Cooling history of a dike as revealed by mineral chemistry: A case study from Mt. Etna volcano

Seven rock samples were systematically collected from innermost to the outermost portion of a dike
outcropping at Mt. Etna volcano. Results show that, from dike core-to-rim, plagioclase, clinopyroxene and
titanomagnetite show compositional variations due to increasing cooling rate. Plagioclase is progressively
enriched in An from innermost to the outermost part of the dike. Similarly, clinopyroxene components En+
CaTs+CaFeTs increase, whereas Di+Hd decrease. The Usp content in titanomagnetite also systematically
decrease from dike core-to-rim. Partition coefficients and thermometers based on the crystal-liquid exchange
reaction indicate that, due to rapid cooling rates at the dike outer portions, early-formed crystal nuclei do not
re-equilibrate with the melt. The chemistry of minerals progressively deviates from that of equilibrium;
consequently, from dike core-to-rim, mineral compositions resemble those of high-temperature formation.
The chemical variations of clinopyroxene and plagioclase in dike samples mirror those obtained from cooling
experiments carried out on alkaline basalts. Accordingly, we used an experimental equation based on
clinopyroxene compositional variation as a function of cooling rate to determine the cooling conditions
experienced by the crystals during dike emplacement. The estimated cooling rates are comparable to those
predicted by thermal modeling based on an explicit finite-difference scheme.

Baginski, B., Dzierzanowski, P., Macdonald, R., Upton, B.G.J., 2009. Complex relationships
among coexisting pyroxenes: the Paleogene Eskdalemuir dyke. Scotland.
Mineral. Mag. 73, 929–942.
Berndt, J., Koepke, J., Holtz, F., 2005. An experimental investigation of the influence of
water and oxygen fugacity on differentiation of MORB at 200 MPa. J. Petrol. 46,
135–167.
Blundy, J., Cashman, K., Humphreys, M., 2006. Magma heating by decompressiondriven
crystallization beneath andesite volcanoes. Nature 443, 76–80.
Brugger, C.R., Hammer, J.E., 2010. Crystallization kinetics in continuous decompression
experiments; implications for interpreting natural magma ascent processes.
J. Petrol. 51, 1941–1965.
Chistyakova, S., Latypov, R., 2009. On the development of internal chemical zonation in
small mafic dykes. Geol. Mag. 147, 1–12.
Coish, R.A., Taylor, L.A., 1979. The effect of cooling rate on texture and pyroxene
chemistry in DSDP Leg 34 basalt: a microprobe study. Earth Planet. Sci. Lett. 42,
389–398.
Conte, A., Perinelli, C., Trigila, R., 2006. Cooling kinetics experiments on different
Stromboli lavas: effects on crystal morphologies and phase composition.
J. Volcanol. Geoth. Res. 155, 179–200.
Corsaro, R.A., Pompilio, M., 2004. Buoyancy-controlled eruption of magmas at Mt Etna.
Terra Nova 16 (1), 16–22.
Corsaro, R.A., Civetta, L., Di Renzo, V., Miraglia, L., 2009. Petrology of lavas from the
2004–2005 flank eruption of Mt. Etna, Italy: inferences on the dynamics of magma
in the shallow plumbing system. Bull. Volcanol. 71, 781–793.
Danyushevsky, L.V., 2001. The effect of small amounts of H2O on crystallisation of midocean
ridge and backarc basin magmas. J. Volcanol. Geotherm. Res. 110, 265–280.
Deer, W.A., Howie, R.A., Zussman, J., 2001. Framework Silicates: Feldspars, second
edition. The Geological Society, London.
Del Gaudio, P., Mollo, S., Ventura, G., Iezzi, G., Taddeucci, J., Cavallo, A., 2010. Cooling
rate-induced differentiation in anhydrous and hydrous basalts at 500 MPa:
implications for the storage and transport of magmas in dikes. Chem. Geol. 270,
164–178.
