AGU 2016

I will be at AGU for the whole week.  On Monday afternoon I will presenting work we have been doing combining new Fe-XANES observations and thermodynamic models of mantle melting to understand solid Earth redox.  On Wednesday afternoon Paula Antoshechkina will be presenting our preliminary model incorporating carbonate melting into the pMELTS thermodynamic framework.  See you in San Francisco!

The solid Earth’s involvement in oxygen cycling: Observations and theory


Authors: Oliver Shorttle, Edward Stolper, Paula Antoshechkina, Paul Asimow, Eleanor Jennings, Glenn Gaetani, David Graham, Margaret Hartley, Helen Williams, Maryjo Brounce, Saemundur Halldorsson

Session: V13B Magmatic and Tectonic Influences on Elemental Cycling and Earth’s Climate and Oxidation State Posters

When/where: Monday 12th December, 13:40 – 18:00 in Moscone South – poster hall

We have undertaken a targeted study of basalts erupted along the South East Indian Ridge to test the relative controls of mantle temperature and chemical heterogeneity on Fe3+/ΣFe.  Among this suite of basalts there is short length scale heterogeneity and a long wavelength transition to cooler mantle.  Despite these factors, the Fe3+/ΣFe and the oxidation state of erupted basalts is remarkably uniform.  This result suggests that basalt  fO2 is being buffered during mantle melt extraction.

Silicate and Carbonatite Melts in the Mantle: Adding CO2to the pMELTS Thermodynamic Model of Silicate Phase Equilibria


Authors: Paula Antoshechkina, Oliver Shorttle

Session: V33C Deep Carbon: From the Mantle to the Surface and Back Again III Posters

When/where: Wednesday 14th December, 13:40 – 18:00 in Moscone South – poster hall

The transport of carbon in the mantle via carbonated melting of peridotite is critical for the solid Earth volatile cycle, yet most models of mantle melting only consider the thermodynamics of silicate melting and treat carbon as a trace species.  To address this issue and form a self-consistent thermodynamic description of carbonated peridotite melting we have expanded and updated the CO2-fluid database constructed by Ghiorso and Gualda (2012, 2015) to include more recent high pressure experiments.  In the initial stages of calibrating the model a key question we will answer is whether a Na2CO3 liquid component is required in addition to CaCO3.

A statistical description of concurrent mixing and crystallisation during MORB differentiation: implications for trace element enrichment

Melt formation, mixing, and transport schematic

A cartoon of the processes operating from mantle to crust, which give rise to the appearance of trace element over-enrichment in mid-ocean ridge basalts. Diverse melts are produced in the mantle, potentially from chemically heterogeneous sources (left). These melts are transported out of the mantle by channelised flow, which preserves some primary heterogeneity of the melts supplied to the crust (centre). In the crust melts fractionate crystal phases and mix (centre and right).  The supply of heterogenous melts to crustal magma chambers, and their subsequent mixing, gives rise to apparent trace element over-enrichment in the final erupted basalt.

Basalts are our window into Earth’s chemical structure, and being a product of mantle melting and transport, constrain the processes by which it continues to differentiate.  However, to interpret the basalt record in terms of mantle source and melting conditions requires our being able to see through the processes that affect basalt chemistry following melting, during their transport through the mantle, and their storage in the crust.  The extent to which basalts reflect mantle processes vs. crustal processes has been a topic of long-running debate, with workers such as Klein and Langmuir (1987) and Gale et al. (2014) arguing for the importance of mantle processes, whereas more recently O’Neill and Jenner (2012) and Coogan and O’Hara (2015) have emphasised the role of crustal magma chambers in modifying the trace and minor element chemistry of basalts.  A key observation in this debate has been the presence of trace element over-enrichment in mid-ocean ridge basalts, whereby differentiated basalts (those with low MgO) appear to have higher concentrations of incompatible trace elements than can be accounted for by simple fractional crystallisation (see figure below).

Trace element enrichment gradients.

The rate of enrichment of trace elements during magmatic differentiation (expressed as the gradient in trace element – MgO space). More negative numbers indicate stepper gradients, which when they fall below the orange line, cannot be accounted for by simple fractional crystallisation.

