Effect of melt composition on the partitioning of trace elements between titanite and silicate melt

Isobaric and isothermal experiments were performed to investigate the effect of melt composition on the partitioning of trace elements between titanite (CaTiSiO₅) and a range of different silicate melts. Titanite-melt partition coefficients for 18 trace elements were determined by secondary ion mass spectrometry (SIMS) analyses of experimental run products. The partition coefficients for the rare earth elements and for Th, Nb, and Ta reveal a strong influence of melt composition on partition coefficients, whereas partition coefficients for other studied monovalent, divalent and most quadrivalent (i.e., Zr, Hf) cations are not significantly affected by melt composition. The present data show that the influence of melt composition may not be neglected when modelling trace element partitioning.It is argued that it is mainly the change of coordination number and the regularity of the coordination space of trace elements in the melt structure that controls partition coefficients in our experiments. Furthermore, our data also show that the substitution mechanism by which trace elements are incorporated into titanite crystals may be of additional importance in this context.     

Geochemical and Sm–Nd isotopic study of titanite from granitoid rocks of the eastern Dharwar craton,southern India

Titanite occurs as an accessory phase in a variety of igneous rocks, and is known to concentrate geologically important elements such as U, Th, rare earth element (REE), Y and Nb. The differences in the abundances of the REEs contained in titanite from granitoid rocks could reflect its response to changes in petrogenetic variables such as temperature of crystallization, pressure, composition, etc. Widespread migmatization in the granodiorite gneisses occurring to the east of Kolar and Ramagiri schist belts of the eastern Dharwar craton resulted in the enrichment of the REEs in titanite relative to their respective host rocks. A compositional influence on the partitioning of REEs between titanite and the host rock/magma is also noticed. The relative enrichment of REEs in titanite from quartz monzodiorite is lower than that found in the granodioritic gneiss. Depletion of REE and HFSE (high field-strength elements) abundances in granitic magmas that have equilibrated with titanite during fractional crystallization or partial melting has been modelled. As little as 1% of titanite present in residual phases during partial melting or in residual melts during fractional crystallization can significantly lower the abundances of trace elements such as Nb, Y, Zr and REE which implies the significance of this accessory mineral as a controlling factor in trace element distribution in granitoid rocks. Sm–Nd isotope studies on titanite, hornblende and whole rock yield isochron ages comparable to the precise U–Pb titanite ages, invoking the usefulness of Sm–Nd isochron ages involving minerals like titanite.     

Kinetically induced compositional zoning in titanite: implications for accessory-phase/melt partitioning of trace elements

Usually it is assumed that the partitioning of trace elements into titanite in metaluminous granitoid plutonic environments takes place under equilibrium conditions and that compositional zoning is due solely to progressive changes in melt chemistry and/or mineral/melt partition coefficients. Examination of titanites from a variety of Caledonian metaluminous granitoids and related rocks has revealed that sector zoning is present, indicating disequilibrium partitioning. The sector zoning in titanites is defined principally by the distribution of the rare earth elements (REE), Y, Nb, Al and Fe. The REE, Y and Nb preferentially occur within the minor (100) sectors relative to the morphologically important (111) sectors. The reverse is true of Al and Fe which preferentially occur within the (111) sectors relative to the (100) sectors. The patterns of sector zoning are complicated by the fact that the relative growth rates of the various crystal faces fluctuated during growth. Sector zoning indicates that crystal-interface kinetics are responsible for the observed patterns of element partitioning. It is concluded that differences in the lateral-layerspreading rates of crystal faces bring about the sector zoning. The results have implications for the use of trace element partition coefficients in the modelling of fractionation processes.     