Etzel, K., Benisek, A., Dachs, E., Cemic, L., 2007. Thermodynamic mixing behavior of
synthetic Ca-Tschermak–diopside pyroxene solid solutions: I. Volume and heat
capacity of mixing. Phys. Chem. Miner. 34, 733–746.Ferlito, C., Lanzafame, G., 2010. The role of supercritical fluids in the potassium
enrichment of magmas at Mount Etna volcano (Italy). Lithos 119, 642–650.
Ferlito, C., Nicotra, E., 2010. The dyke swarm of Mount Calanna (Etna, Italy): an example
of the uppermost portion of a volcanic plumbing system. Bull. Volcanol. 72 (10),
1191–1207.
Ferlito, C., Viccaro, M., Cristofolini, R., 2008. Volatile-induced magma differentiation in
the plumbing system of Mt. Etna volcano (Italy): evidence from glass in tephra of
the 2001 eruption. Bull. Volcanol. 70, 455–473.
Ferlito, C., Coltorti, M., Cristofolini, R., Giacomoni, P.P., 2009. The contemporaneous
emission of low-K and high-K trachybasalts and the role of the NE Rift during the
2002 eruptive event, Mt. Etna, Italy. Bull. Volcanol. 71, 575–587.
France, L., Ildefonse, B., Koepke, J., Bech, F., 2010. A new method to estimate the
oxidation state of basaltic series from microprobe analyses. J. Volcanol. Geotherm.
Res. 189, 340–346.
Franzini, M., Leoni, L., 1972. A full matrix correction in X-ray fluorescence analysis of
rock samples. Atti. Soc. Tosc. Sci. Nat., Mem., Ser. A 79, 7–22.
Gamble, R.P., Taylor, L.A., 1980. Crystal/liquid partitioning in augite: effects of cooling
rate. Earth Plan. Sci. Lett. 47, 21–33.
Gerlach, T.M., 1993. Oxygen buffering of Kilauea volcanic gases and the oxygen fugacity
of Kilauea basalt. Geochim. Cosmochim. Acta 57, 795–814.
Ghiorso, M.S., Sack, R.O., 1995. Chemical mass-transfer in magmatic processes 4. A
revised and internally consistent thermodynamic model for the interpolation and
extrapolation of liquidus–solid equilbria in magmatic systems at elevated
temperatures and pressures. Contrib. Mineral. Petrol. 119, 197–212.
Gibb, F.G.F., 1971. Crystal–liquid relationships in some ultrabasic dykes and their
petrological significance. Contrib. Mineral. Petrol. 30, 103–118.
Gottsmann, J., Harris, A.J.L., Dingwell, D.B., 2004. Thermal history of Hawaiian pahoehoe
lava crusts at the glass transition: implications for flow rheology and emplacement.
Earth Planet. Sci. Lett. 228, 343–353.
Grove, T.L., Bence, A.E., 1977. Experimental study of pyroxene–liquid interaction
in quartz-normative basalt 15597. Proceedings of Lunar and Planetary Science
Conference, 8th, pp. 1549–1579.
Grove, T.L., Bence, A.E., 1979. Crystallization kinetics in a multiply saturated basalt
magma: an experimental study of Luna 24 ferrobasalt. Proceedings of Lunar and
Planetary Science Conference, 10th, pp. 439–478.
Grove, T.L., Raudsepp, M., 1978. Effects of kinetics on the crystallization of
quartznormative basalt 15597: an experimental study. Proceedings of Lunar and
Planetary Science Conference, 9th, pp. 585–599.
Grove, T.L., Gerlach, D.C., Sando, T.W., 1982. Origin of calc-alkaline series lavas at
Medicine Lake Volcano by fractionation, assimilation and mixing. Contrib. Mineral.
Petrol. 80, 160–182.
Hammer, J.E., 2006. Influence of fO2 and cooling rate on the kinetics and energetics of
Fe-rich basalt crystallization. Earth Planet. Sci. Lett. 248, 618–637.
