Carbonatite melt inclusions in coexisting magnetite,apatite and monticellite in Kerimasi calciocarbonatite,Tanzania: melt evolution and petrogenesis

Kerimasi calciocarbonatite consists principally of calcite together with lesser apatite, magnetite, and monticellite. Calcite hosts fluid and S-bearing Na–K–Ca-carbonate inclusions. Carbonatite melt and fluid inclusions occur in apatite and magnetite, and silicate melt inclusions in magnetite. This study presents statistically significant compositional data for quenched S- and P-bearing, Ca-alkali-rich carbonatite melt inclusions in magnetite and apatite. Magnetite-hosted silicate melts are peralkaline with normative sodium-metasilicate. On the basis of our microthermometric results on apatite-hosted melt inclusions and forsterite–monticellite phase relationships, temperatures of the early stage of magma evolution are estimated to be 900–1,000°C. At this time three immiscible liquid phases coexisted: (1) a Ca-rich, P-, S- and alkali-bearing carbonatite melt, (2) a Mg- and Fe-rich, peralkaline silicate melt, and (3) a C–O–H–S-alkali fluid. During the development of coexisting carbonatite and silicate melts, the Si/Al and Mg/Fe ratio of the silicate melt decreased with contemporaneous increase in alkalis due to olivine fractionation, whereas the alkali content of the carbonatite melt increased with concomitant decrease in CaO resulting from calcite fractionation. Overall the peralkalinity of the bulk composition of the immiscible melts increased, resulting in a decrease in the size of the miscibility gap in the pseudoquaternary system studied. Inclusion data indicate the formation of a carbonatite magma that is extremely enriched in alkalis with a composition similar to that of Oldoinyo Lengai natrocarbonatite. In contrast to the bulk compositions of calciocarbonatite rocks, the melt inclusions investigated contain significant amount of alkalis (Na₂O + K₂O) that is at least 5–10 wt%. The compositions of carbonatite melt inclusions are considered as being better representatives of parental magma composition than those of any bulk rock.     

成矿碳酸岩的实验岩石学研究现状与展望

火成碳酸岩及其风化产物是全球战略性关键金属稀土元素(REE)和铌(Nb)的主要来源。因此,对关键金属在火成碳酸岩中的超常富集机理研究具有重要的科学意义。研究表明成矿碳酸岩常常与碱性杂岩体存在密切的时空联系,因而母岩浆应属于碳酸盐化的硅酸盐岩浆,并以霞石岩岩浆为主。针对碳酸岩关键金属矿床的成岩成矿过程,已有实验发现母岩浆在地壳内的演化过程中,既可以通过分离结晶作用,也可以通过液态不混溶作用形成碳酸岩。然而,更加接近自然样品的多组分体系的实验均表明液态不混溶作用总是先于碳酸盐矿物分离结晶作用。因此,液态不混溶作用对关键金属成矿过程有着不可忽视的作用。尽管如此,已有不混溶实验表明当碳酸盐熔体和硅酸盐熔体发生不混溶之后,关键金属REE与Nb总是优先分配到硅酸盐熔体(碱性岩)中,但是在成矿杂岩体中,REE与Nb是高度富集在碳酸岩中。虽然不混溶实验表明REE与Nb在碳酸盐-硅酸盐熔体中的分配系数与含水量有关,即与熔体的聚合程度有关,但是绝大部分成矿碳酸岩成矿过程一般并不富水,所以碳酸岩中REE和Nb等关键金属元素超常富集的机理并不明确。因此未来的研究应重点关注在碳酸岩演化的过程中,除了水以外,其他配体对于关键金属元素在不混溶硅酸盐-碳酸盐熔体之间分配系数是否有影响,从而找到控制碳酸岩中关键金属成矿的关键。     

Is natrocarbonatite a cognate fluid condensate?

