Liquid immiscibility in basic alkaline magmas

On the assumption that very basic silicate magmas contain appreciable amounts of O^2? ions, non-ideal mixing of the melt species may be due to strongly preferred ionic associations. The anions in the melt, O^2? on the one hand, and SiO₄^4? and polymerized aluminosilicate ionic species on the other, discriminate between the cations according to their field strength and polarizing power. K⁺, Na⁺, Ba²⁺, Sr²⁺ and Ca²⁺ associate with singly bonded oxygen, and Mg²⁺, Fe²⁺ and Ni²⁺ attach themselves to O^2? rather than to silicate or aluminosilicate anions. In extreme cases these relations may lead to unmixing in the silicate melt, especially in the presence of water which may lower the liquidus relative to the solvus temperature. Liquid—liquid phase separation in ultrabasic magmas may be related to the present model.     

Meimechites, porphyritic alkaline picrites, and melanephelinites of Siberia: Conditions of crystallization, parental magmas, and sources

The investigation of rocks, minerals, and melt inclusions showed that porphyritic alkaline picrites and meimechites crystallized from different parental magmas. At a similar ultrabasic composition, the alkaline picrite melts were enriched in K₂O relative to Na₂O, and contained up to 0.12–0.13 wt % F and less Cr, Ni, and H₂O (only 0.01–0.16 wt % H₂O, versus 0.6–1.6 wt % in the meimechite melts) compared with the meimechite magmas. The crystallization of alkaline picrite melts occurred under stable conditions at relatively low temperatures without abrupt changes: olivine and clinopyroxene crystallized at 1340–1285 and 1230–1200°C, respectively, as compared with 1600–1450 and 1230–1200°C in the meimechites. The alkaline picrite melts evolved toward melanephelinite, nephelinite, tephrite, and trachydolerite; whereas the meimechite magmas gave rise to subalkaline picritic rocks. The partitioning of vanadium between olivine and melt suggests that the meimechite magma crystallized under more oxidizing conditions compared with the alkaline picrite melts: the K_DV values for the meimechite melts (0.011–0.016) were three times lower than those for the alkaline picrite melts (0.045–0.052). The parental magmas of the alkaline picrites and meimechites were enriched in trace elements relative to mantle levels by factors of tens to hundreds. The alkaline picrite magma showed lower LILE and LREE contents compared with the meimechite magma. The magmas had also different indicator ratios of incompatible elements, including those immobile in aqueous fluids. It was concluded that the meimechite and alkaline picrite melts were derived from different mantle sources. The former were generated at lower degrees of melting of an undepleted mantle source, and the meimechite melts were produced by high-degree melting of a probably lherzolite-harzburgite source.     

Heat effects of assimilation,crystallization, and vesiculation in magmas

The heat balance for crystal fractionation and assimilation processes is the enthalpy difference between the initial and final states of a system. To order the calculations, the process is viewed as one of assimilation; the heat change for a crystallization process is obtained by changing the signs of the pertinent heat effects. The initial state is a mineral assemblage at T _s and P and an initial magma at T _m and P. The final state is a magma at T _m and P.The net heat change results from: (a) Unmixing of solid solutions, (b) Heating (cooling) each component to its fusion temperature, (c) Fusion of each component, (d) Cooling (heating) of each fused component to the magma temperature, (e) Mixing of each fused component in succession with the melt.The heat required to form a basaltic melt from its equilibrium mineral assemblage is approximately twice that required for a granitic melt. A zero heat balance, with the heat of crystallization from phases with which the magma is saturated supplying the energy for assimilation, necessitates that the mass crystallized be approximately twice that assimilated. The heat effects attendant on release of H₂O from silicic melts depends on the state of the H₂O in the external environment; a low fugacity could cause the magma to cool.The uncertainties in the calculations are estimated at ±10%.     

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.     

Genesis and crystallization of ultramafic alkaline carbonatite magmas of Siberia: ore potential,mantle sources,and relationship with plume activity

This paper discusses the genesis of large Siberian alkaline massifs hosting major ore deposits. These reference massifs are grouped based on the predominance of alkalies (K or Na) and their agpaitic index (miaskitic and agpaitic). We proposed new emplacement schemes for the Tomtor, Murun, Burpala, Synnyr, and Bilibino massifs supported by petrochemical and geochemical data, as well as new age estimates. Types of their ore potential and genesis of rare-metal mineralization are discussed. The formational types of carbonatites as the main ore-bearing rocks are given. The depth of magma generation and types of mantle sources are determined using isotopic data from previous studies. A model of plume-related generation of ultramafic alkaline magmas is proposed.     