Hammer, J.E., 2008. Experimental studies of the kinetics and energetics of magma
crystallization. In: Putirka, K.D., Tepley, F.J. (Eds.), Minerals, Inclusions and Volcanic
Processes: Rev. Mineral. Geochem., 69, pp. 9–59.
Hammond, P.A., Taylor, L.A., 1982. The ilmenite-titanomagnetite assemblage: kinetics
of re-equilibration. Earth Planet. Sci. Lett. 61, 143–150.
Heap, M.J., Vinciguerra, S., Meredith, P.G., 2009. The evolution of elastic moduli with
increasing crack damage during cyclic stressing of a basalt from Mt. Etna volcano.
Tectonophysics 471, 153–160.
Heap, M.J., Baud, P., Meredith, G., Vinciguerra, S., Bell, A.F., Main, I.G., 2011. Brittle creep
in basalt and its application to time-dependent volcano deformation. Earth Plan.
Sci. Lett. 307, 71–82. doi:10.1016/j.epsl.2011.04.035.
Iezzi, G., Mollo, S., Ventura, G., Cavallo, A., Romano, C., 2008. Experimental solidification
of anhydrous latitic and trachytic melts at different cooling rates: the role of
nucleation kinetics. Chem. Geol. 253, 91–101.
Iezzi, G., Mollo, S., Torresi, G., Ventura, G., Cavallo, A., Scarlato, P., 2011. Experimental
solidification of an andesitic melt by cooling. Chem. Geol. doi:10.1016/
j.chemgeo.2011.01.024.
Kirkpatrick, R.J., 1975. Crystal growth from the melt: a review. Am. Mineral. 60, 798–814.
Kress, V.C., Carmichael, I.S.E., 1991. The compressibility of silicate liquids containing
Fe2O3 and the effect of composition, temperature, oxygen fugacity and pressure on
their redox states. Contrib. Mineral. Petrol. 108, 82–92.
Lange, R.A., Carmichael, I.S.E., 1987. Densities of Na2O-K2O-CaO-MgO-FeO-Fe2O3-Al2O3-
TiO2-SiO2, liquids: new measurements and derived partial molar properties.
Geochim. Cosmochim. Acta 53, 2195–2204.
Lange, R.A., Carmichael, I.S.E., 1996. The Aurora volcanic field, California-Nevada:
oxygen fugacity constraints on the development of andesitic magma. Contrib.
Mineral. Petrol. 125, 167–185.
Lange, R.A., Frey, H.M., Hector, J., 2009. A thermodynamic model for the plagioclaseliquid
hygrometer/thermometer. Am. Mineral. 94, 494–506.
Latypov, R., Hanski, E., Lavrenchuk, A., Huhma, H., Havela, T., 2011. A‘three-increase
model’ for the origin of the marginal reversal of the Koitelainen layered intrusion,
Finland. J. Petrol. 52, 733–764.
Lofgren, G.E., Huss, G.R., Wasserburg, G.J., 2006. An experimental study of traceelement
partitioning between Ti–Al–clinopyroxene and melt: equilibrium and kinetic
effects including sector zoning. Am. Mineral. 91, 1596–1606.
Longhi, J., Walker, D., Hays, J.F., 1976. Fe and Mg in plagioclase. Proceedings of the Lunar
Science Conference, 7th, pp. 1281–1300.
Loomis, T.P., Welber, P.W., 1982. Crystallization processes in the Rocky Hill Sanodiorite
pluton, California: an interpretation based on compositional zoning of plagioclase.
Contrib. Mineral. Petrol. 81, 230–239.
Mahood, G.A., Baker, D.R., 1986. Experimental constraints on depths of fractionation of
mildly alkalic basalts and associated felsic rocks: Pantelleria, Strait of Sicily. Contrib.
Mineral. Petrol. 93, 251–264.Mathez, E.A., 1984. Influence of degassing on oxidation states of basaltic magmas.
Nature 310, 371–375.
