Volatile and light lithophile elements in high-anorthite plagioclase-hosted melt inclusions from Iceland

Geochemcial records of mantle processes are progressively degraded as magmas differentiate and ascend towards the Earth’s surface. This degradation is particularly severe in the case of volatiles (H2O, CO2, F, S and Cl) that decouple from melts upon reaching vapour saturation. Melt inclusions – pools of silicate liquid that are partially insulated from changes in the external magmatic enronment by their host crystals – are thus appealing targets for investigating the behvaiour of magmatic volatiles. Although numerous recent studies have critically evaluated the effects of syn- and post-entrapment modification on olivine-hosted melt inclusion compositions, little comparable information is available for plagioclase-hosted systems, depite plagioclase’s abundance in mafic magmas.

In order to address this imbalance in undertanding between olivine-hosted and plagioclase-hosted systems, we present volatile and light lithophile element analyses from a large number of mainly plagioclase-hosted melt inclusions from the 10 ka Grímsvötn tephra series from Iceland. Major and trace element data have already  been presented in study into the pre-eruptive evolution and storage of the tephra series (Neave et al., 2015).

Volatile-trace element systematics in matrix glasses and melt inclusions used to distinguish between pre-, syn- and post-entrapment signals of variability. Figure from Neave et al. (2017).

The uniformly low CO2 content of melt inclusions cannot be explained by either shallow entrapment or shrinkage bubble formation, suggesting that inclusion CO2 contents were controlled by decrepitation instead. High H2O/Ce values in primitive plagioclase-hosted inclusions (182–823) are most easily accounted for by diffusive H2O gain following the entrainment of primitive macrocrysts into H2O-rich melts a few days before eruption (e.g., Hartley et al., 2015). Extreme F enrichments in primitive plagioclase-hosted inclusions (F/Nd = 51–216 versus 15 in matrix glasses) possibly reflect the entrapment of inclusions from high-Al/(Al+Si) melt pools formed by dissolution-crystallisation processes (as indicated by HFSE depletions in some inclusions), and into which F was concentrated by uphill di ffusion: F is highly soluble in Al-rich melts. The high S/Dy of inclusions (300) indicates that primary melts were rich in S in comparison with most oceanic basalts. Although primitive plagioclase-hosted melt inclusions from the 10 ka Grímsvötn tephra series record few primary signals in their volatile element contents they nevertheless record information about crustal magma processing that is absent from olivine-hosted melt inclusions suites.

Publication

Neave, D.A., Hartley, M.E., Maclennan, J., Edmonds, M. & Thordarson, T. 2017.  Volatile and light lithophile elements in high-anorthite plagioclase-hosted melt inclusions from Iceland. Geochimica et Cosmochimica Acta 205, 110–118. <Open access>

Goldschmidt: Magma plumbing systems and plagioclase-hosted melt inclusions

In summer 2016, I presented two abstracts at Goldschmidt in Yokohama, Japan. In my invited contribution, I summarised how a range of petrological and geochemical observations can be combined to reconstruct magma plumbing system characteristics (slides). In my second contribution, I discussed the reliability of estimating magma volatile contents by measuring primitve plagioclase-hosted melt inclusions (slides).

Magma pluming systems in th EVZ.
Magma plumbing systems in the Eastern Volcanic Zone of Iceland.

 

Diffusive over-hydration of olivine-hosted melt inclusions

Olivine-hosted melt inclusions are ofen used to estimate the pre-eruptive H2O content of magmas (Métrich & Wallace, 2008). However, it has been noted for a number of years that H2O appears to ‘leak’ out of melt inclusions during ascent and eruption (Massare et al., 2002; Chen et al., 2013). Rare cases of H2O gain have also been noted (Kolezsar et al., 2009). Recent experiments and modelling has clarified the mechanisms of H2O loss– by diffusive re-equilibration through the host crystal – and has opened up the possibily of extracting timescales from the extent of H2O exchange (Gaetani et al., 2012; Bucholz et al., 2013).

In this study, led by Margaret Hartley at the University of Manchester, we showed that different populations of melt inclusions from the Laki and Skuggafjöll eruptions in the Eastern Volcanic Zone of Iceland experienced diffusive loss or diffusive gain of H2O. Some rapidly quenched melt inclusions from the Laki tephra and subglacially-quenched pillow glasses from Skuggafjöll had coherent H2O/Ce values of ~180 that we interpreted as the primary mantle value (e.g., Michael, 1995). However, many inclusions from the Laki lava flow had very low H2O/Ce values consistent with H2O loss during transport in an extensive lava tube network at the surface. Conversely, most inclusions from Skuggafjöll, as well as most low-Ce, primitive inclusions from Laki, had elevated H2O/Ce values of up to ~1000 that are indicative of H2O gain during storage in the crust.

A figure from Hartley et al. (2015) summarising the processes by which diffusive loss and gain of H2O has been observed in the Laki and Skuggafjöll eruptions.

Using the diffusive re-equilibration model of Bucholz et al. (2013), we placed minimum constraints on the residence times of dehydrated inclusions in the Laki lava flow and over-hydrated inclusions in evolved melts immediately prior to the eruptions. The timescales were on the order of days to tens of days in both cases. Finally, we demonstrated that diffusive gain, as well as diffusive loss, can be observed in a number of global datasets where primitive, H2O-poor inclusions are mixed into more enriched and/or evolved melts before eruption. Thus, rather than viewing the open system nature of olivine-hosted melt inclusions as weakness, it can be exploited to gain further insights into pre-eruptive magma processes.

