E. Bruce Watson

Zircon saturation revisited : temperature and composition effects in a variety of crustal magma types

Abstract Hydrothermal experiments in the temperature range 750–1020°C have defined the saturation behavior of zircon in crustal anatectic melts as a function of both temperature and composition. The results provide a model of zircon solubility given by: In D Zr zircon/melt = −3.80−[0.85(M−1)]+12900/T where D Zr zircon/melt is the concentration ratio of Zr in the stoichiometric zircon to that in the melt, T is the absolute temperature, and M is the cation ratio (Na + K + 2Ca)/(Al · Si). This solubility model is based principally upon experiments at 860°, 930°, and 1020°C, but has also been confirmed at temperatures up to 1500°C for M = 1.3. The lowest temperature experiments (750° and 800°C) yielded relatively imprecise, low solubilities, but the measured values (with assigned errors) are nevertheless in agreement with the predictions of the model. For M = 1.3 (a normal peraluminous granite), these results predict zircon solubilities ranging from ∼ 100 ppm dissolved Zr at 750°C to 1330 ppm at 1020°C. Thus, in view of the substantial range of bulk Zr concentrations observed in crustal granitoids (∼ 50–350 ppm), it is clear that anatectic magmas can show contrasting behavior toward zircon in the source rock. Those melts containing insufficient Zr for saturation in zircon during melting can have achieved that condition only by consuming all zircon in the source. On the other hand, melts with higher Zr contents (appropriate to saturation in zircon) must be regarded as incapable of dissolving additional zircon, whether it be located in the residual rocks or as crystals entrained in the departing melt fraction. This latter possibility is particularly interesting, inasmuch as the inability of a melt to consume zircon means that critical geochemical “indicators” contained in the undissolved zircon (e.g. heavy rare earths, Hf, U, Th, and radiogenic Pb) can equilibrate with the contacting melt only by solid-state diffusion, which may be slow relative to the time scale of the melting event.

Partial melting of amphibolite/eclogite and the origin of Archean trondhjemites and tonalites

The generation of trondhjemites and tonalites on a massive scale during the Archean (3.8-2.5 Ga ago) marked the transition from a simatic to a sialic crust, and represents the magmatic contribution to cratonization. Petrogenetic models for the origin of these rocks based on their highly fractionated, HREE-depleted rare earth patterns suggest a mafic crustal source, either through a process of partial melting of amphibolite, garnet-amphibolite, or eclogite, in which hornblende and/or garnet are essential residual phases, or by hornblende-controlled fractionation of hydrous basaltic magma. A series of vapor-absent (i.e., Pfluid< Ptotal) melting experiments on four natural basaltic compositions were conducted at 8, 16, 22 and 32 kbar in order to assess the validity of models for the origin of Archean granitoids which assume a mafic crustal source. Melt compositions produced by 10–40% melting are tonalitic-trondhjemitic at all pressures investigated; residual assemblages are amphibole+plag±opx±FeTi at 8 kbar, garnet+cpx±amphibole±plag±opx±FeTi oxide at 16 kbar, and garnet+cpx±rutile at 22 and 32 kbar. REE patterns for most of the trondhjemitic-tonalitic partial melts, calculated on the basis of estimated modal proportions of melt and residual phases, are highly fractionated (LaYb is 30–50), heavy rare earth-depleted (YbN is 1–10) when garnet is present to some extent in the residue; these REE patterns are similar to those of trondhjemitic and tonalitic gneisses from several Archean “grey gneiss” and granite-greenstone terrains. A consideration of estimated Archean geotherms with respect to the experimental P-T conditions indicates that a temporally diminishing Archean geotherm might have progressively swept through a P-T regime in which trondhjemitic-tonalitic melts could have been generated initially from a water-saturated (Pf=Pt) to undersaturated (Pf<Pt) amphibolite source by partial melting at 5–8 kbar. Subsequent relaxation of the geotherm through the mid- to late-Archean would have produced similar melts by vapor-absent melting of garnet-amphibolite at 16 kbar and eclogite at 22–32 kbar. However, the degree of melting required to produce melts of trondhjemitic-tonalitic composition increases with pressure, 10–15% melting being appropriate at 8 kbar in a amphibole-dominated residue, but 25–35% melting being required at 22–32 kbar, where garnet dominates the residue. Supposing the tendency for melt segregation and/or magma mobilization mechanisms to be more effective at higher degrees of melting, an origin by partial melting of eclogite seems to be the most likely source for massive plutonic trondhjemite-tonalite contributions to the juvenile continents. Such a source is consistent with the generation of trondhjemite-tonalite protocontinental cores in any number of plausible Archean tectono-thermal scenarios, though not necessarily in a conventional subduction-zone setting.