Regional features of primary alkaline magmas of the Atlantic Ocean

In the framework of the GIS project on the geochemistry of Atlantic intraplate magmatism, primary high-magnesian melts were identified there and subdivided into five types: foidites, picrites, basanite-nephelinites, alkaline olivine basalts, and tholeiite. Their relative proportions were determined for both the Atlantic Ocean as a whole and individual magmatic centers. The compositional ranges and average compositions were calculated. It was shown that alkali rocks are predominant, but tholeiite melts account for about 25%. Among ocean-island volcanic rocks, differentiated varieties clearly dominate over primary melts (80 and 20%, respectively). Variations in the proportions of the distinguished types were applied to prepare a map for the petrochemical typification of Atlantic intraplate magmatism. Seven petrochemical zones were provisionally identified, first demonstrating the lateral petrochemical heterogeneity of intraplate sources of the Atlantic Ocean. In addition to the global heterogeneity, each large center of intraplate magmatism (archipelago or island chain) demonstrates local heterogeneities. The variations in the Na/K, Ti/Na, and Si/Ca ratios reflect significant magma generation depths (in the lower mantle) for intraplate magmatism. It was proposed that variations in the Ti/Na ratio in the high-magnesian melts are controlled by a change in the Na and Ti partition coefficients of pyroxene with increasing magma generation depth. A comparison between evolution of the oceanic and continental alkaline magmatism was conducted.     

Compositional range of primary tholeiitic magmas evaluated from major-element trends

The major-element trend for Hawaiian tholciites is well defined and may be represented by straight lines in a Bowen diagram. The trend can neither be related to olivine accumulation nor to olivine fractionation. Other phenocryst control of the trend is also unlikely. It is suggested that the range in magnesia content for primary Hawaiian tholeiites is from at least 13% MgO to above 20%, MgO. The major-element trend for abyssal tholeiites suggests that abyssal tholeiites with 8–9% MgO are primary magmas. The total possible range in magnesia content for primary tholeiitic magmas is considered to be from 8–9% MgO to about 20% MgO.     

Vein-plus-wall-rock melting mechanisms in the lithosphere and the origin of potassic alkaline magmas

A model is developed for the origin of ultrapotassic melts by melting of veined lithosphere; the veins are rich in clinopyroxene and mica, whereas the wall-rocks consist principally of peridotites. The veins originate by solidification of low-degree melts which are themselves the results of earlier, deeper, multistage processes ultimately due to the presence of a transition zone between large-scale channelled and porous flow regimes. The melting event producing the ultrapotassic magma begins in the veins due to the concentration of hydrous phases and incompatible elements, but spreads to include the surrounding wall-rocks by a combination of two mechanisms. The alkaline magma composition is thus a hybrid of vein (V) and wall-rock (W) components.

The melt hybridization mechanisms are: (i) Solid-solution melting: Minerals which from extensive solid-solutions are abundant in the vein assemblages (Cr/Al spinel, F/OH mica, amphibole and apatite). The breakdown of these phases take place over a temperature range between the solidus of the vein assemblage and the elimination of the more refractory end-members. This process bridges the temperature gap between the solid of vein and wall-rock, so that a melt component from the wall-rock is added to that from the vein before elimination of all vein minerals. Phlogopite forms the most effective of these sliding reactions, resulting in its stability at near-liquids temperatures in experiments. (ii) Dissolution of wall-rock minerals: The initial melt fraction in the vein infiltrates the surrounding wall-rock due to the dominance of surface energy minimization on melt flow at the intergranular scale. Following infiltration, dissolution of wall-rock minerals occurs at temperatures lower than their melting temperatures, thus imparting a refractory wall-rock component to the melt composition. Dissolution of olivine and/or orthopyroxene occurs preferentially, since these minerals are furthest from equilibrium with the strongly alkaline, vein-derived melt.

Remobilisation of several generations of veins explains the occurrence within a restricted space and time of rocks bearing chemical characteristics which are generally thought to indicate contrasting tectonic settings (e.g. central Italy). The ultrapotassic rocks are explained as being dominanyly vein-derived (i.e. high V/W ratio): further dilution of the V-component by wall-rock, supplemented by asthenospheric melt in advanced cases, leads to the production of more voluminous basaltic rocks bearing incompatible element signatures reminiscent of those of ultrapotassic rocks.     