Natrocarbonatite flows in the crater of the volcano Oldoinyo Lengai (Tanzania) are the only carbonatite magmas observed to erupt and have provided strong arguments in favor of a magmatic origin for carbonatite. The currently favored explanation for the genesis of these carbonatites by liquid immiscibility between a silicate and a carbonatite melt is questioned based on the extremely low eruption temperatures of 544-593 °C and compositional and mineralogical characteristics not in agreement with experimental constraints. Experimental investigations of the relationship between Oldoinyo Lengai natrocarbonatite and related silicate rock compositions do indicate that alkali-bearing peralkaline carbonatite with liquidus calcite can form by liquid immiscibility. At the same time, these experiments result in evidence which speaks against a liquid immiscibility origin for the highly alkaline and peralkaline Oldoinyo Lengai natrocarbonatite. On the carbonatite side of the miscibility gap, fractional crystallization cannot account for a liquid evolution from alkali-bearing peralkaline carbonatite to highly alkaline natrocarbonatite. Such an evolution does not seem to be compatible with the liquidus mineral assemblages and the chemistry of Oldoinyo Lengai natrocarbonatite. No natural silicate magma is known to produce natrocarbonatite compositions by liquid immiscibility. The best interpretation of the Oldoinyo Lengai natrocarbonatite flows involves expulsion of a cognate, mobile, alkaline, and CO₂-rich fluid condensate. This conclusion is supported by recent studies of silicate and carbonatite melt inclusions in minerals of ultramafic alkaline complexes, trace element partitioning, isotopic constraints, and by experimental data on major element partitioning between coexisting H₂O-CO₂-rich fluid and carbonatitic melt. In contrast to all other suggested modes of formation, an origin of Oldoinyo Lengai natrocarbonatite from cognate fluid appears best to be in agreement with the field observations, the petrography, mineralogy, and geochemistry of Oldoinyo Lengai natrocarbonatite and the dynamics of the Oldoinyo Lengai natrocarbonatite extrusion.     

Deep differentiation of alkali ultramafic magmas: Formation of carbonatite melts

The study of melt microinclusions in olivine megacrysts from meimechites and alkali picrites of the Maimecha–Kotui alkali ultramafic and carbonatite province (Polar Siberia) revealed that the melt compositions corrected for loss of olivine due to post-entrapment crystallization of olivine on inclusion walls (differentiates of primary meimechite magma) match well to the composition of nephelinites and olivine melilitites belonging to carbonatite magmatic series. Modeling of fractional crystallization of meimechite magmas results in the high-alkali melt compositions corresponding to the silicate–carbonate liquid immiscibility field. The appearance of volatile-rich melts at the base of magma-generating plume systems at early stages of partial melting can be explained by extraction of incompatible elements including volatiles, by near-solidus melts at low degrees of partial melting, and meimechites are an example of such magmas. Subsequent accumulation of CO₂ in the residual melt results in generation of carbonate magma.     

Liquid immiscibility in deep-seated magmas and the generation of carbonatite melts

This paper reviews the results of investigations of melt inclusions in minerals of carbonatites and spatially associated silicate rocks genetically related to various deep-seated undersaturated silicate magmas of alkaline ultrabasic, alkaline basic, lamproitic, and kimberlitic compositions. The analysis of this direct genetic information showed that all the deep magmas are inherently enriched in volatile components, the most abundant among which are carbon dioxide, alkalis, halides, sulfur, and phosphorus. The volatiles probably initially served as agents of mantle metasomatism and promoted melting in deep magma sources. The derived magmas became enriched in carbon dioxide, alkalis, and other volatile components owing to the crystallization and fractionation of early high-magnesium minerals and gradually acquired the characteristics of carbonated silicate liquids. When critical compositional parameters were reached, the accumulated volatiles catalyzed immiscibility, the magmas became heterogeneous, and two-phase carbonate-silicate liquid immiscibility occurred at temperatures of ≥1280–1250°C. The immiscibility was accompanied by the partitioning of elements: the major portion of fluid components partitioned together with Ca into the carbonate-salt fraction (parental carbonatite melt), and the silicate melt was correspondingly depleted in these components and became more silicic. After spatial separation, the silicate and carbonate-silicate melts evolved independently during slow cooling. Differentiation and fractionation were characteristic of silicate melts. The carbonatite melts became again heterogeneous within the temperature range from 1200 to 800–600°C and separated into immiscible carbonate-salt fractions of various compositions: alkali-sulfate, alkali-phosphate, alkali-fluoride, alkali-chloride, and Fe-Mg-Ca carbonate. In large scale systems, polyphase silicate-carbonate-salt liquid immiscibility is usually manifested during the slow cooling and prolonged evolution of deeply derived melts in the Earth’s crust. It may lead to the formation of various types of intrusive carbonatites: widespread calcite-dolomite and rare alkali-sulfate, alkali-phosphate, and alkali-halide rocks. The initial alkaline carbonatite melts can retain their compositions enriched in P, S, Cl, and F only at rapid eruption followed by instantaneous quenching.     

