Phase relations governing the derivation of alkaline basaltic magmas from primary magmas at high pressures

A comparison between the variation trend of alkaline basaltic magmas within the CaO-MgO-Al₂O₃-SiO₂ system and experimentally estimated phase relations for this system at high pressures, suggests an olivine reaction relationship, which may explain the transition from primary magmas in equilibrium with olivine to alkaline basaltic magmas in which olivine does not form at high pressures. This reaction relationship is considered to be due to a transition from positive to negative crystallization with respect to olivine along the four phase curve where olivine, diopside, pyrope garnet and liquid are initially in equilibrium. The bimineralic, eclogitic character of alkaline basaltic compositions at high pressures is interpreted as being due to the presence of a thermal minimum on the three phase surface, where dioside and pyrope garnet are in equilibrium with liquid.     

Experimental modeling of the explosion mechanism of basaltic magmas

Processes in the feeders of basaltic volcanoes during Strombolian-type eruptions were examined with the use of a complex apparatus for modeling basaltic eruptions (CAMBE), which was designed and manufactured by the authors for this purpose. The experimental setup consists of modeling and registering units and has a height of 18 m. It was designed with regard for the geometric dimensions of a natural feeding volcanic system: the ratio of the inner diameter of the feeder to its height is approximately 1: 1000. CAMBE was the first modeling equipment making possible passing a flow of gas-saturated liquid through the conduit, which allowed us to study the nucleation of gas bubbles, their growth, coalescence, transformations of the gas structures, and the kinetics of the gas phase. The experiments were carried out in a manner that made it possible to eliminate effects of structural barriers and fluctuations in the liquid flow velocity. As a result of the experiments, a new (previously unknown) regime in the flow of two-phase systems through a vertical conduit was discovered: the cluster regime, which is characterized by systematically alternating dense accumulations of gas bubbles (bubble clusters) and liquid devoid of a free gas phase. It is demonstrated that the liquid, bubbly, cluster, and slug regimes systematically grade into one another and are polymorphic modifications of gas-saturated liquids moving through vertical conduits. Our data led us to propose a new model for the gas-hydrodynamic movement of magmatic melt through the conduit of a basaltic volcano: depending on the gas-hydrodynamic regime in the volcanic vent, various types of eruptive activity (up to explosions) may take place. The analyses of basaltic magma explosions allowed us to describe them from a new standpoint and recognize the following four major modes of their manifestations at the surface: (1) weak ash explosions early during the cluster regime, (2) strong ash explosions during the mature cluster regime, (3) bomb explosions during the slug regime, (4) bomb grading to ash explosions during the slug regime associated with trains of small bubbles.     

Copper partitioning between olivine and melt inclusions and its content in primitive island-arc magmas of Kamchatka

Melt inclusions and hosting them highly magnesian olivine from rocks of Kamchatka and the Western Aleutian island arc were analyzed for copper content by LA-ICP-MS to determine the copper partition coefficient in primitive island-arc magmas. Based on measurements of 45 olivine–melt pairs, this coefficient was determined to be 0.028 ± 0.009 (2σ), which is the lowest value among previously published data. Mass-balance calculations of copper in a typical mantle peridotite using obtained partition coefficient indicate that its content in peridotite and primary mantle magmas is mainly determined by mantle sulfide. The Cu partition coefficient was also used to calculate the copper content in parental magmas of volcanoes of the Central Kamchatka Depression. Estimates obtained using copper content in phenocrysts of primitive olivine (Fo > 88 mol %) from these rocks are, on average, 139 ± 58 ppm (2σ), which exceed copper contents in primitive basalts (MgO > 8.5 wt %) of mid-ocean ridges (MORB 93 ± 31 ppm). This suggests the primary enrichment of Central Kamchatka magmas in copper and correlates with their more oxidizing conditions of formation as compared to MORB.     

