Trace element and isotopic effects of combined wallrock assimilation and fractional crystallization

The chemical composition of subducting sediment and its consequences for the crust and mantle

Knowledge of temperature and pressure, however qualitative, has been central to our views of geology since at least the early 19th century. In 1822, for example, Charles Daubeny presented what may be the very first “Geological Thermometer,” comparing temperatures of various geologic processes (Torrens 2006). Daubeny (1835) may even have been the first to measure the temperature of a lava flow, by laying a thermometer on the top of a flow at Vesuvius—albeit several months following the eruption, after intervening rain (his estimate was 390°F). In any case, pressure ( P ) and temperature ( T ) estimation lie at the heart of fundamental questions: How hot is Earth, and at what rate has the planet cooled. Are volcanoes the products of thermally driven mantle plumes? Where are magmas stored, and how are they transported to the surface—and how do storage and transport relate to plate tectonics? Well-calibrated thermometers and barometers are essential tools if we are to fully appreciate the driving forces and inner workings of volcanic systems.

This chapter presents methods to estimate the P-T conditions of volcanic and other igneous processes. The coverage includes a review of existing geothermometers and geobarometers, and a presentation of approximately 30 new models, including a new plagioclase-liquid hygrometer. Our emphasis is on experimentally calibrated “thermobarometers,” based on analytic expressions using P or T as dependent variables. For numerical reasons (touched on below) such expressions will always provide the most accurate means of P-T estimation, and are also most easily employed. Analytical expressions also allow error to be ascertained; in the absence of estimates of error, P-T estimates are nearly meaningless. This chapter is intended to complement the chapters by Anderson et al. (2008), who cover granitic systems, and by Blundy and Cashman (2008) and Hansteen and Klugel (2008), who consider additional methods …

Thermometers and Barometers for Volcanic Systems

A model for the generation of intermediate and silicic igneous rocks is presented, based on experimental data and numerical modelling. The model is directed at subduction-related magmatism, but has general applicability to magmas generated in other plate tectonic settings, including continental rift zones. In the model mantlederived hydrous basalts emplaced as a succession of sills into the lower crust generate a deep crustal hot zone. Numerical modelling of the hot zone shows that melts are generated from two distinct sources; partial crystallization of basalt sills to produce residual H2O-rich melts; and partial melting of pre-existing crustal rocks. Incubation times between the injection of the first sill and generation of residual melts from basalt crystallization are controlled by the initial geotherm, the magma input rate and the emplacement depth. After this incubation period, the melt fraction and composition of residual melts are controlled by the temperature of the crust into which the basalt is intruded. Heat and H2O transfer from the crystallizing basalt promote partial melting of the surrounding crust, which can include meta-sedimentary and meta-igneous basement rocks and earlier basalt intrusions. Mixing of residual and crustal partial melts leads to diversity in isotope and trace element chemistry. Hot zone melts are H2O-rich. Consequently, they have low viscosity and density, and can readily detach from their source and ascend rapidly. In the case of adiabatic ascent the magma attains a super-liquidus state, because of the relative slopes of the adiabat and the liquidus. This leads to resorption of any entrained crystals or country rock xenoliths. Crystallization begins only when the ascending magma intersects its H2O-saturated liquidus at shallow depths. Decompression and degassing are the driving forces behind crystallization, which takes place at shallow depth on timescales of decades or less. Degassing and crystallization at shallow depth lead to large increases in viscosity and stalling of the magma to form volcano-feeding magma chambers and shallow plutons. It is proposed that chemical diversity in arc magmas is largely acquired in the lower crust, whereas textural diversity is related to shallow-level crystallization.