The behavior of apatite during crustal anatexis: Equilibrium and kinetic considerations

The solubility and dissolution kinetics of apatite in felsic melts at 850°–1500°C have been examined experimentally by allowing apatite crystals to partially dissolve into apatite-undersaturated melts containing 0–10 wt% water. Analysis of P and Ca gradients in the crystal/melt interfacial region enables determination of both the diffusivities and the saturation levels of these components in the melt. Phosphorus diffusion was identified as the rate-limiting factor in apatite dissolution. Results of four experiments at 8 kbar run in the virtual absence of water yield an activation energy (E) for P diffusion of 143.6 ± 2.8 kcal-mol−1 and frequency factor (D0) of 2.23+2.88−1.26 × 109cm2-sec−1. The addition of water causes dramatic and systematic reduction of both E and D0 such that at 6 wt% H2O the values are ~25 kcal-mol−1 and 10−5 cm2-sec−1, respectively. At 1300°C, the diffusivity of P increases by a factor of 50 over the first 2% of water added to the melt, but rises by a factor of only two between 2 and 6%, perhaps reflecting the effect of a concentration-dependent mechanism of H2O solution. Calcium diffusion gradients do not conform well to simple diffusion theory because the release of calcium at the dissolving crystal surface is linked to the transport rate of phosphorus in the melt, which is typically two orders of magnitude slower than Ca. Calcium chemical diffusion rates calculated from the observed gradients are about 50 times slower than calcium tracer diffusion. Apatite solubilities obtained from these experiments, together with previous results, can be described as a function of absolute temperature (T) and melt composition by the expression: In Dapatite/meltP = [(8400 + ((SiO2 − 0.5)2.64 × 104))/T] − [3.1 + (12.4(SiO2 − 0.5))] where SiO2 is the weight fraction of silica in the melt. This model appears to be valid between 45% and 75% SiO2, 0 and 10% water, and for the range of pressures expected in the crust. The diffusivity information extracted from the experiments can be directly applied to several problems of geochemical interest, including I) dissolution times for apatite during crustal anatexis, and 2) pileup of P, and consequent local saturation in apatite, at the surfaces of growing major-mineral phases.

Fluids in the lithosphere, 1. Experimentally-determined wetting characteristics of CO2H2O fluids and their implications for fluid transport, host-rock physical properties, and fluid inclusion formation

Abstract The equilibrium distribution of CO2 H2O fluids in synthetic rock samples (principally dunite and quartzite) has been characterized by measurements of the dihedral wetting angle, θ, resulting from 5-day annealing periods at 950–1150°C and 1 GPa. For fluids in equilibrium with polycrystalline quartz, θ varies systematically from ∼ 57° for pure H2O to ∼ 90° at XCO2 ∼ 0.9. Similarly, for San Carlos olivine, θ varies from ∼ 65° for pure H2O to ∼ 90° at XCO2 ∼ 0.9. The addition of solutes (NaCl, KCl, CaF2, Na2CO3) to H2O causes a major decrease in θ in the quartz/fluid system (to values as low as 40°), but has no effect on fluid wetting in dunite. Reconnaissance experiments on other mono- and polymineralic aggregates indicate universally high wetting angles (θ ≫ 60°) in upper mantle assemblages and for CO2 in felsic compositions. For diopside + H2O, θ ∼ 80°, with large variation due to crystalline anisotropy. In no case does θ approach 0°, the condition necessary for fluid to be present along all grain boundaries. Because a value of θ greater than 60° precludes the existence of an interconnected fluid phase in a rock, our results have important implications not only for fluid transport but also for the physical properties of the bulk fluid/rock system. Any static fluid present in the upper mantle must exist as isolated pores located primarily at grain corners, and transport can occur only by hydrofracture. In the continental crust, aqueous fluids (especially saline ones) are likely to form an interconnected network along grain edges, thus contributing to high electrical conductivity and allowing the possibility of fluid transport by porous flow or surface energy-driven infiltration.