An ion microprobe study of the partitioning of trace elements between clinopyroxene and liquid in the system diopside-albite-anorthite

The partitioning of trace elements (Sc, Ti, Sr and Sm) between diopsidic clinopyroxene and liquid was studied experimentally in the system diopside-albite-anorthite at 1250°C, 1300°C and 1345°C at 1 atm. Twelve different bulk compositions were selected to study the effects of temperature and chemical composition. A Cameca ion microprobe was used to determine trace element concentrations in both clinopyroxene and liquid. Experiments of different run duration $\text{1}\text{4}\text{8}\text{?}$ days) showed that equilibrium was approached in less than 4 days at 1275°C. Equilibrium was also evaluated by a reversal run. A series of runs of constant bulk composition but with variable trace element contents showed that Henry's Law was obeyed over concentration ranges of the trace elements similar to those encountered in natural systems. The partition coefficients show significant ranges: Sc, 0.345~2.61; Ti, 0.084~0.214; Sr, 0.075~0.136; Sm, 0.054~0.328; the values are comparable with those obtained experimentally by other investigators. The partition coefficients vary as a function of both temperature and chemical composition. The experimental results are discussed in terms of exchange equilibria using the Bottinga-Weill silicate melt model. It is demonstrated that analytical uncertainties of both major and trace elements play an important role in understanding trace element exchange equilibria; propagation of analytical errors in the thermodynamic treatment is equally important.     

Partition coefficients for REE between garnets and liquids: implications of non-Henry's Law behaviour for models of basalt origin and evolution

Partition coefficients for the rare earth elements (REE) Ce, Sm and Tm between coexisting garnets and hydrous liquids have been determined at high pressure and temperatures (30 kbar and 1300 and 1500°C). Two synthetic systems were studied, Mg₃Al₂Si₃O₁₂-H₂O and Ca₃Al₂Si₃O₁₂-H₂O, in addition to a natural pyrope-bearing system.Deviations from Henry's Law behaviour occur at geologically relevant REE concentrations. At concentrations < 3 ppm Ce, < 12 ppm Sm, < 80 ppm Tm in pyrope and < 100 ppm Ce, < 250 ppm Sm, < 1000 ppm Tm in grossular (at 30 kbar and 1300°C), D^{garnet liquid}_REE increases as the REE concentration in the garnet decreases. At higher concentrations, D_REE is constant. D^{grossular liquid}_REE also constant when the garnet contains less than about 2 ppm Sm or Tm. The REE concentration at which D_REE becomes constant increases with increasing temperature, decreasing REE ionic radius and increasing Ca content of the garnet.Partitioning behaviour of Ce, Sm and Tm between a natural pyrope-rich garnet and hydrous liquid is analogous to that in the synthetic systems and substantiates the substitution model proposed by Harrison and Wood (1980).Values of D_REE^{garnet/liquid} for which Henry's Law is obeyed are systematically higher for grossular than for pyrope (D^{pyrope/liquid} = 0.067(Ce), 0.108(Sm), 0.155(Tm) and D^{grossular/Liquid} = 0.65(Ce), 0.75(Sm), 4.55(Tm).The implications of non-Henry's Law partitioning of REE for models of basalt petrogenesis involving garnet are far-ranging. Deviations from Henry's Law permit refinements to be made to calculated REE abundances once basic model parameters have been defined.     

Limits of solution of trace elements in minerals according to Henry's law: Review of experimental data

Results of a survey of experimental data on trace element partitioning between crystals and coexisting liquid and between crystals and coexisting aqueous fluid are reported. These studies involve combinations of elements such as Cs, Rb, K, Na, Li, Ba, Sr, Ni and Sm dissolved in minerals such as feldspars, micas, feldspathoids, garnets, pyroxenes, amphibole and olivine. It is shown that the concentration ranges of these elements in minerals with solution behavior according to Henry's law appear to extend to less than 1 wt.% and often to less than 100 ppm of the element in the crystalline phase.The available data indicate that the concentration ranges of solution in minerals according to Henry's law can be positively correlated with the difference of ionic radii between trace element and the host element for which the tracer is assumed to substitute. Furthermore, studies involving crystals and coexisting aqueous fluid have been used to determine whether Henry's law or Raoult's law adequately describes the solution. Based on the assumption that the aqueous fluid solution can be considered ideal, models have been proposed stating that if the difference between the ionic radii of the tracer and the host element in the crystalline phase is less than about 10% (relative to the host element), the solution is ideal (Raoult's law). With larger differences between the ionic radii, there is an excess free energy of mixing, although Henry's law is still obeyed in the concentration ranges where crystalliquid or crystal-fluid partition coefficients are independent of element concentration.     