The alteration of olivine in basaltic and associated lavas

Olivines which cool under oxidizing conditions exsolve iron oxides at high temperature, and at low temperatures break down to essentially chloritic materials. Olivines which cool under non-oxidizing conditions alter at intermediate temperatures to complex assemblages of chlorite and interstratified phyllosilicates containing a smectite. Alteration under oxidizing conditions at low temperature, probably below 140° C, produces iddingsite, an orientated assemblage of goethite and interstratified phyllosilicates also containing a smectite.Post-deuteric alteration extends or initiates the breakdown of olivine to phyllosilicate mixtures often resulting in widespread movement of materials through the flow. Post-deuteric alteration of iddingsite produces strongly pleochroic, highly ordered varieties which eventually break down to green phyllosilicate assemblages.Weathering of olivine may produce orientated assemblages similar to deuteric forms of iddingsite. Weathering of green alteration products results in oxidation and the liberation of discrete iron hydroxides.Alteration in all cases requires exchange of material between interstitial components and olivine. During deuteric alteration, plagioclase and pyroxene are usually unaffected.     

Major element evolution of basaltic magmas: a comparison of the information in CMAS and ALFE projections

Basalt petrologists disagree as to whether the commonly used projection, forsterite-diopside-silica, in the system CMAS (CaO-MgO-Al₂O₃-SiO₂), can adequately resolve differences in basaltic glass compositions for purposes of petrogenetic modelling. Here, we suggest than an analogous plot, the aluminium-factor diagram (ALFE) of Nesbitt and Cramer (1981), has greater diagnostic value than Fo-Di-Sil. A plot of molar (Al₂O₂-CaO-Na₂O-K₂O)/(FeO + MgO) vs FeO/(FeO + MgO), it produces more coherent patterns both for experimental basalt glasses, and for natural lavas. It is, like Fo-Di-Sil, a projection through plagioclase, but has the advantage that it monitors changes in Fe/(Fe + Mg) in melts and associated crystalline phases, and is particularly useful in assessing the timing of clinopyroxene crystallization in a suite of lavas. The diagram owes its greater resolving power to the fact that the computation of its coordinates is less sensitive to analytical uncertainty than for Fo-Di-Sil. In the latter diagram, normative quartz is calculated as a residual and thus manifests the uncertainties in all the major elements.     

Origin and differentiation of recent basaltic magmas from Mount Etna

Summary One hundred and fifty samples of recent Na-alkalic lavas from the south-eastern flank of Mt. Etna, dating from about 5,000 years B.P. to 1886 were analyzed. They grade in time from more acid to more basic lavas, and show an overall range of variation much larger toward the more felsic end than previously known. Chondrite-normalized REE patterns of the least differentiated samples show LREE enrichment and HREE depletion; trace element compositions suggest that Etnean products are similar to WPB, with a weak CAB signature. Sr-isotope ratios ranging from 0.70332 to 0.70355, vary even within samples from the same eruption, and generally tend to increase with time in historic lavas.Our data suggest that processes other than simple crystal fractionation are, in part, responsible for the variation of the analyzed sequence. In fact, RTF processes with successive influxes of mafic melts, each having distinct, slightly different geochemical and isotopic features, into reservoirs of variously differentiated magmas, may explain the overall observed data.The source region for Recent Mongibello lavas is located in the mantle, isotopically zoned, and Rb-depleted with respect to the Bulk Earth composition. Model and experimental data conform well with a low degree (< 5%) modal melting of a garnet Iherzolite source, depleted by an earlier melting event with respect to primitive mantle composition.

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Herkunft und Differentiation von rezenten basaltischen Magmen des Berges Ätna