In this article we demonstrate how apparent trace element over-enrichment during differentiation can result simply from the chemically heterogeneous melts being supplied to the crust.  The key aspect of the model is that once resident in crustal magma chambers, the probability of melts mixing is proportional to their degree of differentiation (a proxy for their residence time).  Therefore, as melts differentiate, they progressively interact with other melts, until at low MgO (~5  wt%), magmas have a composition close to that of the mean melts being supplied from the mantle.  A consequence of this process, which we call concurrent mixing and crystallisation (CMC; Maclennan, 2008), is that the overall trend of trace element enrichment during differentiation is steeper than what it would be predicted in the absence of mixing.  What’s more, the most incompatible elements have the most variable abundance in melts supplied to the crust, and therefore exhibit the greatest degree of over-enrichment.  Thus, this model reproduces the observations presented in the figure above, whereby highly incompatible elements such as Th and U have the steepest enrichment gradients.

The importance of these results is that in our model, although mixing destroys much mantle-derived chemical variability and therefore information on the melting and melt transport process, the mean composition of the magmas supplied from the mantle is not affected.  As such, magmas retain bulk information on their sources and conditions of formation.  This means that global correlations like those established by Klein and Langmuir (1987) and Gale et al. (2014) will be valid, and the elemental ratios forming the basis for isotope evolution models of the Earth’s mantle (e.g., Sm/Nd for the <sup>143</sup>Nd isotope system) will not have been perturbed.


Online [publisher]: https://dx.doi.org/10.1093/petrology/egw056

Reference: Oliver Shorttle, John F. Rudge, John Maclennan, and Ken Rubin. Journal of Petrology (2016): 1-35, doi:10.1093/petrology/egw056.

Fe-XANES analyses of Reykjanes Ridge basalts: Implications for oceanic crust’s role in the solid Earth oxygen cycle

Ferric iron proportions and oxygen fugacity of Reykjanes Ridge basalts.

The ferric iron content (presented as  \rm{Fe^{3+}/\sum{Fe}}) and oxygen fugacity (\rm{\Delta{QFM}_{(10)} (2 kbar)}) in Reykjanes Ridge basalts approaching the Iceland plume. These samples form a 700km transect of mantle chemical structure as the chemical and thermal anomaly of the Iceland mantle plume is approached. Towards Iceland basalts become more oxidised and increasingly enriched in incompatible trace elements. These signals are consistent with ancient recycled oceanic crust present in the Icelandic mantle.

There is abundant evidence for extreme chemical heterogeneity in the Earth’s mantle, resulting from billions of years of differentiation during magma production, and the subsequent recycling of these crustal rocks back into the mantle. One way we can access a record of these processes is by studying the chemistry of recent volcanic eruptions in locations such as Iceland: where the mantle melts, its chemical character is mapped into the magmas produced, which can erupt as basalts to form an accessible archive of mantle composition.

One way we might expect the Earth’s history of subduction recycling to manifest in the composition of basalts is in their oxygen fugacity, as constrained by the proportion of \rm{Fe^{3+}/\sum{Fe}}, oxidised to reduced iron, in the basalt. Material that spends time at Earth’s surface has the potential to become oxidised by interaction with the atmosphere and hydrosphere. By compiling a large database of ocean floor basalt \rm{Fe^{3+}/\sum{Fe}} compositions and the results of scientific drilling studies, Lecuyer and Ricard (1999) showed that igneous ocean crust often becomes significantly oxidised by hydrothermal alteration, shifting an initial composition of \rm{Fe^{3+}/\sum{Fe}\sim{}0.1} to a mean crustal value of \rm{Fe^{3+}/\sum{Fe}=0.22\pm{0.08}}. A recent study by Cottrell and Kelley (2013) found that enriched mantle material, possibly produced by recycling, actually appears reduced compared with ambient mantle. However, the Cottrell and Kelley (2013) sample set specifically avoided mantle plume influenced sections of ridge, such as the Reykjanes Ridge near Iceland. This study therefore aimed to probe the oxidation state of a mantle plume, which we also have good independent evidence for containing recycled oceanic crust.

Performing Fe-XANES analyses on 64 Reykjanes Ridge basalts on beamline I18 at Diamond Light Source we found that as basalts become more enriched closer to Iceland, they also become more oxidised (Figure above). Neither degassing, nor simple fractional melting processes can account for this trend, which we instead attribute to the presence of recycled oxidised material in the Iceland plume. By performing simple fractional melting calculations, assuming reasonable ferric iron partition coefficients (Mallmann and O’Neill, 2009), we find that the oxidised signature of enriched Icelandic basalts is consistent with altered recycled oceanic crust present in the plume source in similar proportions as found by Shorttle et al. (2014).