Zircon saturation in felsic liquids: Experimental results and applications to trace element geochemistry

Hydrothermal experiments were carried out at 2 kbar water pressure, 700 °–800 ° C, with the objective of determining the level of dissolved Zr required for precipitation of zircon from melts in the system SiO2-Al2O3-Na2O-K2O. The saturation level depends strongly upon molar (Na2O + K2O)/Al2O3 of the melts, with remarkably little sensitivity to temperature, SiO2 concentration, or melt Na2O/ K2O. For peraluminous melts and melts lying in the quartz-orthoclase-albite composition plane, less than 100 ppm Zr is required for zircon saturation. In peralkaline melts, however, zircon solubility shows pronounced, apparently linear, dependence upon (Na2O + K2O)/Al2O3, with the amount of dissolvable Zr ranging up to 3.9 wt.% at (Na2O + K2O)/Al2O3 = 2.0. Small amounts (1 wt.% each) of dissolved CaO and Fe2O3 cause a 25% relative reduction of zircon solubility in peralkaline melts.The main conclusion regarding zirconium/zircon behavior in nature is that any felsic, non-peralkaline magma is likely to contain zircon crystals, because the saturation level is so low for these compositions. Zircon fractionation, and its consequences to REE, Th, and Ta abundances must, therefore, be considered in modelling the evolution of these magmas. Partial melting in any region of the Earths crust that contains more than ∼ 100 ppm Zr will produce granitic magmas whose Zr contents are buffered at constant low (< 100 ppm) values; unmelted zircon in the residual rock of such a melting event will impart to the residue a characteristic U- or V-shaped REE abundance pattern. In peralkaline, felsic magmas such as those that form pantellerites and comendites, extreme Zr (and REE, Ta) enrichment is possible because the feldspar fractionation that produces these magmas from non-peralkaline predecessors does not drive the melt toward saturation in zircon.Zircon solubility in felsic melts appears to be controlled by the formation of alkali-zirconosilicate complexes of simple (2:1) alkali oxide: ZrO2 stoichiometry.

Two-liquid partition coefficients: Experimental data and geochemical implications

Partition coefficients for Cs, Ba, Sr, Ca, Mg, La, Sm, Lu, Mn, Ti, Cr, Ta, Zr, and P between immiscible basic and acidic liquids in the system K2O-Al2O3-FeO-SiO2 were experimentally determined at 1,180 °C and 1 atm. Phosphorus is most strongly enriched in the basic melt (by a factor of 10), followed by rare earth elements, Ta, Ca, Cr, Ti, Mn, Zr, Mg, Sr, and Ba (enriched by a factor of 1.5). Of the elements studied, only Cs is enriched in the acidic melt. The two-liquid partition coefficients of Zr, Ta, Sm, and Mn are constant for concentrations ranging from <0.1% to as high as 1 wt.-%, suggesting that Henrys law is applicable in silicate melts (at least for these elements) to concentrations well above typical trace element levels in rocks. The strong relative preference of many elements for the basic melt implies that the structural characteristics of basic melts more readily permit stable coordination of cations by oxygen. Partitioning of elements between crystal and liquid in a magma must therefore be influenced by the composition (and consequent structure) of the liquid.Application of the two-liquid partition coefficients to possible occurrences of liquid immiscibility in magmas reveals that typical basalt-rhyolite associations are probably not generated by two-liquid phase separation. However, liquid immiscibility cannot be discounted as a possible origin for lamprophyric rocks containing felsic segregations.