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The Genesis of Intermediate and Silicic Magmas in Deep Crustal Hot Zones

Every large eruption of nonbasaltic magma taps a magma reservoir that is thermally and compositionally zoned. Most small eruptions also tap parts of heterogeneous and evolving magmatic systems. Several kinds of compositionally zoned ash flow tuffs provide examples of preemptive gradients in T and ƒO2, in chemical and isotopic composition, and in the variety, abundance, and composition of phenocrysts. Such gradients help to constrain the mechanisms of magmatic differentiation operating in each system. Roofward decreases in both T and phenocryst content suggest water concentration gradients in magma chambers. Wide compositional gaps are common features of large eruptions, proving the existence of such gaps in a variety of magmatic systems. Nearly all magmatic systems are ‘fundamentally basaltic’ in the sense that mantle-derived magmas supply heat and mass to crustal systems that evolve a variety of compositional ranges. Feedback between crustal melting and interception of basaltic intrusions focuses and amplifies magmatic anomalies, suppresses basaltic volcanism, produces and sustains crustal magma chambers, and sometimes culminates in large-scale diapirism. Degassing of basalt crystallizing in the roots of these systems provides a flux of He, CO2, S, halogens, and other components, some of which may influence chemical transport in the overlying, more silicic zones. Basaltic magmas become andesitic by concurrent fractionation and assimilation of partial melts over a large depth range during protracted upward percolation in a plexus of crustal conduits. Zonation in the andesitic-dacitic compositional range develops subsequently within magma chambers, primarily by crystal fractionation. Some dacitic and rhyolitic liquids may separate from less-silicic parents by means of ascending boundary layers along the walls of convecting magma chambers. Many rhyolites, however, are direct partial melts of crustal rocks, and still others fractionate from crystal-rich intermediate parents. The zoning of rhyolitic magma is accomplished predominantly by liquid state thermodiffusion and volatile complexing; liquid structural gradients may be important, and thermal gradients across magma chamber boundary layers are critical. Intracontinental silicic batholiths form where extensional tectonism favors coalescence of crustal partial melts instead of hybridization with the intrusive basaltic magma. Cordilleran batholiths, however, result from prolonged diffuse injection of the crust by basalt that hybridizes, fractionates, and preheats the crust with pervasive mafic to intermediate forerunners, culminating in large-scale diapiric mobilization of partially molten zones from which granodioritic magmas separate. Much of the variability among magmatic systems probably reflects the depth variation of relative rates of transport of magma, heat, and volatile components, as controlled in turn by the orientation and relative magnitudes of principal stresses in the lithosphere, the thickness and composition of the affected crust, and variations in the rate and longevity of basaltic magma supply. Extension of the lithosphere may reduce the susceptibility of basaltic magmas to hybridization in the crust, but it can also enhance the role of mantle-derived volatiles in chemical transport.

Gradients in silicic magma chambers: Implications for lithospheric magmatism

Given a set of comagmatic lavas of similar composition but varying crystallinity, a diagram can be constructed using only the modes of the phenocrysts that quantitively shows the sequence of crystallization This is done by plotting the amount of each phenocryst against the total crystallinity or percentage of melt of the lava itself A histogram of the total phenocryst content measures the probability of the magma to be erupted as lava This eruption probability (P

 E
 ) is the product of the probability of finding the magma at any state of crystallinity (thermal probability, P

 T
 ) and the rheological probability (P

 R
 ) of the magma being physically able to erupt (ie P

 E
 
=P

 T
 
P

 R
 ) It is shown that P

 E
 is given by dX/dT, where X is the crystallinity of the magma as a function of temperature (T) Because crystal production is generally nonlinear—in most rocks it is step-like—P

 E
 is a bellshaped curve stradling the temperature at which the magma is one half crystallized Near the liquidus it is most favorable rheologically for the magma to erupt But the probability is small of sampling a magma near its liquidus, because it cools quickly there It is maximum when there are high rates of crystal production, because it then cools slowly As the crystallinity increases, it reaches a critical point of maximum packing (ie lowest porosity) around 50–60% crystals where it becomes rheologically impossible to erupt The magma looses its potential to become a lava and it becomes a pluton From a histogram of crystallinity and P