Silicate perovskite-melt partitioning of trace elements and geochemical signature of a deep perovskitic reservoir

We have determined the partitioning of a wide range of trace elements between silicate melts and CaSiO₃ and MgSiO₃ perovskites using both laser ablation-ICPMS and ion microprobe techniques. Our results show that, with the exception of Sc, Zr, and Hf, all trace elements we considered are incompatible in MgSiO₃ perovskite, from highly incompatible for U, Th, Ba, La, Sr and monovalent elements to slightly incompatible for heavy rare earth elements. MgSiO₃ perovskite-melt partition coefficients increase slightly with Al content in the perovskite. These observations contrast strongly with partitioning between CaSiO₃ perovskite and silicate melts. In the latter case, all rare earth elements are clearly compatible as are U and Th. Our data also suggest that, contrary to pressure and temperature, melt composition can significantly affect CaSiO₃ perovskite-melt partitioning; partition coefficients for rare earth elements and U and Th increase with decreasing CaO melt content. The presence of ∼0.4 wt% water in melt makes little difference, however. Partitioning of trace elements into the large site of both MgSiO₃ and CaSiO₃ perovskites follows the near-parabolic dependence on ionic radius predicted from the lattice strain model. The peaks of the parabolae are much higher for the CaSiO₃ phase, perhaps suggesting that the mechanisms of charge compensation for heterovalent substitution are different in the two cases. Our partitioning data have been used to assess the potential effect of perovskite fractionation into the lower mantle during early Earth history. Crystallisation of less than 8% of a mixture of CaSiO₃ and MgSiO₃ perovskites could have led to a ‘layer’ enriched in U and Th without disturbing the chondritic pattern of refractory lithophile elements in the primitive upper mantle. The resultant reservoir could have high Sm/Nd, U/Pb, Sr/Rb, Lu/Hf ratios similar to the HIMU component of ocean island basalts, but would not balance the observed depletion of the primitive upper mantle in Si and Nb.     

Trace element partitioning and substitution mechanisms in calcium perovskites

We have determined the partition coefficients of a large number of trace elements between CaTiO₃ perovskite and anhydrous silicate melts at atmospheric pressure and 3 GPa. Determination of the concentration limits of Henrys law behaviour in the CaO-Al₂O₃–SiO₂–TiO₂ system reveals that the incorporation of rare earth elements (REE) and tetravalent large ion lithophile elements (LILE⁴⁺ such as U and Th) at the Ca-site of CaTiO₃ perovskite occurs with charge compensation through Ca-vacancy formation rather than by coupled substitution of Al for Ti. When melt composition is varied, we find that partition coefficients for REE and Th are strong functions of the CaO content of the melt. The observed trends are in excellent agreement with those predicted from the Ca-vacancy model. Given that they adopt the same crystal structure and have similar trace element partitioning behaviour, CaTiO₃ perovskite and the deep mantle phase CaSiO₃ perovskite can be considered analogous to one another. When the analogy is pursued in detail, we find that partitioning into both phases follows the composition-dependence predicted by the Ca-vacancy model. Thus, substitution of REE, U⁴⁺ and Th into CaSiO₃ in the lower mantle also occurs with Ca-vacancy formation to balance charge. Furthermore when 2+, 3+ and 4+ partition coefficients for both phases are plotted as functions of CaO melt content, the trends for CaSiO₃ and CaTiO₃ appear to be continuous. This surprising result means that partitioning into Ca-perovskite is independent of pressure and temperature and also of whether or not the host is CaSiO₃ or CaTiO₃. One implication is that CaSiO₃ crystallising from a peridotitic magma ocean may have partition coefficients for Th and U up to about 400. Crystallisation and sequestration of as little as 0.25 volume% of this phase in the lower mantle early in earth history would make a significant contribution to current mantle heat production.Electronic Supplementary Material Supplementary material is available for this article at     