Shonkinites and minettes of the Ryabinovyi massif (Central Aldan): composition and crystallization conditions

Dikes of biotitic shonkinites and minettes of the complex Ryabinovyi alkaline massif (Central Aldan) have been studied. The dikes are localized in a neck of K-picrites in the northeast of the massif, which intrudes gold-bearing microcline–muscovite metasomatites (Muscovitovyi site). The obtained data on the chemical and trace-element compositions of the rocks and minerals and study of melt inclusions in clinopyroxenes indicate that the biotitic shonkinites and minettes crystallized from the same deep-seated high-pressure alkaline ultrabasic magma during its evolution. Apparently, at the early stage of crystallization of diopside in the biotitic shonkinites, homogeneous carbonate–silicate melt was separated into immiscible fractions of silicate, carbonate–salt, and carbonate melts. The temperature of melt immiscibility was > 1120–1190 °C, i.e., higher than the homogenization temperature of silicate inclusions in the diopside. The contents of trace elements in the biotitic shonkinites and rock-forming clinopyroxenes were one or two orders of magnitude higher than the mantle values. The Eu/Eu* ratios of both the considered rocks and the clinopyroxenes were close to those of chondrites, which testifies to their crystallization from mantle magma. The HREE/LREE ratio indicates that the magma source was localized at the depths where garnet-spinel assemblages existed. The negative Nb and Ti anomalies in the trace-element spectra and the high (> 5) La/Nb ratios in the rocks and clinopyroxenes point to the influence of crustal material on the parental magma. Crystallization of magma took place in reducing conditions, which is evidenced by the low (4–7) Ti/V ratios in clinopyroxenes and the presence of chloride–sulfate inclusions in them. Since gold in the Ryabinovyi massif is associated with late sulfate–chloride and sulfate–carbonate fluids, it might have been transported by alkaline chloride–sulfate and carbonate (carbonatite) melts, found as inclusions in clinopyroxenes of the biotitic shonkinites, at the early stages of Mesozoic magmatism.     

http://www.sciencedirect.com/science/article/pii/S1674987111000429

The three most crucial factors for the formation of large and super-large magmatic sulfide deposits are: (1) a large volume of mantle-derived mafic-ultramafic magmas that participated in the formation of the deposits; (2) fractional crystallization and crustal contamination, particularly the input of sulfur from crustal rocks, resulting in sulfide immiscibility and segregation; and (3) the timing of sulfide concentration in the intrusion. The super-large magmatic Ni-Cu sulfide deposits around the world have been found in small mafic-ultramafic intrusions, except for the Sudbury deposit. Studies in the past decade indicated that the intrusions hosting large and super-large magmatic sulfide deposits occur in magma conduits, such as those in China, including Jinchuan (Gansu), Yangliuping (Sichuan), Kalatongke (Xinjiang), and Hongqiling (Jilin). Magma conduits as open magma systems provide a perfect environment for extensive concentration of immiscible sulfide melts, which have been found to occur along deep regional faults. The origin of many mantle-derived magmas is closely associated with mantle plumes, intracontinental rifts, or post-collisional extension. Although it has been confirmed that sulfide immiscibility results from crustal contamination, grades of sulfide ores are also related to the nature of the parental magmas, the ratio between silicate magma and immiscible sulfide melt, the reaction between the sulfide melts and newly injected silicate magmas, and fractionation of the sulfide melt. The field relationships of the ore-bearing intrusion and the sulfide ore body are controlled by the geological features of the wall rocks. In this paper, we attempt to demonstrate the general characteristics, formation mechanism,tectonic settings, and indicators of magmatic sulfide deposits occurring in magmatic conduits which would provide guidelines for further exploration.     