 T
 
,P

 R
 can be found This technique, as well as the construction of the mode-crystallization (M-C) diagram, is illustrated using a set of Aleutian lavas These lavas also show that the point of critical crystallinity decreases with increasing silica content of the lava Because this critical crystallinity is much lower for granitic magmas, they are much more probable than basaltic magmas to become plutons Beyond this point, granitic magmas can only erupt as ash flows This correlation of critical crystallinity and silica content is used to show a method by which the viscosity of the magma can be estimated as a function of crystallinity This variation is found to compare favorably with Roscoe's equation of the dependence of viscosity on the concentration of suspended solids These results show that differentiation probably can not normally take place beyond this critical crystallinity The extraction of melt beyond this critical point by filter pressing is unlikely because the assemblage dilates upon stressing Only if the phenocrysts deform viscously can additional melt be extracted, and this can probably only occur with large (−30km) bodies

On the crystallinity, probability of occurrence, and rheology of lava and magma

Crystal-size in crystalline rocks is a fundamental measure of growth rate and age. And if nucleation spawns crystals over a span of time, a broad range of crystal sizes is possible during crystallization. A population balance based on the number density of crystals of each size generally predicts a log-linear distribution with increasing size. The negative slope of such a distribution is a measure of the product of overall population growth rate and mean age and the zero size intercept is nucleation density. Crystal size distributions (CSDs) observed for many lavas are smooth and regular, if not actually linear, when so plotted and can be interpreted using the theory of CSDs developed in chemical engineering by Randolph and Larson (1971). Nucleation density, nucleation and growth rates, and orders of kinetic reactions can be estimated from such data, and physical processes affecting the CSD (e.g. crystal fractionation and accumulation, mixing of populations, annealing in metamorphic and plutonic rocks, and nuclei destruction) can be gauged through analytical modeling. CSD theory provides a formalism for the macroscopic study of kinetic and physical processes affecting crystallization, within which the explicit affect of chemical and physical processes on the CSD can be analytically tested. It is a means by which petrographic information can be quantitatively linked to the kinetics of crystallization, and on these grounds CSDs furnish essential information supplemental to laboratory kinetic studies. In this three part series of papers, Part I provides the general CSD theory in a geological context, while applications to igneous and metamorphic rocks are given, respectively, in Parts II and III.

Crystal size distribution (CSD) in rocks and the kinetics and dynamics of crystallization

Crystal size distribution (CSD) theory has been applied to drill core samples from Makaopuhi lava lake, Kilauea Volcano, Hawaii. Plagioclase and Fe-Ti oxide size distribution spectra were measured and population densities (n)were calculated and analyzed using a steady state crystal population balance equation: n=n0 exp(-L/Gτ). Slopes on ln(n) versus crystal size (L) plots determine the parameter Gτ, a. product of average crystal growth rate (G) and average crystal growth time (τ). The intercept is J/G where J is nucleation rate. Known temperature-depth distributions for the lava lake provide an estimate of effective growth time (τ), allowing nucleation and growth rates to be determined that are independent of any kinetic model. Plagioclase growth rates decrease with increasing crystallinity (9.9−5.4×10−11 cm/s), as do plagioclase nucleation rates (33.9−1.6×10−3/cm3 s). Ilmenite growth and nucleation rates also decrease with increasing crystallinity (4.9−3.4 ×10−10 cm/s and 15−2.2×10−3/cm3 s, respectively). Magnetite growth and nucleation rates are also estimated from the one sample collected below the magnetite liquidus (G =2.9×10−10 cm/s, J=7.6×10−2/cm3 s). Moments of the population density function were used to examine the change in crystallization rates with time. Preliminary results suggest that total crystal volume increases approximately linearly with time after ∼50% crystallization; a more complete set of samples is needed for material with <50% crystals to define the entire crystallization history. Comparisons of calculated crystallization rates with experimental data suggests that crystallization in the lava lake occurred at very small values of undercooling. This interpretation is consistent with proposed thermal models of magmatic cooling, where heat loss is balanced by latent heat production to maintain equilibrium cooling.