Métrich, N., Rutherford, M.J., 1998. Low pressure crystallization paths of H2O-saturated
basaltic-hawaiitic melts from Mt Etna: implications for open-system degassing of
basaltic volcanoes. Geochim. Cosmochim. Acta 62, 1195–1205.
Mevel, C., Velde, D., 1976. Clinopyroxenes in Mesozoic pillow lavas from the French
Alps: influence of cooling rate on compositional trends. Earth Planet. Sci. Lett. 32,
158–164.
Mollo, S., Del Gaudio, P., Ventura, G., Iezzi, G., Scarlato, P., 2010. Dependence of
clinopyroxene composition on cooling rate in basaltic magmas: implications for
thermobarometry. Lithos 118, 302–312.
Mollo, S., Putirka, K., Del Gaudio, P., Scarlato, P., in press-a. Plagioclase-melt (dis)
equilibrium due to cooling dynamics: implications for thermometry, barometry
and hygrometry. Lithos. doi:10.1016/j.lithos.2011.02.008.
Mollo, S., Vinciguerra, S., Iezzi, G., Iarocci, A., Scarlato, P., Heap, M.J., Dingwell, D.B., in
press-b. Volcanic edifice weakening via devolatilisation reactions. Geophys. J. Int.
doi:10.1111/j.1365-246X.2011.05097.x.
Morimoto, N., 1988. Nomenclature of pyroxenes. Mineral. Mag. 52, 535–550.
Muñoz, M., Sagredo, J., 1974. Clinopyroxenes as geobarometric indicators in mafic and
ultramafic rocks from Canary Islands. Contrib. Mineral. Petrol. 44, 139–147.
Mysen, B.O., Richet, P., 2005. Silicate Glasses and Melts: Properties and Structure.
Elsevier, Amsterdam.
Nakada, S., Motomura, Y., 1999. Petrology of the 1991–1995 eruption at Unzen: effusion
pulsation and groundmass crystallization. J. Volcanol. Geotherm. Res. 89, 173–196.
Nakamura, M., 1995. Continuous mixing of crystal mush and replenished magma in the
ongoing Unzen eruption. Geology 23, 807–810.
Phinney, W.C., 1992. Partitioning coefficients for iron between plagioclase and basalt as
a function of oxygen fugacity: implications for Archean and lunar anorthosites.
Geochim. Cosmochim. Acta 56, 1885–1895.
Pietranik, A., Koepke, J., Puziewicz, J., 2006. The study of crystallization and resorption
in plutonic plagioclase: implications on evolution of granodiorite magma (Gęsiniec
Granodiorite, Strzelin Crystalline Massif, SW Poland). Lithos 86, 260–280.
Potuzak, M., Dingwell, D.B., 2001. Temperature-dependent thermal expansivities
of multicomponent natural melts between 993 and 1803 K. Chem. Geol. 229,
10–27.
Putirka, K., 1999. Clinopyroxene+liquid equilibria. Contrib.Mineral. Petrol. 135, 151–163.
Putirka, K., 2005. Igneous thermometers and barometers based on plagioclase+liquid
equilibria: test of some existing models and new calibrations. Am. Mineral. 90,
336–346.
Putirka, K.D., 2008. Thermometers and barometers for volcanic systems. In: Putirka,
K.D., Tepley, F. (Eds.), Minerals, Inclusions, and Volcanic Processes: Rev. in Mineral:
Geochem., 69, pp. 61–120.
Putirka, K., Johnson, M., Kinzler, R., Walker, D., 1996. Thermobarometry of mafic
igneous rocks based on clinopyroxene–liquid equilibria, 0–30 kbar. Contrib.
Mineral. Petrol. 123, 92–108.
Putirka, K., Ryerson, F.J., Mikaelian, H., 2003. New igneous thermobarometers for mafic
and evolved lava compositions, based on clinopyroxene+liquid equilibria. Am.
Mineral. 88, 1542–1554.
Roeder, P.L., Emslie, R.F., 1970. Olivine–liquid equilibrium. Contrib. Mineral. Petrol. 29,
275–289.