Identifying Accessory Mineral Saturation during Differentiation in Granitoid Magmas: an Integrated Approach

Numerical reconstructions of processes that may have operatedduring igneous petrogenesis often model the behaviour of importanttrace elements. The geochemistry of these trace elements maybe controlled by accessory mineral saturation and fractionation.Determination of the saturation point of accessory mineralsin granitoid rocks is ambiguous because assumptions about crystalmorphology and melt compositions do not always hold. An integratedapproach to identifying accessory mineral saturation involvingpetrography, whole-rock geochemical trends, saturation calculationsand mineral chemistry changes is demonstrated here for a compositionallyzoned pluton. Within and between whole-rock samples of the BoggyPlain zoned pluton, eastern Australia, the rare earth element(REE)-enriched accessory minerals zircon, apatite and titaniteexhibit compositional variations that are related to saturationin the bulk magma, localized saturation in intercumulus meltpools and fractionation of other mineral phases. Apatite isidentified as having been an early crystallizing phase overnearly the whole duration of magma cooling, with zircon (andallanite) only saturating in more felsic zones. Titanite andmonazite did not saturate in the bulk magma at any stage ofdifferentiation. Although some trace elements (P, Ca, Sc, Nb,Hf, Ta) in zircon exhibit compositional variation progressingfrom mafic to more felsic whole-rock samples, normalized REEpatterns and abundances (except Ce) do not vary with progressivedifferentiation. This is interpreted to be a result of limitationsto both simple ‘xenotime’ and complex xenotime-typecoupled substitutions. Our data indicate that zircon REE characteristicsare not as useful as those of other REE-rich accessory mineralsas a petrogenetic indicator. KEY WORDS: saturation; zircon; apatite; titanite; magma differentiation; trace elements; REE patterns     

Equilibrium vs. disequilibrium melting relations in theHigher Himalayan Crystalline (HHC) pelitic migmatites,Sikkim Himalaya

Higher Himalayan Crystalline (HHC) complex of the Sikkim Himalaya predominantly consists of high-grade pelitic migmatites. In this study, reaction textures, mineral/bulk rare earth elements (REE), trace element partition coefficients and trace element zoning profiles in garnet are used to demonstrate a complex petrogenetic process during crustal anatexis. With the help of equilibrium REE and trace element partitioning model, it is shown that strong enrichment of Effective Bulk Composition (EBC) is responsible for the zoning in garnet in these rocks. The data strongly support disequilibrium element partitioning and suggest that the anatectic melts associated with mafic selvedges are likely produced by disequilibrium melting because of fast melt segregation process.     

皖南姚村岩体花岗岩风化壳稀土元素赋存特征

皖南地区花岗岩风化壳中稀土元素普遍富集，局部已成为矿床，其中，郎溪县姚村岩体风化壳富集程度较高。LA- ICP- MS锆石U- Pb定年表明，姚村花岗岩体的形成年龄为127.9±1.4 Ma，属于皖南地区燕山期晚期岩浆作用的产物。风化壳可细分为残坡积层（A）、强半风化层（C1）、过渡层（C2）、弱风化层（C3）和基岩（D）五层。稀土总量在纵向剖面上呈“波浪式”分布，各层稀土分布型式表现出对原岩的继承性。风化壳稀土配分型式与基岩一致， 富集LREE，轻重稀土分馏明显(La/Yb)N=15.6），但总含量明显更高。基岩∑REE为338×10-6，半风化层∑REE最高达642×10-6，富集约两倍。风化壳物质由风化残余主矿物（石英、钾长石、斜长石、黑云母）、黏土矿物（高岭石、埃洛石、伊利石、三水铝石等）和副矿物（锆石、磷灰石、榍石等）等组成。黏土矿物以伊利石含量最高，指示风化壳发育不成熟。REE与埃洛石含量明显正相关，与其他黏土矿物关系不明显。（含）稀土矿物（尤其是榍石）对风化壳中稀土元素的贡献量超过百分之五十，其次为斜长石，是风化壳中REE的重要来源。     