Genesis of kalsilite melilitite at Cupaello,Central Italy: Evidence from melt inclusions

The paper presents data on primary carbonate–silicate melt inclusions hosted in diopside phenocrysts from kalsilite melilitite of Cupaello volcano in Central Italy. The melt inclusions are partly crystalline and contain kalsilite, phlogopite, pectolite, combeite, calcite, Ba–Sr carbonate, baryte, halite, apatite, residual glass, and a gas phase. Daughter pectolite and combeite identified in the inclusions are the first finds of these minerals in kamafugite rocks from central Italy. Our detailed data on the melt inclusions in minerals indicate that the diopside phenocrysts crystallized at 1170–1190°C from a homogeneous melilitite magma enriched in volatile components (CO₂, 0.5–0.6 wt % H₂O, and 0.1–0.2 wt % F). In the process of crystallization at the small variation in P-T parameters two-phase silicate-carbonate liquid immiscibility occurred at lower temperatures (below 1080–1150°C), when spatially separated melilitite silicate and Sr-Ba-rich alkalicarbonate melts already existed. The silicate–carbonate immiscibility was definitely responsible for the formation of the carbonatite tuff at the volcano. The melilitite melt was rich in incompatible elements, first of all, LILE and LREE. This specific enrichment of the melt in these elements and the previously established high isotopic ratios are common to all Italian kamafugites and seem to be related to the specific ITEM mantle source, which underwent metasomatism and enrichment in incompatible elements.     

The role of liquid immiscibility in the genesis of carbonatites — An experimental study

The two-liquid field between alkali-carbonate liquids and phonolite or nephelinite magmas from the Oldoinyo Lengai volcano has been determined between 0.7 and 7.6 kb and 900°–1,250° C. The miscibility gap expands with increase in and decrease in temperature. Concomitantly there is a rotation of tie-lines so that the carbonate liquids become richer in CaO. The element distribution between the melts indicates that a carbonate liquid equivalent in composition to Oldoinyo Lengai natrocarbonatite lava would have separated from a phonolitic rather than a nephelinitic magma. CO₂-saturated nephelinites coexist with carbonate liquids much richer in CaO than the Lengai carbonatites, but even so these liquids have high alkali concentrations. If the sövites of hypabyssal and plutonic ijolite-carbonatite complexes originated by liquid immiscibility, then large quantities of alkalis have been lost, as is suggested by fenitization and related phenomena. The miscibility gap closes away from Na₂O-rich compositions, so that the tendency to exsolve a carbonatite melt is greater in salic than in mafic silicate magmas. The two-liquid field does not approach kimberlitic compositions over the range of pressures studied, suggesting that the globular textures observed in many kimberlite sills and dykes may be the result of processes other than liquid immiscibility at crustal pressures.     

Silicate--Carbonate Immiscibility at Oldoinyo Lengai

For approximately the last 50 years eruptions at Oldoinyo Lengaihave produced passive natrocarbonatite lavas interspersed withmixed silicate-natrocarbonatite events approximately every 15–25years. In 1993 an unusual blocky lava erupted and preserveddetailed mixed silicate-natrocarbonatite textures clearly indicatingan immiscible origin. The 1993 blocky flow consists of natrocarbonatitewith small silicate crystal aggregates which constitute 2–5%of the rock. These inclusions are composed of nepheline, melanite,clinopyroxene and wollastonite occurring both as isolated crystalsand ijolite micro-xenoliths. Most significantly, these ijoliticinclusions are surrounded by ‘globules’ of a fine-grainedintergrowth of nepheline, wollastonite and gregoryite, interpretedas quenched melt. Petrographic textures are characteristic ofliquid immiscibility between coexisting natrocarbonatite andsilicate melts. The presence of gregoryite within the silicatemelt globules is particularly important as it represents thecommon liquidus phase between the silicate and natrocarbonatitemelts theoretically required to demonstrate immiscibility betweentwo conjugate liquids. This is the first time that liquid immiscibilityhas been so clearly demonstrated in natural rock samples fromOldoinyo Lengai and agrees very closely with recent experimentalwork. Our detailed model for the petrogenesis of the natrocarbonatitesat Oldoinyo Lengai involves extensive fractionation of a carbonate-richalkaline silicate magma followed by immiscible separation ofnatrocarbonatite at low pressures. KEY WORDS: Oldoinyo Lengai; natrocarbonatite; silicate-carbonate immiscibility; East Africa ^*Corresponding author. Present address: Department of Mineralogy, The Natural History Museum, Cromwell Road, London SW_{7 5}BD, UK     

Primary Ca-rich carbonatite magma and carbonate-silicate-sulphide liquid immiscibility in the upper mantle