Publication

Hartley, M.E., Neave, D.A., Maclennan, J., Edmonds, M. & Thordarson, T. 2015. Diffusive over-hydration of olivine-hosted melt inclusions. Earth and Planetary Science Letters 425, 168–178. <Open Access>

Melt mixing causes negative correlation of trace element enrichment and CO2 content prior to an Icelandic eruption

Dissolved volatile elements play important roles in driving volcanic eruptions and controlling the physical properties of magmas. Degassing of magmatic volatiles also links deep geochemcial reservoirs with the Earth’s surface, closing global element cycles (e.g., Marty & Tolstikhin, 1998). However, determing the original CO2 content of mantle melts is difficult because most melts reach volatile saturation long before eruption. Measuring melt inclusions isolated hosted in primitive crystals that remained isolated from their carrier melt provides one way of investigating the CO2 content of basaltic magmas (e.g., Moore, 2008).

In this paper, we presented major, trace and volatile element analyses from >100 primitive olivine-hosted melt inclusions from a sub-glacial eruption in the Eastern Volcanic Zone of Iceland – the Skuggafjöll eruption. While our melt inclusion compositions preserved a record of primitive melt heterogeneity similar to that observed in other Icelandic systems including Laki (Neave et al., 2013), the most striking feature of our dataset was an enigmatic negative correlation between CO2 and incompatible trace element enrichment:

 

Negative correlation between melt inclusion CO2 and Ce/Y contents. The solid black line shows a mixing line between a depleted end-member shown with a black diamond and an enriched end-member shown with a white diamond that explains much of the correlated varibility in tha sample suite. Many inclusions have experineced further exsolution as illustrated by the discrepancy between predicted and measured CO2 contents. Modifued from Neave et al. (2014).
Negative correlation between melt inclusion CO2 and Ce/Y contents. The solid black line shows a mixing line between a depleted end-member shown with a black diamond and an enriched end-member shown with a white diamond that explains much of the correlated varibility in tha sample suite. Many inclusions have experineced further exsolution as illustrated by the discrepancy between predicted and measured CO2 contents. Modified from Neave et al. (2014).

We suggested that a negative correlation between CO2 and incompatibe trace element enrichment may result from the concurrent mixing, crystallisation and exsolution of CO2 from melts that have experienced varying degrees of previous CO2 loss: mixing may have been triggered by the injection of a depleted and possibily CO2-supersaturated melt (CO2/Nb > 350) into a relatively shallow magma reservoir containing an enriched melt that has already lost much of its CO2.

Another inportant finding  concerned the CO2 content of shrinkage bubbles in melt inclusions. Many recent studies have demonstrated that CO2 can be sequestered into bubbles during the cooling of melt inclusions (e.g., Hartley et al., 2014; Mironov et al., 2015; Wallace et al., 2015; Moore et al., 2015). However, despite investigating a large number number of shrinkage bubbles by Raman spectroscopy and microthermometry, we found no CO2-bearing bubbles. We therefore suggested that our subglacially quenched samples cooled sufficiently quickly to for CO2 sequestration to have been kinetically inhibited, an observation that has implications for interpreting the CO2 content of inclusions from other settings that experince rapidly quenched, such as those from mid-ocean ridges.

Comparison of the CO2 content of melt inclusions with and without inclusion-hosted bubbles: bubbles have no systematic effect on inclusion CO2 content.
Comparison of the CO2 content of melt inclusions with and without inclusion-hosted bubbles: bubbles have no systematic effect on inclusion CO2 content.

Publication

Neave, D.A., Maclennan, J., Edmonds, M. & Thordarson, T. 2014. Melt mixing causes negative correlation of trace element enrichment and CO2 content prior to an Icelandic eruption. Earth and Planetary Science Letters 400, 272–283. <Open Access>

Melting, differentiation and degassing at the Pantelleria volcano, Italy

Pantellerites are Fe- and volatile-rich, peralkaline rhyolites that erupt primarily in continental rift settings. As no eruptions of pantelleritic magma have been observed, interpreting the diversity of volcanic phenomena at pantelleritic volcanoes is challenging. Explosive eruptions range in scale from large ignimbrite-forming events like the ~45 ka Green Tuff eruption on Pantelleria to small cone-forming events. Effusive eruptions form structures as diverse as low-aspect-ratio lava domes and high-aspect-ratio lava shields. Although fewer in number than their calcalkaline counterparts, peralkaline rhyolite volcanoes nevertheless present a range of hazards.

The evolution of peralkaline magmas has been the subject of much recent debate, with some authors advocating for pantellerite genesis by melting alkali gabbros (e.g., Avanzinelli et al., 2004), and others favouring extensive fractional crystallisation (e.g., White et al., 2009). The volatile content of pantellerite melts had also been the subject of considerable uncertainty until a recent studied have confirmed the water-rich nature of pantelleritic melts.

In this paper, we presented major element, trace element and volatile compositions from glasses, crystals and melt inclusions from a number of post-Green Tuff eruptions from Pantelleria. The main outcomes were:

  1. A quantification of the degree of aluminous lherzolite melting required to generate the alkali basalts present around northwest coast of Pantelleria (~2%).
  2. A confirmation that pantellerites can be generated by extensive fractional crystallisation (~95%) of alkali basalts.
  3. High precision analyses of glass and melt inclusion volatile contents (H2O, CO2, Li, F, Cl, S) that confirm the H2O- and halogen-rich of pantellerite melts
  4. An evaluation that explosive peralkaline eruptions may emit much more sulphur than metauluminous eruptions of an equivalent size, up to ~100 Mt for a Green Tuff-sized eruption, becasue of the high sulphur solubilty in Fe- and alkali-rich melts.

Dammusi on Pantellieria
Dammusi on Pantellieria

Publication

Neave, D.A., Fabbro, G., Herd, R.A., Petrone, C.M. & Edmonds, M. 2012. Melting, Differentiation and Degassing at the Pantelleria Volcano, Italy. Journal of Petrology 53, 637–663.