Although more work needs to be done on the petrological modelling of ferric iron during crustal and mantle processing, our results are an indication of the role the solid Earth may have the global oxygen cycle. During the last 500 million years of Earth history oxygenation of the oceans may have enabled a flux of oxygen back into the mantle through oxidation of igneous crust at the ridge axis. In this way oxygen levels at Earth’s surface are coupled to the redox evolution of the mantle, as oxidised material is returned into it at subduction zones for long term storage. Occasionally, in locations such as Iceland, we may sample the return flux of this oxidised material to the shallow mantle, where it is involved in melting.


Online [publisher, open access]: http://dx.doi.org/10.1016/j.epsl.2015.07.017

Reference: Oliver Shorttle, Yves Moussallam, Margaret Hartley, John Maclennan, Marie Edmonds, Bramley Murton. Earth and Planetary Science Letters 427 (2015): 272-285.

Data: The published version of the ferric iron data file is space separated rather than comma separated.  Download a comma separated version here.

Publicity: From fiery giants

Concurrent mixing and crystallisation in MORB

Concurrent mixing and crystallisation in MORB over a range of length scales.

As MgO drops during crystallisation basalts become more mixed. This concurrent mixing and crystallisation is tracked by a measure of chemical variability at a given MgO (σ*), shown here for La/Yb in a global compilation of mid-ocean ridge basalts (Gale et al., 2013). In the plot to the left the amount of chemical variability present at a given MgO is represented by points coloured red for high variability and blue for low. Each horizontal band of colour indicates how variability changes during differentiation, for a suite of MORB geographically normalised over a particular length scale. Taken together, these σ*-MgO profiles record how coherent mixing patterns emerge from global datasets as the length scale of sample grouping becomes progressively more local. Plots to the right indicate the normalised data distribution of La/Yb at 10,000 km and 50 km. Figure modified from Shorttle (2015).

The basalts sampled at mid-ocean ridges and ocean islands provide critical insight into the chemical evolution of the Earth: with their isotope ratio and trace element abundances capturing processes as diverse as planetary accretion and the recent subduction of organic sediments.  Basalts are used in this way with the understanding that their composition reflects that of the solid mantle source from which they were derived. However, we can only use the chemical inventory of basalts to probe mantle geochemistry if we are confident that we can ‘see through’ the chemical signals that have been imparted to them in the tens to thousands of years preceding their eruption. During this interval basalts are produced by partial melting of the mantle, extracted by porous and focussed flow, aggregated in mantle and crustal magma chambers and cooled, leading to their crystallisation. At each of theses stages there is the opportunity for basalts to mix, leading to a reduction in the amount of information they carry about their source, and therefore limiting our ability to reconstruct mantle composition and history.

This paper focusses on the mixing basalts experience during crustal (and upper mantle) storage in magma chambers. I use Iceland as a case study, which nicely illustrates the chemical signature of mixing in whole rock and melt inclusion records, to then explore mixing systematics along the more sparsely sampled submarine portions of the mid-ocean ridge system. The significance of magma mixing in mid-ocean ridge basalts (MORB) has previously been recognised from global compilations of MORB (e.g. Rubin et al., 2001) and from micro-analytical studies of melt inclusions (e.g. Sobolev & Shimizu (1993) and Maclennan (2008)), amongst other observations. In this paper I focus on investigating the length scale at which coherent mixing relationships become visible in suites of basalts, and the spatial statistical methods we can use to understand the meaning of this length scale.

Applying geographic normalisation to the global dataset of Gale et al., (2013), I find that coherent mixing relationships are visible at length scales < 300 km – approximately the scale of first order ridge segmentation. Statistical tests repeatedly randomly repositioning samples demonstrate that this result is only apparent in the real dataset – i.e. spatial structure exists in the samples of natural MORB that statistically relates them to one another over ~100 km length scales. This observation is another hint at the geochemical provincialism present in basalts (e.g. Shorttle et al. 2013). Yet, it remains challenge to identify at which point in the system, from mantle to crust, that basalts erupting > 100 km apart gain similarity to one another. One possibility is that this relates to a decorrelation length scale in mantle compositional structure.

The challenge posed by magma mixing from a mantle geochemical perspective is even knowing that the information loss has occurred. If primitive basalts are erupted, containing early crystallising phases, then perhaps concurrent mixing and crystallisation (CMC) will be caught in the act and basalts will be only partially mixed. However, extensive mixing may occur before a crystal record is even produced, for example during transport out of the mantle (Rudge et al., 2013). In this case it is important to appreciate how mixing may bias the accessible geochemical record of basalts. In particular, developing an understanding of magma mixing is going to be important for understanding the relationship of ocean island basalt chemistry to that of MORB.  As their very different geodynamic settings will likely translate into different magma storage and transport histories, of which we are unable to fully predict the geochemical consequences.


