Biotites as Indicators of Fluorine Fugacities in Late-Stage Magmatic Fluids: the Gardar Province of South Greenland

The major element chemistry and fluorine contents of biotitesfrom the Gardar alkaline province of South Greenland providean insight into the F contents of late-stage fluids associatedwith the magmatism. Biotites were taken from composite intrusionsranging from alkali gabbro to syenites, nepheline syenites andalkali granites. In each complex they show a large range ofFe/(Fe+Mg) (from 0•2 to 1) and exhibit strong Fe-F avoidance.There is considerable variation in F for any value of Fe/(Fe+Mg)but for each centre maximum F values plotted against Fe/(Fe+Mg)define a nearly straight line of characteristic slope towardslow or zero F at pure annite. Micas in the SiO₂ undersaturatedcentres have higher F contents than those from oversaturatedcentres. Cl is low (0•69 wt%) except in the Kûngnâtintrusion, where it reaches 1•4 wt%. Phase equilibriumand textural considerations suggest that most or all biotitesgrew subsolidus in a pervasive deuteric fluid. ¹⁸O values suggestthat these fluids were largely magmatic in character and thatextensive reactions with envelope fluids did not occur. Metasomaticresetting of F in biotites in early intrusive units in the aureoleof later units can be demonstrated. Experimental data of Munoz (Mineralogical Society of America,Reviews in Mineralogy 13, 469–494, 1984) were used tocalculate families of curves showing variation in F with Fe/(Fe+Mg)for biotites in equilibrium with fluids of fixed fugacity ratio,f(HF)/f(H₂O), at fixed P and T. The resulting curves cut sharplyacross the maximum fluorine lines observed in the natural examples.As it seems highly unlikely that changes in fluid compositionand T, acting together, could produce the observed linear relationship,we conclude that the partitioning of F between fluid and micain the plutonic environment is not well modelled by the experiments.Possible explanations are short-range order (SRO) of Fe andMg on octahedral sites in biotite (Mason, Canadian Mineralogist30, 343–354, 1992) or effects resulting from differentF speciation in alkaline fluids. If perfect Fe-F avoidance isassumed, Fe-Mg SRO can increase maximum F content. The F levelsseen in the silica-saturated centres are broadly consistentwith a cooling-rate related control. It is possible that thehigher F in biotites in the undersaturated centres reflectsdifferent speciation in the fluid rather than higher F contents,with strongly bound SiF₄° complexes more common. KEY WORDS: biotites; Gardar; fluorine; alkaline rocks; fluids