Hollandite–strontiomelane solid solutions coexisting with kanonaite and braunite in late quartz veins of the Stavelot Massif, Ardennes, Belgium

In a newly found type of quartz vein cross-cutting the famous "viridine"-bearing phyllites at Le Coreux, hollandite, ideally BaMn₈O₁₆, was discovered for the first time at this locality and in Belgium. Because the crystals contain up to 60 mol% of the Sr end member, this is also the second occurrence of strontiomelane. The coexisting "viridine" (= kanonaite) contains the highest amount (88 mol%) of the ideal end member MnAlSiO₅ ever found worldwide. The hollandite-type minerals are intimately intergrown with braunite containing appreciable Ca and Mg. Ba-bearing muscovite, Fe-poor excess-Al clinochlore (not quite trioctahedral), and albite are the remaining accessory minerals in the dominant quartz matrix. Microprobe analyses of all phases show rather extreme element fractionations: nearly all K is located in muscovite and none in the hollandite phase despite the existence of the end member KMn₈O₁₆ (cryptomelane). Similarly, nearly all Na is in albite and not in hollandite (no NaMn₈O₁₆=manjiroite component). Nearly all Mn resides in the two oxide phases and in kanonaite. Mg is strongly fractionated into chlorite. The small amounts of Fe and Ti present are predominantly partitioned into the hollandite phase, which also accommodates most of the Ba and Sr. Indeed, the hollandite phase is stabilized by the latter two elements relative to other Mn oxides. Kanonaite is stabilized by Al. Although no requisite sites are available in its crystal structure, braunite always contains small amounts of Ba and Sr. However, the Sr/(Sr+Ba) ratios in braunite are spurious and unrelated to those of the directly adjoining hollandite phases The conditions of formation of these veins may be well below 300 °C at low pressures (1-2 kbar), in agreement with the experimental results that the maximum Mn contents in kanonaite increase with falling temperatures.