Zusammenfassung Es wurden 150 Proben von rezenten, Na-alkalischen Laven von der Südflanke des Ätna, die mit 5000 Jahren vor Christus bis 1886 datieren, analysiert. Die Laven zeigen mit der Zeit einen graduellen Übergang von sauer zu zunehmend basisch und weisen generell eine größere Variationsbreite in Richtung sauer auf als bisher angenommen. Chondrit-normalisierte REE Verteilungskurven der am geringsten differentierten Proben zeigen LREE Anreicherung und eine Verarmung der HREE. Die Spurenelement-Zusammensetzungen deuten an, daß die Ätna-Produkte Ähnlichkeit mit WPB mit einer schwachen CAB-Signatur aufweisen. Die Sr-Isotopenverhältnisse reichen von 0.70332 bis 0.70355, variieren sogar innerhalb Proben aus ein und derselben Eruption und tendieren generell zu ansteigenden Werten mit der Zeit.Unsere Daten weisen darauf hin, daß andere Prozesse als einfache Kristallfraktionierung, zumindest teilweise, für die Variation der analysierten Sequenz verantwortlich sind. In der Tat können RTF Prozesse mit sukzessiver Zufuhr von mafischen Schmelzen, jede mit leicht unterschiedlicher Geochemie und definierten Isotopenverhältnissen, in Reservoirs von unterschiedlich differentiierten Magmen, die vorliegenden Daten erklären.Die Herkunftsregion der rezenten Mongibello Laven ist im Mantel angesiedelt, der bezüglich der Isotopenzusammensetzung zoniert und, verglichen mit der Erdzusammensetzung, an Rb verarmt ist. Die Modell- und experimentellen Daten stehen in guter Übereinstimmung mit einem niedrigen Grad ( < 5%) der Aufschmelzung eines Granat-Lherzolites als Ausgangsmaterial, das, im Vergleich zum primitiven Mantel, durch einen früheren Aufschmelzungsvorgang verarmt ist.

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With 9 Figures     

The rheology of crystal-bearing basaltic magmas from Stromboli and Etna

Our ability to forecast volcanic hazards at active volcanoes stems from our knowledge of parameters affecting eruption dynamics. Persistent activity displayed by basaltic volcanic systems, such as Etna and Stromboli, is governed mainly by the textural evolution and rheological properties of eruptive products. Here, we investigate the high temperature (1131 °C < T < 1187 °C) rheological behavior and textural evolution of remelted natural basaltic magmas from Stromboli and Etna volcanic systems upon cooling and crystallization at atmospheric conditions. The pure liquid and subliquidus isothermal viscosities are investigated using a concentric cylinder apparatus by varying strain rate applied to the investigated materials. Detailed textural analysis has been performed in order to evaluate the effect of crystal distribution on the rheological evolution of magmas. At subliquidus conditions, the mineralogical assemblage is dominated by the presence of spinel and plagioclase with the occurrence of stable clinopyroxene only at the lowest temperatures (1157 and 1131 °C for the Stromboli and the Etna samples, respectively). The overall crystal fraction (?) varies between 0.06 and 0.27. In the high T regime the viscous response to applied stress and strain rate is strongly affected by the presence of even small amounts of crystals. Large discrepancies between measured and predicted viscosities obtained using the Einstein-Roscoe (ER) equation are also found at low crystal fractions. We find here that, at the investigated conditions, the physical effect caused by the presence of elongated crystals is orders of magnitude higher than that predicted by existing models which only account for spherical particles. It also appears that a weak shear thinning behavior occurs at the lowest temperatures investigated. Crystal shape and, with it, the strain-rate dependence of the rheological properties appear to play primary roles in influencing the transport properties of these basaltic magmas.     

Density changes during the fractional crystallization of basaltic magmas: fluid dynamic implications

The dynamical behaviour of basaltic magma chambers is fundamentally controlled by the changes that occur in the density of magma as it crystallizes. In this paper the term fractionation density is introduced and defined as the ratio of the gram formula weight to molar volume of the chemical components in the liquid phase that are being removed by fractional crystallization. Removal of olivine and pyroxene, whose values of fractionation density are larger than the density of the magma, causes the density of residual liquid to decrease. Removal of plagioclase, with fractionation density less than the magma density, can cause the density of residual liquid to increase. During the progressive differentiation of basaltic magma, density decreases during fractionation of olivine, olivine-pyroxene, and pyroxene assemblages. When plagioclase joins these mafic phases magma density can sometimes increase leading to a density minimum. Calculations of melt density changes during fractionation show that compositional effects on density are usually greater than associated thermal effects.In the closed-system evolution of basaltic magma, several stages of distinctive fluid dynamical behaviour can be recognised that depend on the density changes which accompany crystallization, as well as on the geometry of the chamber. In an early stage of the evolution, where olivine and/or pyroxenes are the fractionating phases, compositional stratification can occur due to side-wall crystallization and replenishment by new magma, with the most differentiated magma tending to accumulate at the roof of the chamber. When plagioclase becomes a fractionating phase a zone of well-mixed magma with a composition close to the density minimum of the system can form in the chamber. The growth of a zone of constant composition destroys the stratification in the chamber. A chamber of well-mixed magma is maintained while further differentiation occurs, unless the walls of the chamber slope inwards, in which case dense boundary layer flows can lead to stable stratification of cool, differentiated magma at the floor of the chamber.In a basaltic magma chamber replenished by primitive magma, the new magma ponds at the base and evolves until it reaches the same density and composition as overlying magma. Successive cycles of replenishment of primitive magma can also form compositional zonation if successive cycles occur before internal thermal equilibrium is reached in a chamber. In a chamber containing well-mixed, plagioclase — saturated magma, the primitive magma can be either denser or lighter than the resident magma. In the first case, the new magma ponds at the base and fractionates until it reaches the same density as the evolved magma. Mixing then occurs between magmas of different temperatures and compositions. In the second case a turbulent plume is generated that causes the new magma to mix immediately with the resident magma.     