皖南姚村岩体花岗岩风化壳稀土元素赋存特征

皖南地区花岗岩风化壳中稀土元素普遍富集，局部已成为矿床，其中，郎溪县姚村岩体风化壳富集程度较高。LA- ICP- MS锆石U- Pb定年表明，姚村花岗岩体的形成年龄为127. 9±1. 4 Ma，属于皖南地区燕山期晚期岩浆作用的产物。风化壳可细分为残坡积层（A）、强半风化层（C1）、过渡层（C2）、弱半风化层（C3）和基岩（D） 5层。稀土总量在纵向剖面上呈“波浪式”分布，各层稀土分布型式表现出对原岩的继承性。风化壳稀土配分型式与基岩一致， 富集LREE，轻重稀土分馏明显\[(La/Yb)N=15. 6\]，但总含量明显更高。基岩∑REE为338×10-6，半风化层∑REE最高达642×10-6，富集约两倍。风化壳物质由风化残余主矿物（石英、钾长石、斜长石、黑云母）、黏土矿物（高岭石、埃洛石、伊利石、三水铝石等）和副矿物（锆石、磷灰石、榍石等）等组成。黏土矿物以伊利石含量最高，指示风化壳发育不成熟。REE与埃洛石含量明显正相关，与其他黏土矿物关系不明显。（含）稀土矿物（尤其是榍石）对风化壳中稀土元素的贡献量超过 50%，其次为斜长石，是风化壳中REE的重要来源。     

Non-Henry’s Law behavior of REE partitioning between fluorapatite and CaF2-rich melts: Controls of intrinsic vacancies and implications for natural apatites

The partitioning of rare-earth elements (REEs: Gd and multiple REEs), Sr, and Mn between fluorapatite and CaF₂-rich melts was investigated over a wide range of REE concentrations (i.e., from 0.8 ± 0.1 to 25,000 ± 2600 ppm Gd in fluorapatite) in two different sample assemblies (i.e., tightly covered Pt crucibles and sealed Pt capsules) at 1220 °C and atmospheric pressure. Attainment of equilibrium is indicated by selected reversal experiments. The partition coefficient D(Gd) decreases from ∼2 to ∼0.5 with increasing Gd in fluorapatite, hence a marked non-Henry’s Law behavior, but becomes independent of composition at and above ∼5000 and ∼1000 ppm Gd for experiments in Pt crucibles and Pt capsules, respectively. Non-Henry’s Law behavior is also observed in experiments involving multiple REEs. All REE patterns are convex upward in shape with maxima between Nd and Gd, and D(La)/D(Nd) and D(Nd)/D(Yb) decrease systematically with increasing total REEs in fluorapatite, suggesting that REE fractionations are partly related to non-Henry’s Law behavior. These experimental results and local structural data from previous electron paramagnetic resonance spectroscopic studies suggest that the non-Henry’s Law behavior of REE partitioning between fluorapatite and melt is controlled by intrinsic Ca²⁺ vacancies in the c-axis channels. The D(Sr) and D(Mn) values are independent of composition and, therefore, do not deviate from the Henry’s Law in their respective compositional ranges investigated in this study.Nonstoichiometry, such as Ca²⁺ and F⁻ vacancies in the c-axis channels, is well known in natural apatites, particularly in biogenic apatites. Therefore, the observed non-Henry’s Law behavior of REE partitioning is expected to have important implications for REE geochemical modeling involving apatites and for the uptake of REEs by natural apatites. Particularly, the non-Henry’s Law behavior of REE partitioning is at least partly responsible for the commonly observed, bell-shaped REE patterns in fossil biogenic apatites.     