Apatite/liquid partition coefficients for the rare earth elements and strontium

Abstract Sixteen sets of apatite/liquid partition coefficients (Dap/liq) for the rare earth elements (REE; La, Sm, Dy, Lu) and six values for Sr were experimentally determined in natural systems ranging from basanite to granite. The apatite + melt (glass) assemblages were obtained from starting glasses artificially enriched in REE, Sr and fluorapatite components; these were run under dry and hydrous conditions of 7.5–20 kbar and 950–1120°C in a solid-media, piston-cylinder apparatus. An SEM-equipped electron microprobe was used for subsequent measurement of REE and Sr concentrations in coexisting apatites and quenched glasses. The resulting partition coefficient patterns resemble previously determined apatite phenocryst/groundmass concentration ratios in the following respects: (1) the rare earth patterns are uniformly concave downward (i.e., the middle REE are more compatible in apatite than the light and heavy REE); (2) DREEap/liq is much higher for silicic melts than for basic ones; and (3) strontium (and therefore Eu2+) is less concentrated by apatite than are the trivalent REE. The effects of both temperature and melt composition on DREEap/liq are systematic and pronounced. At 950°C, for example, a change in melt SiO2 content from 50 to 68 wt.% causes the average REE partition coefficient to increase from ∼7 to ∼30. A 130°C increase in temperature, on the other hand, results in a two-fold decrease in DREEap/liq. Partitioning of Sr is insenstitive to changes in melt composition and temperature, and neither the Sr nor the REE partition coefficients appear to be affected by variations in pressure or H2O content of the melt. The experimentally determined partition coefficients can be used not only in trace element modelling, but also to distinguish apatite phenocrysts from xenocrysts in rocks. Reported apatite megacryst/host basalt REE concentration ratios [12], for example, are considerably higher than the equilibrium partition coefficients, which suggest that in this particular case the apatite is actually xenocrystic. A reversal experiment incorporated in our study yielded diffusion profiles of REE in apatite, from which we extracted a REEαCa interdiffusion coefficient of 2–4×10−14 cm2/s at 1120°C. Extrapolated downward to crustal temperatures, this low value suggests that complete REE equilibrium between felsic partial melts and residual apatite is rarely established.

Basalt contamination by continental crust: Some experiments and models

Chemical interaction between molten basalt and felsic minerals of the continental crust (quartz, K-feldspar, and oligoclase) was examined in static and dynamic experiments at 1,200°–1,400° C. Under circumstances of continuous stirring at 1,400°, β-quartz dissolves in tholeiite melt at a rate of 3.3×10−6 g/s per cm2 of contact area; at 1,300°, the solution rate is 1.5×10−6 g/cm{cm2}s. The feldspars are molten at the experimental conditions, and interact with contacting basalt melt by diffusion in the liquid state. This is a complex process characterized by rapid initial diffusion of alkalies to establish a distribution between felsic melt and basalt similar to that observed in cases of actual two-liquid equilibrium (both alkalies reach concentrations in the felsic melt 1.5–3 times those in the basalt). Alkali diffusion may be “uphill” or “downhill”, depending on which direction of net flux is required to produce a two-liquid type distribution. Once this distribution is attained, subsequent diffusion of all melt species is slow and apparently limited by the diffusivity of SiO2, which is 10−9-l0−10 cm2/s at 1,200° C. Interdiffusion experiments involving molten basalt and synthetic granite confirm the behavior illustrated by the feldspar/basalt results, and give similar SiO2 diffusivities.The solution rates and interdiffusion data can be used to model basalt contamination processes likely to occur in the continental crust. For the restricted case of solid quartzitic xenoliths, the uptake of SiO2 in a well-mixed basalt magma is quite fast: appreciable SiO2 contamination may occur over exposure times of only days to years. If basalt magma induces local melting of crustal rocks, the assimilation process becomes one of liquid-state interdiffusion. In this case, the varying diffusivities of ions and their differing preferences for silicic relative to basaltic melts can produce marked selective contamination effects. Selective contamination of ascending basaltic magmas is particularly likely in the case of K2O, which may be introduced in substantial amounts even when other elements remain unaffected. The Na2O content of mantle-derived magmas is buffered against contamination by crustal materials, and K2O is buffered against further increases once it reaches a level of 1–1.5 wt.%.