Primary magmas at Oldoinyo Lengai: The role of olivine melilitites

The paper describes olivine melilitites at Oldoinyo Lengai, Tanzania, and from tuff cones from the Tanzanian rift valley in the vicinity of Oldoinyo Lengai. Oldoinyo Lengai is the only active carbonatite volcano and is distinguished by its alkali-rich natrocarbonatites. Lengai is also unique for its extreme peralkaline silicate lavas related directly to the natrocarbonatites. Primitive olivine melilitites are, according to their Mg# and Ni, Cr contents, the only candidates in the Lengai area for primary melt compositions. Incompatible trace elements, including REE, constrain the melting process in their sub-lithospheric sources to very low degrees of partial melting in the garnet stability field. The strong peralkaline trend at Oldoinyo Lengai is already recognisable in these primary or near-primary melts. More evolved olivine melilitites, with Mg# < 60 allow the fractionation line in its major and trace element expressions to be followed. Nevertheless, a large compositional gap separates the olivine melilitites and olivine-poorer melilitites from the phonolites and nephelinites that form the bulk of the Lengai cone. These silicate lavas show a high degree of peralkalinity and are highly evolved with very low Mg, Ni and Cr. Prominent examples of the recent evolution are the combeite–wollastonite nephelinites that are unique for Lengai. In their Sr, Nd, and Pb isotope relationships the olivine melilitites define a distinct group with the most depleted Sr and Nd ratios and the most radiogenic Pb isotopes. They are closest to a supposed HIMU end member of the Lengai evolution, which is characterised by an extreme spread in isotopic ratios, explained as a mixing line between HIMU and EM1-like mantle components.     

The solubility of olivine in basaltic liquids: an ionic model

A simple ionic model which describes the solution of the forsterite component of olivine in silicate liquids is reported. The melting relation is represented: (Mg₂SiO₄)_ol = 2(Mg²⁺)_L + (SiO₄^4?_L and is extended to all silicate liquids by normalizing their compositions to 4 oxygens. At 1 bar, the temperature at which olivine is in equilibrium with any alkali-depleted basaltic composition can be calculated to within ±30°C. This error is increased considerably when applied to terrestrial basalts which contain several weight percent alkalis. Alkalis interfere with the equilibrium by generating strongly repulsive interionic forces which can be crudely modelled in a manner consistent with constraints imposed by regular solution theory.The model quantifies the reduced activity of SiO₄^4? monomers due to increasing SiO₂ concentrations in the melt. This is a consequence of polymerization which does not appear to operate gradually over the entire spectrum of mafic and ultramafic compositions. The coordination of alumina in melts which precipitate olivine only appears to be dominantly octahedral. Titanium acts as a polymerizing agent by interconnecting previously isolated SiO₄^4? monomers. Calcium associated with normative diopside tends to exhibit small but perceptible repulsive forces involving Mg²⁺.     