Online [publisher]: http://dx.doi.org/10.1016/j.epsl.2015.04.035

Online [preprint]: http://www.shorttle.com/paper_store/os_mix2015.pdf

Reference: Oliver Shorttle. Geochemical variability in MORB controlled by concurrent mixing and crystallisation. Earth and Planetary Science Letters 424 (2015): 1-14.

AGU 2014

Come and find me or any of my collaborators at AGU this year to discuss our latest results.  Margaret Hartley and I have some great new XANES data collected at Diamond Light Source probing fO2 in enriched mantle domains and tracking its evolution during magmatic processes. I have an invited talk in V038: The Geochemical Diversity of the Mantle Inferred from Hotspots: Five Decades of Debate, where I will present evidence for the ubiquity of concurrent mixing and crystallisation in destroying the primary chemical diversity leaving the mantle at mid-ocean ridges. With Mark Hoggard’s fantastic record of dynamic support in the world’s ocean basins, we have begun to reconstruct spatio-temporal variability in mantle potential temperature over the last 100Ma.

Controls on OIB and MORB Geochemical Variabilty


Authors: Oliver Shorttle & John Maclennan

Concurrent mixing and crystallisation is visible on a local scale looking at melt inclusion and whole rock suites. Here we show that this basic magmatic process extends not only off of Iceland onto the adjacent Reykjanes Ridge, but by spatial statistical analysis can be seen to be present in global MORB datasets. Homogenisation of primary mantle chemical diversity is therefore a ubiquitous phenomenon occurring in magmatic systems. Understanding how this operates is going to be key for reconstructing mantle compositional diversity.


Authors: Oliver Shorttle & Yves Moussallam, Margaret E Hartley, Marie Edmonds, John Maclennan and Bramley J Murton

Recent evidence from Cottrell and Kelley (2013) has indicated that the mantle heterogeneity sampled by MORB and typically identified from studying radiogenic isotope tracers, may also be associated with redox heterogeneity in the mantle. This compelling observation has major implications for the flux of redox sensitive elements throughout the Earth system, for mantle dynamics, and for the melting process itself. In this work we have characterised the changes in mantle fO2 that occur towards the Iceland plume using a suite of basalt samples.


Authors: Margaret E Hartley, Oliver Shorttle, John Maclennan, Yves Moussallam and Marie Edmonds

Melt inclusions record the primary diversity of melts leaving the mantle in terms of their trace and isotopic compositions, and there is the potential for melt inclusions to also record redox heterogeneity of the source.  However, post entrapment processes such as diffusion and crystallisation may compromise the melt inclusion record, resetting melt inclusion fO2 during shallow level processes. To investigate the potential of the melt inclusion archive in terms of fO2 we have studied a suite of melt inclusions from the AD 1783 Laki eruption, Iceland.

A History of Global Mantle Potential Temperatures from Oceanic Crustal Thicknesses


Authors: Mark Hoggard, Nicholas J White and Oliver Shorttle

We know from geophysical observations of gravity anomalies and petrological measurements on primitive basalts that mantle potential temperature is likely to vary by several hundred degrees in the modern Earth.  A record of potential temperature variation in the past is preserved in the crustal thickness of old seafloor, which will be thicker if high potential temperatures during its formation increased melt production. Here, we use Mark’s extensive compilation of reflection and wide-angle seismic profiles to constrain crustal thicknesses throughout the oceanic realm. These observations when combined with a mantle melting model allow us to back out a unique record of spatio-temporal syn- and post-rift variations in mantle temperature.

Quantifying lithological heterogeneity

Melt production as a function of lithology

Combining constraints on melt production (crustal thickness, tc) and the fraction of melts supplied by pyroxenite melting (from geochemistry, Fpx) unique source lithologies can be identified beneath Iceland. In these triangular diagrams position denotes the proportion of each lithology in the source, whilst colour indicates the relative proportion of enriched and depleted melts produced. Figure modified from Shorttle et al. (2014).

The presence of lithological diversity in the mantle has major implications for solid Earth dynamics, the mantle melting process and potentially the environmental impact of eruptions. In this paper we consider the processes affecting the representation of lithological diversity in erupted basalts, such as the biasing effect of the melting process, in order to construct quantitative estimates of the abundance of different lithologies in the mantle. Being able to form such estimates is the first step for understanding how lithological heterogeneity is affecting melt production and ultimately influencing the solid Earth’s interaction with the surface environment.