Experimental constraints on crystallization differentiation in a deep magma ocean

Major and trace element mineral/melt partition coefficients are presented for phases on the liquidus of fertile peridotite at 23-23.5 GPa and 2300 °C. Partitioning models, based on lattice-strain theory, are developed for cations in the ‘8-fold’ sites of majorite and Mg-perovskite. Composition-dependant partitioning models are made for cations in the 12-fold site of Ca-perovskite based on previously published data. D^min/melt is extremely variable for many elements in Ca-perovskite and highly correlated with certain melt compositional parameters (e.g. CaO and Al₂O₃ contents). The 8-fold sites in Mg-perovskite and majorite generally have ideal site radii between 0.8 and 0.9 Å for trivalent cations, such that among rare-earth-elements (REE) D^min/melt is maximum for Lu. Lighter REE become increasingly incompatible with increasing ionic radii. The 12-fold site in Ca-perovskite is larger and has an ideal trivalent site radius of ∼1.05 Å, such that the middle REE has the maximum D^min/melt. Trivalent cations are generally compatible to highly compatible in Ca-perovskite giving it considerable leverage in crystallization models. Geochemical models based on these phase relations and partitioning results are used to test for evidence in mantle peridotite of preserved signals of crystal differentiation in a deep, Hadean magma ocean.Model compositions for bulk silicate Earth and convecting mantle are constructed and evaluated. The model compositions for primitive convecting mantle yield superchondritic Mg/Si and Ca/Al ratios, although many refractory lithophile element ratios are near chondritic. Major element mass balance calculations effectively preclude a CI-chondritic bulk silicate Earth composition, and the super-chondritic Mg/Si ratio of the mantle is apparently a primary feature. Mass balance calculations indicate that 10-15% crystal fractionation of an assemblage dominated by Mg-perovskite, but with minor amounts of Ca-perovskite and ferropericlase, from a magma ocean with model peridotite-based bulk silicate Earth composition produces a residual magma that resembles closely the convecting mantle.Partition coefficient based crystal fractionation models are developed that track changes in refractory lithophile major and trace element ratios in the residual magma (e.g. convecting mantle). Monomineralic crystallization of majorite or Mg-perovskite is limited to less than 5% before certain ratios fractionate beyond convecting mantle values. Only trace amounts of Ca-perovskite can be tolerated in isolation due to its remarkable ability to fractionate lithophile elements. Indeed, Ca-perovskite is limited to only a few percent in a deep mantle crystal assemblage. Removal from a magma ocean of approximately 13% of a deep mantle assemblage comprised of Mg-perovskite, Ca-perovskite and ferropericlase in the proportions 93:3:4 produces a residual magma with a superchondritic Ca/Al ratio matching that of the model convecting mantle. This amount of crystal separation generates fractionations in other refractory lithophile elements ratios that generally mimic those observed in the convecting mantle. Further, the residual magma is expected to have subchondritic Sm/Nd and Lu/Hf ratios. Modeling shows that up to 15% crystal separation of the deep mantle assemblage from an early magma ocean could have yielded a convecting mantle reservoir with ¹⁴³Nd/¹⁴⁴Nd and ¹⁷⁶Hf/¹⁷⁷Hf isotopic compositions that remain internal to the array observed for modern oceanic volcanic rocks. If kept in isolation, the residual magma and deep crystal piles would grow model isotopic compositions that are akin to enriched mantle 1 (EM1) and HIMU reservoirs, respectively, in Nd-Hf isotopic space.     

The partitioning of trace elements between clinopyroxene and trachybasaltic melt during rapid cooling and crystal growth