Origin of basaltic magmas in the Mojave Desert area,California

The basaltic lavas erupted throughout the Mojave Desert are basanites (SiO₂<46%, normative nepheline>5%, and K₂O>1.5%), alkali-olivine basalts (SiO₂=46–48%; ne=0–5%; and K₂O=1.0–1.5%), and low-alumina, sub-alkaline basalts (SiO₂=48–51%; ne=0; K₂O<1.0%). One volcano, Pisgah Crater, erupted five times, with lava from each successive phase containing more silica and less potash than the one proceeding it. This compositional trend is the reverse of that expected from differentiation of a single alkalic magma, and therefore, may represent a succession of magmas tapped from a zone of continuing partial melting in the mantle.These lava compositions suggest that first melting was under high water pressure and was followed by relatively dry partial melting of gamet-orthopyroxene-clinopyroxene-olivine assemblages. The successive increase in silica and alkali decrease also requires that the partial melting zone move to shallower levels.All lavas sampled in the Mojave Desert area have compositions that can best be explained by the extraction of magma from such a rising melting zone, analogous to the mantle diapirs suggested by Green and Ringwood.     

Nature of the clinopyroxene and iron enrichment in alkalic and transitional basaltic magmas

Iron enrichment and clinopyroxene composition are considered to be good indicators of the magmatic parentage of volcanic series produced by fractionation of basaltic magma. Tholeiitic series are in fact believed to be constantly more iron enriched than alkalic series and systematic differences in the clinopyroxene mineralogy of the two suites seem also to be well established. The aim of this paper is to demonstrate that such generalization cannot be accepted, as natural conditions can be realized under which the fractionation of alkalic or mildly alkalic basalts may produce series with strong iron enrichment and with clinopyroxene mineralogy atypical for basalts of alkaline affinity.In the Erta'Ale volcanic range (Northern Danakil Depression, Ethiopia), an example of such a serie is found, with a mildly alkalic basaltic magma fractionating under low and falling oxygen fugacity and giving rise to a series with some tholeiitic chemical and mineralogical features.     

Temperature dependence of sulfide and sulfate solubility in olivine-saturated basaltic magmas

The sulfur concentration at pyrrhotite- and anhydrite-saturation in primitive hydrous basaltic melt of the 2001-2002 eruption of Mt. Etna was determined at 200 MPa, T = 1050-1250 °C and at log fO₂ from FMQ to FMQ+2.2 (FMQ is Fayalite-Magnetite-Quartz oxygen buffer). At 1050 °C Au sample containers were used. A double-capsule technique, using a single crystal olivine sample container closed with an olivine piston, embedded in a sealed Au₈₀Pd₂₀ capsule, was developed to perform experiments in S-bearing hydrous basaltic systems at T > 1050 °C. Pyrrhotite is found to be a stable phase coexisting with melt at FMQ-FMQ+0.3, whereas anhydrite is stable at FMQ+1.4-FMQ+2.2. The S concentration in the melt increases almost linearly from 0.12 ± 0.01 to 0.39 ± 0.02 wt.% S at FeS-saturation and from 0.74 ± 0.01 to 1.08 ± 0.04 wt.% S at anhydrite-saturation with T ranging from 1050-1250 °C. The relationships between S concentration at pyrrhotite and/or anhydrite saturation, MgO content of the olivine-saturated melt, T, and log fO₂ observed in this study and from previous data are used to develop an empirical model for estimating the magmatic T and fO₂ from the S and MgO concentrations of H₂O-bearing olivine-saturated basaltic melts. The model can also be used to determine maximum S concentrations, if fO₂ and MgO content of the melt are known. The application of the model to compositions of melt inclusions in olivines from Mt. Etna indicates that the most primitive magmas trapped in inclusions might have been stored at log fO₂ slightly higher than FMQ+1 and at T = 1100-1150 °C, whereas more evolved melts could have been trapped at T ? 1100 °C. These values are in a good agreement with the estimates obtained by other independent methods reported in the literature.     