We focus our study on Iceland, and first use high MgO basalts from Iceland’s neovolcanic zones to characterise the trace element enriched and depleted endmember melts entering the Icelandic crust. These compositions can then be used in a mass balance with the average Icelandic crustal composition (as represented by evolved, mixed, basalts) to calculate the proportion of melt on Iceland being supplied from enriched vs. depleted mantle domains. With this estimate of enriched and depleted melt proportions, and knowing that the lithologies contributing to melting in the Icelandic mantle (pyroxenite and lherzolite, Shorttle et al. 2011), it is possible to construct a melting model to determine how abundant each lithology must be in the Icelandic source. However, as can be seen from the figure above, using only the constraint on proportion of enriched and depleted endmembers does not uniquely constrain a valid source lithology. To achieve a unique result we add in the constraint that the total melt production must be consistent with the volume of melt production on Iceland (the crustal thickness).

Even using enriched-depleted melt proportions and crustal thickness, source lithology remains non-unique unless mantle potential temperature is also known. Specifically, there is a strong trade off in harzburgite abundance against lherzolite proportion in the source – all valid solutions have ~10% pyroxenite component. To obtain added constraints on source we consider the buoyancy of the possible Icelandic source lithologies, and whether they would be consistent with recent volume flux estimates (Jones et al. 2014). Considering this additional dynamical constraint, the Icelandic source is required to have significant (>20%) harzburgite component. Although there is this uncertainty on the maximum temperature of the plume source, our model nonetheless constrains its minimum temperature to be significantly above ambient mantle, by ~130ºC (see figure above).


Online [publisher, open access]: http://dx.doi.org/10.1016/j.epsl.2014.03.040

ReferenceShorttle, Oliver, John Maclennan, and Sarah Lambart. Quantifying lithological variability in the mantle. Earth and Planetary Science Letters 395 (2014): 24-40.

Thesis: Characteristics of a heterogeneous mantle

A copy of my PhD thesis, carried out at the University of Cambridge between Oct. 2009 and Oct. 2012 can be found here. I was supervised by John Maclennan and Alex Piotrowski.

A more digestible read of Chapters 4, 5 and 6 can be found in the associated papers, which are respectively:

 

Identifying lithological heterogeneity

Concurrent mixing and crystallisation seen through to reveal lithological heterogeneity.

Concurrent mixing and crystallisation destroys the primary geochemical variability leaving the mantle. MgO tracks the progressive crystallisation of basalts, whilst Nb/Zr, an incompatible trace element ratio records the collapse in primary chemical diversity that occurs in response to magma mixing in the crust. Primitive basalts, with MgO > 9.5 wt%, show the greatest geochemical diversity, which correlates with major element composition, implying lithological heterogeneity in the source. Figure modified from Shorttle & Maclennan (2011).

Our understanding of the mantle, long thought to be largely homogeneous in its major element composition, has undergone significant revision in the last decade as increasing evidence points towards it containing lithological heterogeneity. In this paper we present new evidence from Iceland that demonstrates the presence of pyroxenitic components in the plume source. Using a novel data projection (shown above) we account for fractional crystallisation processes and concurrent mixing and crystallisation to see through to the major element – trace element relationships characteristic of enriched and depleted mantle domains.

We also consider the consequences of lithological heterogeneity for melt production. Iceland is characterised by high crustal thicknesses, perhaps up to 40 km at the island’s centre (Darbyshire et al., 2000), and the eruption of enriched basalts. This combination has led some to claim that an enriched, fusible, source lithology is alone enough to explain the high crustal thickness observed (Foulger & Anderson, 2005). However, the thermodynamic modelling we present in this paper of a bi-lithological peridotite-pyroxenite mantle shows that the latent heat cost of melting requires significant excess temperature (> 100°C) even in the case of a pure pyroxenite mantle.


Online [Department repository, full text]: http://eprints.esc.cam.ac.uk/2228/7/ggge2058.pdf

Online [Publisher]: http://dx.doi.org/10.1029/2011GC003748

ReferenceShorttle, Oliver, and John Maclennan. Compositional trends of Icelandic basalts: Implications for short–length scale lithological heterogeneity in mantle plumes. Geochemistry, Geophysics, Geosystems 12, no. 11 (2011).