Rotherkopfite, KNa₂(Fe²⁺2.5Ti⁴⁺1.5)Fe²⁺(Si₄O₁₂)₂, a new neptunite-group mineral without essential lithium, from Rother Kopf, Eifel volcanic fields, Germany

Rotherkopfite, KNa2(Fe2.52+Ti1.54+)Fe2+(Si4O12)2, is a new member of the neptunite group, from Rother Kopf, Roth, near Gerolstein, Eifel volcanic fields, Rhineland-Palatinate, Germany. It is found in cavities in a quartz–sanidine xenolith embedded in a vesicular alkaline basalt and is associated with fluorophlogopite and an amphibole supergroup mineral that is zoned from potassic-magnesio-fluoro-arfvedsonite on the exterior to potassic-fluoro-richterite in the core. It is presumed to have formed as the result of contact metasomatism of the xenolith by the alkaline basalt melt. Rotherkopfite occurs as brownish-red equant or tabular crystals, up to about 0.2 mm in maximum dimension. The mineral has a light-orange streak, a vitreous lustre, a Mohs hardness of ∼4.5, a brittle tenacity, a curved fracture and a density of 3.20(2) g cm−3. Optically, rotherkopfite crystals are biaxial (+), with α=1.668(5), β=1.678(5), γ=1.720(5) (white light) and 2V(meas) = 53.2(6)°. The empirical formula from electron microprobe analyses, secondary ion mass spectrometry and structure refinement is (K0.87Na0.20)Σ1.07(Na1.99Ca0.01)Σ2.00M1+M2(Fe1.662+Ti1.48Mg0.79Mn0.02)Σ3.95M3(Fe0.642+Li0.16Ti0.15Al0.01)Σ0.96(Si8.00O24). Rotherkopfite is monoclinic with space group C2/c and unit-cell parameters a=16.4599(17), b=12.5457(6), c=10.0487(7) Å, β=115.669(7)°, V=1870.3(3) Å3 and Z=4. The crystal structure (R1=0.0268 for 1324 reflections with I>2σI) is based on two interwoven three-dimensional frameworks: (1) a silicate framework made up of pyroxene-like chains of corner-sharing SiO4 tetrahedra and (2) an octahedral framework made up of chains of edge-sharing metal–oxygen octahedra. The two interwoven frameworks are bound to one another by corner sharing. K and Na are hosted in channels in the combined framework.