i.e., hydroxylwagnerite is the OH-dominant analogue of wagnerite [β-Mg2PO4(OH)] and a high-pressure polymorph of althausite, holtedahlite, and α- and ε-Mg2PO4(OH). We suggest that the group of minerals related to wagnerite, triplite and triploidite constitutes a triplite–triploidite super-group that can be divided into F-dominant phosphates (triplite group), OH-dominant phosphates (triploidite group), O-dominant phosphates (staněkite group) and an OH-dominant arsenate (sarkinite). The distinction among the three groups and a potential fourth group is based only on chemical features, i.e., occupancy of anion or cation sites. The structures of these minerals are all based on the average triplite structure, with a modulation controlled by the ratio of Mg, Fe2+, Fe3+ and Mn2+ ionic radii to (O,OH,F) ionic radii.

Valle d’Aosta section of the Sesia Zone: multi-stage HP metamorphism and assembly of a rifted continental margin

The spectrum characteristic of the EMC ranges from eclogites (containing omphacite and/or jadeite, garnet, phengite, glaucophane, zoisite, chloritoid, rutile) to phengite schists, calcschists, and marbles, as well as a variety of orthogneisses. Despite the intense polyphase deformation and HP-metamorphic recrystallization, it is possible in some locations to recognize pre-Alpine characteristics in some of the protoliths. For instance, two types of felsic orthogneiss can be distinguished in the Aosta Valley, one derived from Permian granitoids (with local preservation of intrusive contacts, magmatic inclusions, leucocratic veins and other magmatic structures; Stop 3), the other derived from pre-Variscan leuco-monzogranite, such as the building stone mined at the “Argentera” quarry near Settimo Vittone / Montestrutto (Stop 2; so-called “Verde Argento” contains jadeite, phengite, K-feldspar, quartz). Polycyclic and more rarely monocyclic metasediments contain evidence of a complex Alpine PTDt-evolution, locally including relics of their prograde history from blueschist, one or more stages at eclogite facies. Recent petrochronological studies have dated this HP-evolution of the Sesia Zone in some detail. In the area visited, clear evidence of HP-cycling has been identified in one km-size tectonic slice (Stop 1), but not in adjacent parts of the EMC, indicating “yo-yo tectonics”. Partial retrogression and attendant ductile to brittle deformation of the HP-rocks is evident in one of the outcrops (Stop 4). Apart from the four localities in the Sesia Zone, a final outcrop introduces HP-rocks of the adjacent Piemonte oceanic unit, specifically calc-schists and ophiolite members of the “Zermatt-Saas” zone. The hilltop outcrop (Stop 5) displays foliated antigorite schist with peridotite relics (clinopyroxene, spinel) containing lenses derived from doleritic dykes. These fine-grained metarodingites and the folded veins containing Mg-chlorite and titanoclinohumite within serpentinite once again indicate equilibration under low-temperature eclogite facies conditions. However, these units reached that HP stage more than 20 Ma after the youngest eclogite facies imprint recognized in the Sesia Zone. Despite nearly half a century of intense study in the Sesia Zone, the complex assembly of its HP-terranes and their relation to more external parts of the Western Alps remains incompletely understood. This field guide merely introduces a few of the classic outcrops and discusses some of the critical evidence they contain, but it could not incorporate details on each stage of the evolution recognized so far.

Bedload composition, transport and modification in rivers of Westland, New Zealand, with implications for the distribution of alluvial pounamu (jade)

River bedload surveyed at 50 sites in Westland is dominated by Alpine Schist or Torlesse Greywacke from the Alpine Fault hanging wall, with subordinate Pounamu Ultramafics or footwall-derived Western Province rocks. Tumbling experiments found ultramafics to have the lowest attrition rates, compared with greywacke sandstone and granite (which abrade to produce silt to medium-sand), or incompetent schist (which fragments). Arahura has greater total concentrations (103–105 t/km2) and proportions (5–40%) of ultramafic bedload compared with Hokitika and Taramakau catchments (101–104 t/km2, mostly <10%), matching relative areas of mapped Pounamu Ultramafic bedrock, but enriched relative to absolute areal proportions. Western Province rocks downthrown by the Alpine Fault are under-represented in the bedload. Enriched concentrations of ultramafic bedload decrease rapidly with distance downstream from source rock outcrops, changing near prominent ice-limit moraines. Bedload evolution with transport involves both downstream fining and dilution from tributaries, in a sediment supply regime more strongly influenced by tectonics and the imprint of past glaciation. Treasured New Zealand pounamu (jade) is associated with ultramafic rocks. Chances of discovery vary between catchments, are increased near glacial moraines, and are highest near source-rock outcrops in remote mountain headwaters.

The Rasikajy civilization in northeast Madagascar: a pre-European Chinese community?

Archaeological excavations in northern Madagascar during the first half of the 20th century have revealed the presence of a former prosperous civilisation known as the Rasikajy civilisation. Little is known about the origin of this civilisation and how and when they first arrived in Madagascar. The most striking evidence for the Rasikajy civilisation comes from excavations at a necropolis in Vohemar located along the northeast coast, where more than 600 tombs containing spectacular objects were unearthed in the 1940s (Vernier & Millot 1971). The findings in the tombs included, amongst others, Chinese ceramics, silver and gold jewellery, iron weapons, glassware, bronze mirrors and chlorite-schist objects (ibid.). The latter objects were produced from chlorite schist mined at quarries in northern and eastern Madagascar and there is evidence that jewellery and iron objects were also produced by the Rasikajy from locally available raw material. Chlorite-schist objects have not only been found in coastal sites in Madagascar, but also in the Comores and eastern Africa suggesting an active engagement of the Rasikajy in western Indian Ocean trade. Our re-evaluation of published literature on archaeological sites in northern Madagascar indicates that the majority of Chinese ceramics found in the tombs at Vohemar dates from the 15th and first half of the 16th century with some dating back to the 14th century or earlier. Our comparative analysis of burial objects at Vohemar shows that locally produced chlorite-schist tripod vessels exhibit remarkable resemblances to ancient Chinese bronze ritual tripod vessels. The objects encountered in the tombs and their positions with respect to the body indicate that the Rasikajy practiced burial rites similar to those practised in the past in China. Our re-evaluation of the literature suggests that communities with Chinese roots were present in northeastern Madagascar prior to the arrival of the first Europeans in 1500 and participated in the Indian Ocean trade network. The demise of the Rasikajy civilisation seems to have occurred in the second half of the 16th century when production of chlorite-schist objects ceased. It is still unclear why this occurred.