Feldspar crystallization trends in leucite-bearing and related assemblages

Feldspar chemical variations in representative leucite-bearing and related rocks from well-known localities in Italy, Germany, Uganda and Australia demonstrate that phenocrystal core to rim variations may not represent the feldspar crystallization trend in the host lava and only the groundmass feldspar zoning trend is a reliable indicator of crystal-liquid relationships. Textural relationships indicate that coexisting plagioclase and alkali feldspar crystallized sequentially, the latter after the former, rather than cotectically.Groundmass alkali feldspar show Ca-, Na-depletion and K-enrichment zoning trends. Plagioclase crystallization follows Ca-depletion, Na and K-enrichment trends. Typically, Sr and Ba solid solubility is significant, particularly in groundmass feldspar.The alkali feldspar variation trend from groundmass assemblages is not consistent with the theoretical phase relationships in the system NaAlSiO₄-KAlSiO₄ CaAl₂Si₂O₈-SiO₂ (The phonolite pentahedron) proposed by Carmichael et al. (1974).Factors believed to be important in controlling feldspar crystallization trends are the Sr-Ba feldspar components, the role of the coexisting pyroxene and the presence of F, Cl and/or their alkali compounds.     

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.     

A theory for some pyroxene crystallization trends

Changes in solid solution limits, which must occur as crystallization proceeds, are used to interpret crystallization trends of pyroxenes from the Bushveld Intrusion, from oxidised and reduced basaltic lavas, and from lunar lavas.     

Some implications of xenolith glasses for the mantle sources of alkaline mafic magmas

The assumption that mafic alkaline magmas are derived from mantle sources with a lherzolite mineralogy has become entrenched in the petrologic literature. Although it is commonly assumed that highly alkaline magmas require metasomatised mantle sources, there is little understanding of the spatial relation of such sources with respect to those of associated more Si-rich transitional magmas. Glasses developed in mantle xenoliths represent natural experiments which may provide some insight on this problem. Highly silica undersaturated glasses developed in the amphibole-garnet clinopyroxenite portion of a composite xenolith from Nunivak Island, Alaska, become quartz normative where they penetrate adjacent spinel lherzolite. A comparison of glass compositions in mantle pyroxenite and lherzolite xenoliths reveals that glasses developed in amphibole pyroxenite xenoliths are in general more silica undersaturated than those in lherzolite xenoliths. This suggests that some highly silica undersaturated magmas such as nephelinites may in fact be derived by the preferential melting of amphibole or amphibole-garnet pyroxenite veins and that the spectrum from nephelinite to transitional alkaline basalt that characterizes many individual alkaline volcanic suites is produced by mixing with melt derived from the host lherzolite as the degree of partial melting increases.     

The volatile component of some pumice-forming alkaline magmas from the Azores and Canary Islands

The abundances of pre-eruptive magmatic volatile species in the system H-O-S may be determined by application of thermodynamic methods to phenocryst assemblages commonly found in volcanic rocks, as demonstrated by Rutherford and Heming (1978). These methods are applied to alkaline pumice deposits, of airfall and ignimbrite type, from Tenerife (Canary Islands), Sao Miguel and Faial (Azores). It is argued that reliable temperature and fO₂ buffering mechanisms found in rhyolitic magmas appear not to operate in more alkaline liquids. fH₂O is estimated using biotite; the high values found are shown to be compatible with the violently explosive nature of the magmas concerned. fS₂ is estimated from pyrrhotite composition. fH₂, fH₂S, fSO₂, fSO₃ are calculated from gas equilibria. Water fugacity may be very roughly estimated for non-biotite bearing samples from data on the sulphur species. Abundances of these species are similar in alkaline and calc-alkaline salic magmas. Volcanological implications, relating to the release of volatiles during explosive eruptions, are considered.     

The fluid regime of crystallization of water-saturated granitic and pegmatitic magmas: a physicochemical analysis