Ryabchikov, I.D., Kogarko, L.N., 2006. Magnetite compositions and oxygen fugacities of
the Khibina magmatic system. Lithos 91, 35–45.
Sisson, T.W., Grove, T.L., 1993. Experimental investigations of the role of H2O in calcalkaline
differentiation and subduction zone magmatism. Contrib. Mineral. Petrol.
113, 143–166.
Smith, C.B., 1983. Pb, Sr and Nd isotopic evidence for sources of Southern African
Cretaceous kimberlites. Nature 30, 51–54.
Smith, J.V., Brown,W.L., 1988. FeldsparMinerals: 1. Crystal Structures, Physical, Chemical,
and Microtextural Properties, 2nd edition. Springer-Verlag, New York. 828 pp.
Smith, D., Lindsley, D.H., 1971. Stable and metastable augite crystallization trends in a
single basalt flow. Am. Mineral. 56, 225–233.
Smith, B.M., Prévot, M., 1977. Variation of the magnetic properties in a basaltic dyke
with concentric cooling zones. Phys. Earth Planet. Inter. 14, 120–136.
Stormer, J.C., 1983. The effects of recalculation on estimates of temperature and oxygen
fugacity from analyses of multicomponent iron–titanium oxides. Am. Mineral. 68,
586–594.
Sugawara, T., 2001. Ferric iron partitioning between plagioclase and silicate liquid:
thermodynamics and petrological applications. Contrib. Mineral. Petrol. 141,
659–686.
Tanguy, J.C., Condomines, M., Kieffer, G., 1997. Evolution of the Mount Etna magma:
constraints on the present feeding system and eruptive mechanism. J. Volcanol.
Geotherm. Res. 75, 221–250.
Tegner, C., 1997. Iron in plagioclase as a monitor of the differentiation of the Skaergaard
intrusion. Contrib. Mineral. Petrol. 128, 45–51.
Toplis, M.J., 2005. The thermodynamics of iron and magnesium partitioning between
olivine and liquid: criteria for assessing and predicting equilibrium in natural and
experimental systems. Contrib. Mineral. Petrol. 149, 22–39.
Ujike, O., 1982. Microprobe mineralogy of plagioclase, clinopyroxene and amphibole as
records of cooling rate in the Shirotori-Hiketa dike swarm, northeastern Shikoku,
Japan. Lithos 15, 281–293.
Ussler III, W., Glazner, A.F., 1989. Phase equilibria along a basalt-rhyolite mixing line:
implications for the origin of calc-alkaline intermediate rocks. Contrib. Mineral.
Petrol. 101, 232–244.
Venezky, D.Y., Rutherford, M.J., 1997. Preeruption conditions and timing of dacite–andesite
magma mixing in the 2.2 ka eruption at Mount Rainier. J. Geophys. Res. 102,
20069–20086.Viccaro, M., Ferlito, C., Cortesogno, L., Cristofolini, R., Gaggero, L., 2006. Magma mixing
during the 2001 event at Mount Etna (Italy): effect on the eruptive dynamics.
J. Volcanol. Geotherm. Res. 149, 139–159.
Whittington, A.G., Hofmeister, A.M., Nabelek, P.I., 2009. Temperature-dependent
Thermal Diffusivity of the Earth's Crust and Implications for Magmatism.
Wilding, M.C., Webb, S.L., Dingwell, D.B., 1995. Evaluation of a relaxation geospeedometer
for volcanic glasses. Chem. Geol. 125, 137–148.
Wohletz, K.H., Orsi, G., Civetta, L., 1999. Thermal evolution of the Phlegraean magmatic
system. J. Volcanol. Geotherm. Res. 91, 381–414.
Zhou, W., Van der Voo, R., Peacor, D.R., Zhang, Y., 2000. Variable Ti-content and grain
size of titanomagnetite as a function of cooling rate in very young MORB. Earth
Planet. Sci. Lett. 179, 9–20.