We present the variation in trace element partition coefficients measured at the interface between rapidly cooled clinopyroxene crystals and co-existing melts. Results indicate that, as the cooling rate is increased, clinopyroxene crystals are progressively depleted in Si, Ca and Mg counterbalanced by enrichments in Al (mainly tetrahedral Al^iv), Na and Ti. Partition coefficients (Ds) for rare earth elements (REE), high field strength elements (HFSE) and transition elements (TE) increase with increasing cooling rate, in response to clinopyroxene compositional variations. The entry of REE into the M2 site is facilitated by a coupled substitution where either Na substitutes for Ca on the M2 site or Al^iv substitutes for Si in the tetrahedral site. The latter substitution reflects an increased ease of locally balancing the excess charge at M2 as the number of surrounding Al^iv atoms increases. Due to the lower concentration of Ca in rapidly cooled clinopyroxenes, divalent large ion lithophile elements (LILE) on M2 decrease at the expense of monovalent cations. Conversely, higher concentrations of HFSE and TE on the M1 site are facilitated as the average charge on this site increases with the replacement of divalent-charged cations by Al^vi. Although crystallization kinetics modify clinopyroxene composition, deviations from equilibrium partitioning are insufficient to change the tendency of a trace element to be compatible or incompatible. Consequently, there are regular relationships between ionic radius, valence of the trace element and D. At both equilibrium and cooling rate conditions, Ds for isovalent cations define parabola-like curves when plotted against ionic radius, consistent with the lattice strain model, demonstrating that the partitioning of trace elements is driven by charge balance mechanisms; cation substitution reactions can be treated in terms of the energetics of the various charge-imbalanced configurations.     

Henry’s and non-Henry’s law behavior of Br in simple marine systems

Experimental studies for the partitioning of Br as a trace element between aqueous and solid solutions were carried out in simple marine systems. The evaporation experiments were performed at 25°C and 1 atm in the systems of halite (NaCl), sylvite (KCl), kainite (KMgClSO₄ · 2.75H₂O), carnallite (KMgCl₃ · 6H₂O), and bischofite (MgCl₂ · 6H₂O). The partition coefficients for the systems investigated are constant only at a restricted concentration range. For concentrations lower than 100 to 300 μg Br/g aqueous solutions, D_Br increases with decreasing concentrations. Various evaporation experiments indicate that this observation is not due to kinetic effects (evaporation rates). To find a link between the partition coefficient and the Henry’s law behavior, the activity coefficients of the trace components in the solid solutions were recalculated from the experimentally derived data. It can be shown from these calculations that constant activity coefficients or Henry’s law behavior is reached for higher mole fractions of the trace component in the solid solution in halite and sylvite and thus correspond to constant partition coefficients. For bischofite and carnallite, Henry’s law behavior is restricted to the lower mole fractions, where D_Br is not constant. This behavior is caused by the activity of the trace component in the aqueous solution, which is powered by the stoichiometric factor of this component in the Br-end-member solid solution. For halite, sylvite, and kainite, this factor equals 1 and is 2 for bischofite and 3 for carnallite. However, it is thus impossible to correlate Henry’s law behavior with constant partition coefficients for solid solution systems where the stoichiometric factor of the trace component is greater than 1.     

Thermodynamics of element partitioning: (1) Systematics of transition metals in crystalline and molten silicates and (2) Defect chemistry and “the Henry's law problem”

The distribution of Mg, Mn, Fe, Co and Ni among olivine, orthopyroxene, calcic clinopyroxene and liquid can be described by exchange reactions of the form: M (phase A) + Mg (phase B) = M (phase B) + Mg (phase A). The thermochemical data predict the observed partitioning within the limits of error of both sets of data when assumptions of ideal solid solution are used, except for Mn-Mg exchange. Because ΔS and ΔV for these exchange reactions are generally small, K_D varies relatively little with temperature and pressure, although individual ion distribution coefficients (D values) are more sensitive to these variables and to changing liquid composition.Trace elements present at the ppm level can enter crystals in normal lattice sites, can participate in point defect equilibria and can enter various defect sites present metastably in the crystal as a result of its P,T history. Metastable defect equilibria, in which the number of sites (grain boundaries, surfaces, intergrowths, etc.) is fixed, can lead to enhanced trace element solubility in the crystal at very low concentrations and thus to apparent deviations from Henry's law.     