Miarolitic granite pegmatites are a unique natural object that makes it possible to study magmatic processes that lead to the formation of ore-forming media and systems. This paper summarizes modern views on phase transformations in aqueous silicate systems at parameters close to those of the transition from magmatic to hydrothermal crystallization. Comparison of phase diagrams and the results of study of pegmatite-forming media permits making conclusions about the crystallization of the water-saturated magmas of miarolitic granite pegmatites. The fluid regime of aqueous granite systems of simple composition, not enriched in fluxing components, is determined mainly by magma degassing or the supply of volatiles with flows of transmagmatic fluids. These processes cause the separation of essentially carbon dioxide or essentially hydrous fluid. During the evolution of such magmas, crystallization from silicate melt is separated in PT-space and, possibly, in time from the crystallization from aqueous or mixed carbon dioxide-aqueous super- and subcritical solutions. The evolution of chambers of water-saturated granitic and pegmatitic magma enriched in F, B, and alkali metals presupposes the formation of a heterogeneous mineral-forming medium in which crystallization occurs in the magmatic melt at high-temperature stages; as temperature decreases, crystallization can proceed in hydrous fluid, hydrosilicate, and/or hydrosaline liquids simultaneously. Hydrothermal crystallization can also take place in a heterogeneous medium consisting of aqueous solutions of different salinities and vapor or vapor-carbon dioxide gas mixture. The relationship between different fluid regimes during the evolution of volatile-saturated granitic and pegmatitic magmas determines the variety of postmagmatic rocks accompanying granite massifs.     

Fractional crystallization and mantle-melting controls on calc-alkaline differentiation trends

The phase relations of primitive magnesian andesites and basaltic andesites from the Mt. Shasta region, N California have been determined over a range of pressure and temperature conditions and H₂O contents. The experimental results are used to explore the influence of H₂O and pressure on fractional crystallization and mantle melting behavior in subduction zone environments. At 200-MPa H₂O-saturated conditions the experimentally determined liquid line of descent reproduces the compositional variation found in the Mt. Shasta region lavas. This calc-alkaline differentiation trend begins at the lowest values of FeO*/MgO and the highest SiO₂ contents found in any arc magma system and exhibits only a modest increase in FeO*/MgO with increasing SiO₂. We propose a two-stage process for the origin of these lavas. (1) Extensive hydrous mantle melting produces H₂O-rich (>4.5--6 wt% H₂O) melts that are in equilibrium with a refractory harzburgite (olivine + orthopyroxene) residue. Trace elements and H₂O are contributed from a slab-derived fluid and/or melt. (2) This mantle melt ascends into the overlying crust and undergoes fractional crystallization. Crustal-level differentiation occurs under near-H₂O saturated conditions producing the distinctive high SiO₂ and low FeO*/MgO characteristics of these calc-alkaline andesite and dacite lavas. In a subset of Mt. Shasta region lavas, magnesian pargasitic amphibole provides evidence of high pre-eruptive H₂O contents (>10 wt% H₂O) and lower crustal crystallization pressures (800 MPa). Igneous rocks that possess major and trace element characteristics similar to those of the Mt. Shasta region lavas are found at Adak, Aleutians, Setouchi Belt, Japan, the Mexican Volcanic Belt, Cook Island, Andes and in Archean trondhjemite--tonalite--granodiorite suites (TTG suites). We propose that these magmas also form by hydrous mantle melting.Editorial responsibility: J. Hoefs     

Alkaline-ultrabasic mantle-derived magmas, their sources, and crystallization features: Data of melt inclusion studies

To find out the reasons responsible for the diversity of igneous rocks forming the alkaline-ultrabasic carbonatite Krestovskiy massif (the Maimecha–Kotui province, Russia) we have studied melt inclusions in clinopyroxene of trachydolerites, porphyric melanephelinites, and tholeiites. It was established that the homogenization temperatures of inclusions in these rocks are rather close: 1140–1180 °C, 1190–1230 °C, and 1150–1210 °C, respectively. Compositions of melt inclusions in clinopyroxenes from different rocks are significantly different. The chemical composition of clinopyroxene of trachydolerites corresponds to that of trachybasalts and their derivatives. The inclusions are enriched in Sr, Ba, P, and S and their total sum of alkalies (at K ≥ Na) is never less than 5–6 wt.%. Inclusions from the rims of clinopyroxene phenocrysts in porphyric melanephelinites are similar in composition also to inclusions in trachydolerites. But in the cores of clinopyroxene phenocrysts the composition of inclusions corresponds to nephelinite melt. The composition of some melt inclusions in the intermediate and cores zones of clinopyroxene from porphyric melanephelinite has high SiO₂ (53–55 wt.%), MgO (8–9 wt.%) and a low (1–2 wt.%) total sum of alkalies (at Na ≥ K) and is depleted in Al₂O₃ (6–7 wt.%), which is similar to the composition of basaltic komatiites. The composition of inclusions in tholeiites is also basic, highly magnesian, and low-alkaline, Sr and Ba are rare to absent. Compared to the inclusions of basaltic komatiite composition, the inclusions in tholeiites are enriched in Al and depleted in Ca, Ti, and P. The melts trapped in clinopyroxenes from different rocks contain low (0.014–0.018 wt.%) water but they are enriched in F: from 0.37 wt.% in nephelinite melts to 0.1–0.06 wt.% in tholeiite and basaltic komatiite melts. Inclusions in all the rocks under study, host clinopyroxene, and the rocks themselves are significantly enriched in incompatible elements (1–2 orders of magnitude relative to the mantle norm). In tholeiites, the partitioning of these elements is rather uniform, while in trachydolerites and especially in melanephelinites it is contrasting with a drastic depletion in HREE relative to LREE, MREE, and HFSE. A conclusion is made that the Krestovskiy massif was formed by no less than three mantle-derived magmas: melanephelinite, tholeiite and basaltic komatiite. Magmas were generated in different magma sources at different depths with various degrees of enrichment in incompatible elements. These magmas were, most likely, dominated by melanephelinite magma. In intermediate chambers this magma differentiated to form derivative melts of nephelinite, trachydolerite–trachyandesite–trachyte compositions. Komatiite-basalt melts were, most likely, derivatives of primitive meimechite magmas.     