Crystal size distribution (CSD) in rocks and the kinetics and dynamics of crystallization II: Makaopuhi lava lake

holocrystalline under a wide spectrum of cooling regimes implies batch system. Instead, the CSDs of each system reflect a combination that cooling and crystallization can be uncoupled and considered of kinetic and dynamic influences on crystallization. Heterogeneous separately. This is tantamount to realizing that the Avrami number nucleation and annexation of small crystals by larger ones, enis large in most igneous systems. Crystallization automatically trainment of earlier grown and ripened crystals, rate of solidification adjusts through nucleation and growth to the cooling regime, and front advance, and protracted transit of a well-established mush all aspects of the ensuing crystal population reflect the relative roles column are some of the eVects revealed in the observed CSDs. There of nucleation and growth, which reflect the cooling regime. The may be an overall CSD evolution, reflecting the maturity of characteristic scales of crystal size, crystal number, and crys- the magmatic system, from simple straight nonkinked CSDs in tallization time are intimately tied to the characteristic rates of monogenetic systems to multiply kinked, piecewise continuous CSDs nucleation and growth, but it is the crystal size distributions (CSDs) in well-established systems such as Hawaii and Mount Etna. This that provide fundamental insight on the time variations of nucleation is not unlike the evolution of CSDs in some industrial systems. and growth and also on the dynamics of magmatic systems. Crystal Finally, the fact that comagmatic CSDs are not often captured size distributions for batch systems are calculated by employing evolving systematically through large changes in nucleation rates, the Johnson‐Mehl‐Avrami equation for crystallinity related to even in low crystallinity systems, may suggest that magma is always exponential variations in time of both nucleation and growth. The laced with high population densities of nuclei, supernuclei, and slope of the CSD is set by the diVerence a ‐ b, where a and b crystallites or clusters that together set the initial CSD at high are exponential constants describing, respectively, nucleation and characteristic population densities. Further evolution of the CSD growth. The batch CSD has constant slope and systematically occurs through sustained heterogeneous nucleation and rapid anmigrates to larger crystal size (L) with increasing crystallinity. The nealing at all crystallinities beginning at the liquidus itself and diminution in nucleation with loss of melt is reflected in the CSD operating under more or less steady (not exponentially increasing) at late times by a strong decrease in population density at small rates of nucleation. crystal sizes, which is rarely seen in igneous rocks themselves. Observed CSDs suggest that a ‐ b ~6‐10 and that b ~0. That is, growth rate is approximately constant and nucleation rate apparently increases exponentially with time. Correlations among CSD slope, intercept, and maximum crystal size for both batch and open systems suggest that certain diagnostic relations may be useful in interpreting the CSD of comagmatic sequences. These systematics are explored heuristically and through the detailed