Cenozoic alkali basaltic magmas of western Germany and their products of differentiation

Analytical data on major elements and 31 trace elements in olivine nephelinites, nepheline basanites, basanitic alkali olivine basalts and their differentiates (tephrites, hawaiites, mugearites, benmoreites, latites, phonolites and trachytes) from Hegau, Kaiserstuhl, Rhön, Hessian Depression, Vogelsberg, Westerwald, Siebengebirge, E Eifel and Hocheifel are evaluated. They were based on 400 samples with new or unpublished data on about one third of the rocks. The Sr–Nd isotopic compositions for 78 rocks are included. The alkali basaltic volcanism is caused by adiabatic decompression of asthenospheric mantle updomed to a minimum depth of 50 km in connection with the Alpine continent collision. The chemical compositions of the primary basaltic melts from the different areas are similar containing about one hundred-fold enrichment of highly incompatible elements relative to the primitive mantle from partial melting of depleted and secondarily enriched peridotite. The elements Cs, K, Pb and Ti are specifically depleted in the basalts partly because of phlogopite being residual at partial melting. The Tertiary alkali basalts range in Nd-isotopic composition from 0.51288 to 0.51273 and in Sr-isotopic ratios from 0.7032 to 0.7042. These ranges indicate mixtures of HIMU, depleted and enriched mantle components in the metasomatically altered peridotite source which resembles that of certain ocean islands. The Nd-Sr-isotopic compositions of the Quaternary E Eifel are close to bulk Earth ratios. East and W Eifel plots differ distinctly from the Tertiary Hocheifel which is geographically intermediate. This isotopic difference, beside specific K/Na ratios, is probably caused by separate metasomatic pulses that immediately preceded the respective periods of volcanism. The metasomatically altered mantle had partly primitive mantle signatures (Nb/Ta, Zr/Sm and Th/U ratios) and partly ocean island (or MORB) source properties (Rb/Cs). A MORB source can be excluded because of the low K/Rb and high Th/U ratios. A correlation of D with ⁸⁷Sr/⁸⁶Sr in amphibole and phlogopite and a slightly larger ¹⁸O than in MORB is conformable with a seawater and crustal impact on the source of alkali basalts. Slightly higher than average water concentrations in the source of certain primary basaltic melts (indicated by amphibole phenocrysts in their basalts) are required for differentiation of these basalts in magma chambers of the upper crust. Model calculations are presented to explain compositions of differentiates which range from about 60% to about 20% residual melt. The latter are represented by phonolites and trachytes. The Nd- and Sr-isotopic signatures of the majority of differentiates indicate contamination by a granitic partial melt from the wall rocks of magma chambers. Olivine nephelinite magma was the common source of contaminated differentiates.     

Crystal clots,amphibole fractionation and the evolution of calc-alkaline magmas

Petrographic and microprobe investigations of calc-alkaline (CA) rocks from the High Cascade Range (i.e., Mt. St. Helens, Mt. Jefferson, Crater Lake and Mt. Shasta) of western North America show that crystal clots represent primary igneous phase assemblages and are not products of amphibole reactions with melt. For each eruptive complex, crystal clots display diverse modal proportions even within a single eruptive unit. Nevertheless, in all cases the crystal-clot minerals are also represented in the rock as phenocrysts or microphenocrysts. Basalts contain clots of ol+plag+mgt, ol+mgt, cpx+ plag+mgt, cpx+mgt and plag+mgt; andesites, clots of cpx+mgt, opx+mgt, cpx+opx+plag+mgt, cpx+plag+mgt, opx+plag+mgt and plag±mgt; and dacites, clots of opx+mgt, cpx+opx+plag+ mgt, opx+plag+mgt, amph+plag+mgt±ilm, amph+mgt±ilm and plag±mgt. The bulk compositions of most of these clot assemblages could not have been derived from amphibole percursors. Although some amphiboles in dacitic rocks display a breakdown reaction of amph=plag+cpx+opx +mag, these mineral clusters, unlike those of clots, typically have a relict amphibole crystal outline and a fine-grained metamorphic texture. Plagioclase grains in the mineral clusters lack oscillatory zoning which is typical of crystal clot plagioclase grains. The euhedral to subhedral shapes of most clot minerals and the oscillatory zoning present in most clot plagioclase grains are not likely to have formed from the breakdown of amphibole. Crystal clots are also observed in Hawaiian and ocean floor basalts, although amphibole fractionation has not been proposed for those lavas. Magnetite fractionation may be the controlling process limiting iron enrichment in CA magmas rather than amphibole fractionation. Textural evidence indicates that magnetite is an early-forming phase in CA magmas. V, which is concentrated in magnetite, shows a strong decrease with increasing silica in many CA rocks, supporting a magnetite fractionation model.Hawaii Institute of Geophysics Contrib. No. 969     