Some trace element relationships among liquid and solid phases in the course of the fractional crystallization of magmas

The classical equations relating the trace element concentrations of the liquid and solid phases coexisting in the simple fractional crystallization of a parental magma have been put in a simple graphical form, which allows rapid analysis of the possible genetic relationships in a given rock suite. The effects of an incomplete separation between the two phases are taken into account. The approach does not require the use of otherwise estimated partition coefficients. Trace element data concerning the minerals of cumulates, where available, may provide an independent estimation of the effective mineral-liquid partition coefficients. With reasonable assumptions, this approach may even be applied to plutonic rocks. Interpretation of the published rare earth element data from the Southern California Batholith by this procedure suggests that a tonalitic parental magma could generate a granodioritic liquid by crystallizing 40–50 wt % of a solid residue of gabbroic composition, in agreement with Larsen's (Mem. Geol. Soc. Amer. 29, 1948) calculations. The calculated mineral-liquid partition coefficients for the REE fall in the range of published phenocryst-groundmass values for acidic volcanic rocks.     

Phlogopite- and clinopyroxene-dominated fractional crystallization of an alkaline primitive melt: petrology and mineral chemistry of the Dariv Igneous Complex,Western Mongolia

We present field relationships, petrography, and mineral major and trace element data for the Neoproterozoic Dariv Igneous Complex of the Altaids of Western Mongolia. This unique complex of high-K plutonic rocks is composed of well-exposed, km-scale igneous intrusions of wehrlites, phlogopite wehrlites, apatite-bearing phlogopite clinopyroxenites, monzogabbros, monzodiorites, and clinopyroxene-bearing monzonites, all of which are intruded by late stage lamprophyric and aplitic dikes. The biotite-dominated igneous complex intrudes depleted harzburgitic serpentinite. The observed lithological variability and petrographic observations suggest that the plutonic rocks can be ascribed to a fractionation sequence defined by olivine + clinopyroxene ± Fe–Ti oxides → phlogopite + apatite → K-feldspar + plagioclase → amphibole + quartz. Notably, phlogopite is the dominant hydrous mafic mineral. Petrogenesis of the observed lithologies through a common fractionation sequence is supported by a gradual decrease in the Mg# [molar Mg/(Fe_total + Mg) × 100] of mafic minerals. Crystallization conditions are derived from experimental phase petrology and mineral chemistry. The most primitive ultramafic cumulates crystallized at ≤0.5 GPa and 1,210–1,100 °C and oxygen fugacity (fO₂) of +2–3 ?FMQ (log units above the fayalite–quartz–magnetite buffer). Trace element modeling using clinopyroxene and apatite rare earth element compositions indicates that the dominant mechanism of differentiation was fractional crystallization. The trace element composition of a parental melt was calculated from primitive clinopyroxene compositions and compares favorably with the compositions of syn-magmatic lamprophyres that crosscut the fractionation sequence. The parental melt composition is highly enriched in Th, U, large ion lithophile elements, and light rare earth elements and has a pronounced negative Nb–Ta depletion, suggestive of an alkaline primitive melt originating from a subduction-imprinted mantle. Comparison with a global compilation of primitive arc melts demonstrates that Dariv primitive melts are similar in composition to high-K primitive melts found in some continental arcs. Thus, the high-K fractionation sequence exposed in the Dariv Igneous Complex may be a previously unrecognized important fractionation sequence resulting in alkali-rich upper crustal granitoids in continental arc settings.