Using In Situ Trace-Element Determinations to Monitor Partial-Melting Processes in Metabasites

Peak metamorphism (800–850°C, 8–10 kbar) inthe Harts Range Meta-Igneous Complex (Harts Range, central Australia)was associated with localized partial melting by the reactionhornblende + plagioclase + quartz + H₂O = garnet + clinopyroxene+ titanite + melt. In situ trace-element determinations of prograde,peak and retrograde minerals in migmatitic metabasites and associatedtonalitic melts using laser-ablation ICP–MS has allowedmonitoring of a range of partial-melting processes (melting,melt segregation and back-reaction between crystallizing meltand restitic minerals). Mass balance calculations indicate thattitanite is a major carrier of trace elements such as Ti, Nb,Ta, Sm, U and Th, and therefore may be an important accessoryphase to control the redistribution of these elements duringthe partial melting of amphibolites. Titanite preferentiallyincorporates Ta over Nb and, hence, residual titanite mightassist in the formation of melts with high Nb/Ta. The fact thatsingle minerals record different rare earth element (REE) patterns,from prograde to peak to retrograde conditions, demonstratesthat REE diffusion is not significant up to 800°C. Therefore,trace-element analysis in minerals can be a powerful tool toinvestigate high-grade metamorphic processes beyond the limitsgiven by major elements. KEY WORDS: Harts Range; laser-ablation ICP–MS; metabasites; partial melting; trace elements     

Trace element partitioning between apatite and silicate melts

We present new experimental apatite/melt trace element partition coefficients for a large number of trace elements (Cs, Rb, Ba, La, Ce, Pr, Sm, Gd, Lu, Y, Sr, Zr, Hf, Nb, Ta, U, Pb, and Th). The experiments were conducted at pressures of 1.0 GPa and temperatures of 1250 °C. The rare earth elements (La, Ce, Pr, Sm, Gd, and Lu), Y, and Sr are compatible in apatite, whereas the larger lithophile elements (Cs, Rb, and Ba) are strongly incompatible. Other trace elements such as U, Th, and Pb have partition coefficients close to unity. In all experiments we found D_Hf > D_Zr, D_Ta ≈ D_Nb, and D_Ba > D_Rb > D_Cs. The experiments reveal a strong influence of melt composition on REE partition coefficients. With increasing polymerisation of the melt, apatite/melt partition coefficients for the rare earth elements increase for about an order of magnitude. We also present some results in fluorine-rich and water-rich systems, respectively, but no significant influence of either H₂O or F on the partitioning was found. Furthermore, we also present experimentally determined partition coefficients in close-to natural compositions which should be directly applicable to magmatic processes.     

Experimentally determined mineral-melt partition coefficients for Sc,Y and REE for olivine,orthopyroxene, pigeonite,magnetite and ilmenite

Our current lack of understanding of the partitioning behavior of Sc, Y and the REE (rare-earth elements) can be attributed directly to the lack of a sufficiently large or chemically diverse experimental data set. To address this problem, we conducted a series of experiments using several different natural composition lavas, doped with the elements of interest, as starting compositions. Microprobe analyses of orthopyroxene, pigeonite, olivine, magnetite, ilmenite and co-existing glasses in the experimental charges were used to calculate expressions that describe REE partitioning as a function of a variety of system parameters. Using expressions that represent mineral-melt reactions (versus element ratio distribution coefficients) it is possible to calculate terms that express low-Ca pyroxene-melt partitioning behavior and are independent of both pyroxene and melt composition. Compositional variations suggest that Sc substitution in olivine involves either a paired substitution with Al or, more commonly, with vacancies. The partitioning of Sc is dependent both on melt composition and temperature. Our experimentally determined olivine-melt REE Ds (partition coefficients) are similar to, but slightly higher than those reported by McKay (1986) and support their conclusions that olivines are strongly LREE depleted. Y and REE mineral/melt partition coefficients for magnetite range from 0.003 for La to 0.02 for Lu. Ilmenite partition coefficients range from 0.007 for La to 0.029 for Lu. These experimental values are two orders of magnitude lower than many of the published values determined by phenocryst/matrix separation techniques.