The distribution of Fe and Mg between olivine and lunar basaltic liquids

We have examined the Fe and Mg distribution between coexisting olivine and lunar basaltic liquids produced by equilibrium partial melting of natural lunar samples. In agreement with the findings of Roeder and Emslie (Contrib. Mineral. Petrol. 29, 275–289) on terrestrial compositions, the logarithms of the conventional distribution coefficients, K_ol-L^Fe and K_ol-L^Fe-Mg, are nearly linear functions of inverse temperature; and the exchange coefficient, K_D = K_ol-L^Fe-Mg, is nearly independent of temperature and composition within a given magma group. There are, however, small but significant differences in conventional and exchange distribution coefficients from one magma group to another, e.g. low-Ti vs high-Ti lunar basalts. It is possible to achieve slightly greater precision for the inverse temperature functions by including terms approximating silica activity in the conventional distribution coefficients. The term ($\text{2Si}\text{O}\text{)}{}_{\mathrm{L}}$ is apparently the best simple approximation for silica activity in olivine-saturated liquids based upon data for Fe, Mg, Mn, Ca, Ti and Cr. Pressure has noticeable effects upon Fe and Mg distribution between olivine and liquid only above 5 kbar.The excellent linear correlation of the logarithms of the distribution coefficients with inverse temperature allows calculation of approximate values of $\text{Δ}\text{H}\text{?}{}^0$ for the reactions : 2MgO_L + SiO_2LaiMg₂SiO_4ol and 2FeO_L + SiO_2LaiFe₂SiO_4ol. Values obtained, approx ?26 kcal/mole, are comparable with values of the heats of fusion of forsterite and fayalite calculated by Bradley (Am. J. Sci.260, 550–554) and measured by Orr (J. Am. Chem. Soc. 75, 528–529).The exchange distribution coefficient for Fe and Mg, K_D, is sensitive to large changes in liquid chemistry. Although K_D is explicitly independent of silica activity, K_D apparently changes with silica concentration. This change is a reflection of changes in the mixing properties of Fe and Mg in liquids with different chemistry and hence structure. Regular solution theory predicts that as the mixing properties of an element in a solution change, the most radical changes in activity coefficients occur in the range of dilute concentrations. Therefore, the distribution coefficients for trace elements will also be dependent upon large changes in liquid chemistry, even if corrections for silica and other liquid component activities are applied.     

Limestone assimilation by basaltic magmas: an experimental re-assessment and application to Italian volcanoes

The results of an experimental study of limestone assimilation by hydrated basaltic magmas in the range 1,050–1,150°C, 0.1–500 MPa are reported. Alkali basalts doped with up to 19 wt% of Ca, Mg-carbonates were equilibrated in internally heated pressure vessels and the resulting phase relationships are described. The major effects of carbonate incorporation are: (1) generation of CO₂-rich fluid phases; (2) change in liquidus phase equilibria; the crystallization of Ca-rich clinopyroxene is favored and the other phases (e.g. olivine, plagioclase), present in the absence of carbonate assimilation, are consumed. As a consequence of the massive clinopyroxene crystallization, the residual melt is strongly silica-depleted and becomes nepheline-normative. Compositional and mineralogical evolutions observed in Mt. Vesuvius eruptive products match those documented in our experiments with added carbonates, suggesting the possibility that carbonate assimilation increased during the last 25 ka of activity. In Central-Southern Italy, carbonate assimilation at shallow levels probably superimposes on deeper source heterogeneities.     

Two methods for estimating the degree of melting and trace element concentrations in the sources of primary magmas

The degree of partial melting of primary magmas can be estimated using the ratios of trace element concentrations of lavas with different compositions. In addition, the source concentrations of the trace elements can be estimated. Two methods are demonstrated that use either linear or hyperbolic regression of trace element pairs. The accuracy of the methods is mainly limited by the assumption of constant source concentration ratios, and the accuracy of the applied distribution coefficients. The degrees of melting of nephelinite and alkali olivine basalt from Kauai, Hawaii are estimated as about 9% and 12%, respectively. Presently, the accuracy of estimates of the degrees of partial melting is rather limited by the accuracy of the available distribution coefficients.