Diffusion in Zircon

Despite its low abundance in most rocks, zircon is extraordinarily useful in interpreting crustal histories. The importance of U-Th-Pb isotopic dating of zircon is well and long established (Davis et al., this volume; Parrish et al., this volume). Zircon also tends to incorporate trace elements useful as geochemical tracers, such as the REE, Y, and Hf. A number of characteristics of zircon encourage the preservation of internal isotopic and chemical variations, often on extremely fine scale, which provide valuable insight into thermal histories and past geochemical environments. The relative insolubility of zircon in crustal melts and fluids, as well as its general resistance to chemical and physical breakdown, often result in the existence of several generations of geochemical information in a single zircon grain. The fact that this information is so frequently retained (as evidenced through backscattered electron or cathodoluminescence imaging that often reveal fine-scale zoning down to the sub-micron scale) has long suggested that diffusion of most elements is quite sluggish in zircon. In this chapter, we present an overview of the findings to date from laboratory measurements of diffusion of cations and oxygen in zircon. Because of its importance as a geochronometer, attempts have been made to measure diffusion (especially of Pb) for over 30 years. But only in the last decade or so have profiling techniques with adequate depth resolution been employed in these studies, resulting in a plethora of new diffusion data. These findings have important implications for isotopic dating, interpretation of stable-isotope ratios, closure temperatures, and formation and preservation of primary chemical composition and zoning in zircon. Efforts have been made for some time to quantify and characterize diffusion in zircon, most notably of Pb, in deference to its significance in interpreting Pb isotopic signatures and refining understanding of thermal histories. As is evident from …

Kinetics of zircon dissolution and zirconium diffusion in granitic melts of variable water content

The experimental dissolution of zircon into a zircon-undersaturated felsic melt of variable water content at high pressure in the temperature range 1,020° to 1,500° C provides information related to 1) the solubility of zircon, 2) the diffusion kinetics of Zr in an obsidian melt, and 3) the rate of zircon dissolution. Zirconium concentration profiles observed by electron microprobe in the obsidian glass adjacent to a large, polished zircon face provide sufficient information to calculate model diffusion coefficients. Results of dissolution experiments conducted in the virtual absence of water (<0.2% H2O) yield an activation energy (E) for Zr transport in a melt ofM=1.3 [whereM is the cation ratio (Na+K+2Ca)/(Al·Si)] of 97.7±2.8 kcal-mol−1, and a frequency factor (D0) of 980−580+1,390 cm2-sec−1. Hydrothermal experiments provide an E=47.3±1.9 kcal-mol−1 andD0=0.030−0.015+0.030 cm2-sec−1. Both of these results plot close to a previously defined diffusion compensation line for cations in obsidian. The diffusivity of Zr at 1,200° C increases by a factor of 100 over the first 2% of water introduced into the melt, but subsequently rises by only a factor of five to an apparent plateau value of ∼2×10−9 cm2-sec−1 by ∼6% total water content. The remarkable contrast between the wet and dry diffusivities, which limits the rate of zircon dissolution into granitic melt, indicates that a 50 μm diameter zircon crystal would dissolve in a 3 to 6% water-bearing melt at 750° C in about 100 years, but would require in excess of 200 Ma to dissolve in an equivalent dry system. From this calculation we conclude that zircon dissolution proceeds geologically instantaneously in an undersaturated, water-bearing granite. Estimates of zircon solubility in the obsidian melt in the temperature range of 1,020° C to 1,500° C confirm and extend an existing model of zircon solubility to these higher temperatures in hydrous melts. However, this model does not well describe zircon saturation behavior in systems with less than about 2% water.