Titan-aegirine from early Tertiary ash layers in northern Denmark

Microprobe analyses on a xenocrystic suite of salites, aegirine-augites, aegirines, titan-aegirines and acmites from a lower Tertiary ash layer in northern Denmark are presented. The sodic pyroxenes show an unusual titan-enrichment and up to 42 mol.% of the component $\text{NaTi}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}{}^{\mathrm{4+}}\text{M}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}{}^{\mathrm{2+}}\text{Si}{}_3\text{O}{}_6\text{(}\text{M = Fe}{}^{\mathrm{2+}}\text{,}\text{Mn or Mg}\text{)}$, is estimated. Optical absorption measurements show no evidence for Ti³⁺. The titan-aegirines were formed during late to post-magmatic crystallization in a system with a high Ti⁴⁺/Fe²⁺ ratio and were followed by acmite showing enrichment in jadeite. Comparison with experimentally investigated titan-aegirine indicates crystallization far below the Mn₂O₃Mn₃O₄f₀₂ buffer.