On the Interpretation of Crystal Size Distributions in Magmatic Systems

From G. F. Becker's and L. V. Pirsson's early enunciations linking the dynamics of magma chambers to the rock records of sills and plutons to this day, two features stand at the centre of nearly every magmatic process: solidification fronts and phenocrysts. The structure and behaviour of the envisioned solidification front, however, has been mostly that akin to non-silicate, non-multiply-saturated systems, which has led to confusion in appreciating its role in magmatic evolution. The common habit of intruding magmas to carry significant amounts of phenocrysts, which can lead to efficient fractionation, layering, and interstitial melt flow within extensive mush piles, when coupled with solidification fronts, allows a broad understanding of the processes leading to the rock records of sills and lava lakes. These same processes are fundamental to understanding all magmas. The spatial manifestation of the liquidus and solidus is the Solidification Front (SF); all magmas, stationary or in transit, are encased by SFs. In the ideal case of an initially crystal-free, cooling magma, crystallinity increases from nucleation on the leading liquidus edge to a holocrystalline rock at the trailing solidus. The package of SF isotherms advances inward, thickening with time and, depending on location — roof, floor, or walls — and the initial crystallinity of the magma, is instrumental in controlling magmatic evolution. Bimodal volcanism as well as much of the structure of the oceanic crust may arise from the behaviour of SFs. In mafic magmas, somewhere near a crystallinity (N) of 55% (vol), depending on the phase assemblage, the SF changes from a viscous fluid (suspension (0<N<25) and mush (25<N<55%)) to an elastic crystalline network (rigid crust (55<N<100%)) of some strength containing interstitial residual melt. With thickening of the roofward SF of some mafic magmas, the weight of the leading, viscous portion repeatedly tears the crust near N ∼ 55–60%, efficiently segregating the local residual melt into zones of interdigitating silicic lenses. This is SF instability (SFI), a process of possible importance in continental crust initiation and evolution, in producing silicic segregations in oceanic crust, and in recording the inability of the viscous part of the upper SF ever to detach wholly in typical (<∼ 1 km) sheet-like magmas. These granophyric and pegmatitic segregations, individually reaching 1–2 m in thickness and 30–50 m in length, form thick (∼ 50–75 m) zones that can be misconstrued as sandwich horizons where the last liquids might have accumulated. In effectively splitting the magma chemically and spatially, SFI is, in essence, a form of chaos (i.e. silicic chaos). Differentiation of initially crystal-free, stationary magmas is limited to processes occurring within SFs, which operate in competition with the rate of inward advancement of solidification. Local processes operating on characteristic time scales longer than the time for the SF to advance a distance equal to its own thickness are suppressed. Enormous increases in viscosity outward within the viscous, leading portion of the SF efficiently partition the distribution of melt accessible to eruption. Eruptible melts lie essentially inward of the SF and are thus severely restricted in silica enrichment. The silica-enriched SFI melts are thus generally inaccessible to collection and eviction unless the host SF is reprocessed or “burned back” through, respectively, later regional magmatism or massive, late-stage re-injection. And because of large viscosity contrasts between SFI melts and host basalts, once freed, SFI melts are literally impossible to homogenize back into the system and may collect and compact against the roof to form large silicic masses. Unusually voluminous, bulbous masses of silicic granophyre present along, and sometimes warping, the roofs of large diabase sills may reflect collections of remobilized blobs of SFI melts. These bulbous masses may be later added to the continental crust through solid state creep. In sheets made of phenocryst-rich, singly saturated magma, most phenocrysts are able through settling or floating to avoid capture by the advancing SFs. Significant differentiation is possible through extensive settling of initial phenocrysts and upward leakage of interstitial residual melt from the associated cumulate pile, which over-thickens the lower SF, greatly tipping the competitive edge against suppression of melt leakage by advancing solidification. Dense interstitial melts may similarly drain from roofward cumulates of light phenocrysts. The variation in crystal size and modal abundance in these cumulate piles are intimate records of prior crystallization, transport, and filling. Magmas in transit erode SFs and thoroughly charge the magma with crystals, facilitating fractionation and differentiation, especially if the body occasionally comes to rest. The key to protracted differentiation through fractional crystallization is not crystallization in stationary, closed chambers, but the repeated transport and chambering of magma or the periodic resupply to chambers of phenocryst-rich magma. This is punctuated differentiation, which may be the general case. Close corollaries are that thick, closed sheets of initially crystal-free, multiply-saturated magma undergo precious little overall differentiation, and that deciphering the sequence and crystallinity, including in transit phenocryst entrainment, growth, and sorting, of the filling events is central to unravelling intrusive history. Variations in temperature, whether on phase diagrams or in actual magmas, are intrinsically linked to commensurate variations in space and time in magmatic systems. The spectrum of all physical and chemical processes associated with magma is accordingly strongly partitioned in space and time. The idea of a magma chamber as a vat of low crystallinity melt crystallizing everywhere within and differentiating through crystal settling is unrealistic. A magma chamber formed of any number of crystal-laden inputs, encased by inward-propagating, dynamic solidification fronts, and where significant differentiation is tied to the dynamics of late-stage, interstitial melt within extensive mush piles is more in accord with the rock record.

Bruce D. Marsh

Papers

On the crystallinity, probability of occurrence, and rheology of lava and magma

Crystal size distribution (CSD) in rocks and the kinetics and dynamics of crystallization

Crystal size distribution (CSD) in rocks and the kinetics and dynamics of crystallization II: Makaopuhi lava lake

On the Interpretation of Crystal Size Distributions in Magmatic Systems

Solidification fronts and magmatic evolution