A primary carbonate phase with Ca/(Ca+Mg) in the range 0.85–0.95 has been identified in a metasomatized, depleted harzburgite nodule from Montana Clara Island, Canary Islands; textural relations show that this carbonate represents a quenched liquid. Although magnesian carbonate melts have been described from upper mantle peridotites, this is the first reported occurrence of a primary magma within peridotite nodules which has the composition of calciocarbonatite, by far the most common carbonatite type occurring in crustal complexes. The carbonate in the Montana Clara harzburgite host is restricted to wehrlitic alteration zones and is intimately associated with a second generation of minerals, mainly olivine, clinopyroxene and spinel, with glass of syenitic composition, and with Fe−Cu-rich sulphides. The metasomatic assemblage was formed by reaction of a sodiumbearing dolomitic melt, derived from a somewhat deeper level in the upper mantle, with the harzburgite mineral assemblage at a pressure of 15 kbars, or lower. As a result of the reaction the residual carbonatite melt became more enriched in calcium. The calciocarbonatite and sulphide phases almost invariably form globules in the silicate glass, indicating the existence of three immiscible liquids under upper mantle conditions. Several alkaline complexes contain carbonatites occurring with syenitic rock types and its seems feasible that the formation of such close associations might have been influenced by processes of liquid immiscibility which took place under upper mantle conditions. Editorial responsibility: I. Parsons     

岩浆通道系统与岩浆硫化物成矿研究新进展

大型-超大型岩浆硫化物矿床的形成需要满足3个基本条件:(1)大量幔源岩浆参与成矿;(2)岩浆演化导致硫化物熔离;(3)硫化物在有限空间聚集。然而,除Sudbury矿床外,全球与镁铁质岩浆有关的超大型铜镍硫化物矿床都发现于小的镁铁-超镁铁岩体中。近10年来的研究表明这些含矿岩体实际上都是岩浆通道系统的一部分,中国金川、杨柳坪、喀拉通克、红旗岭等大型和超大型Ni-Cu-(PGE)硫化物矿床都形成于岩浆通道系统中,正是岩浆通道这样特殊的开放系统为大规模岩浆硫化物矿床提供了成矿条件。总结国内外最新研究结果,可以发现与成矿有关的岩浆通道系统都分布在深大断裂附近,大规模的幔源岩浆补充与地幔柱、大陆裂谷、碰撞造山后伸展等地质事件有密切的关系。尽管研究证明硫化物熔离都与地壳物质的混染有关,但矿石各种元素的品位却受母岩浆性质、硫化物熔离强度、与新注入镁铁质岩浆反应、以及硫化物本身结晶分异等多重因素的影响;含矿岩体和硫化物矿体的形态和大小都强烈地受围岩地质特征的控制。进一步明确这类矿床的地质特征、形成机制、成矿背景和成矿标志,对未来的研究和找矿工作都是非常必要的。     

Experimental evidence for a relationship between liquid immiscibility and ore-formation in felsic magmas

Geological studies demonstrate that liquid immiscibility in felsic magma closely associates with the ore forming process. In order to obtain experimental evidence demonstrating the relationship between the ore forming process and liquid immiscibility in felsic magma, we carried out a series of experiments at high temperature and atmospheric pressure. The experimental results show that the granite ∼ KBF₄∼Na₂MoO₄ system is a homogeneous melt at high temperature. With decrease in temperature, however, the melt decomposes into two immiscible melts: silicate melt and ore-forming melt. The ore-forming melt exists as globules in the silicate phase. Molybdenm, Ca, Na, Mg, P, Mn, F, B, and OH are concentrated in these globules. The ore forming melt is characterized with very low SiO₂ and Al₂O₃ concentrations but the concentration of MoO₃ and CaO is very high. In contrast, the silicate melts are significantly enriched in SiO₂ and Al₂O₃, and depleted in MoO₃ and CaO. In the silicate melt the concentrations of network modifying elements (e.g. Mo, Ca, Na, P, Mg) and volatiles (F, OH) are very low. The differences between the two immiscible melts exist not only in chemical composition but also in structure. The ore-forming melt structurally consists of [MoO₄], [MoOF₄], [B(OH)₄], and OH, while the silicate melt is [Si0₄]. Because of the difference in composition and structure the two immiscible melts possess different physical properties. Compared to silicate melt, the ore-forming melt has a lower density and viscosity, which permits the globules to behave as bubbles in granite magma and to move and concentrate in the upper part of magma chamber. This process is probably responsible for the concentration of ore-forming elements in the upper part of granite bodies and their immediate aureoles. The present experimental results suggest that liquation in felsic magma can be the first step in the ore-forming process during granitoid evolution.     

Multiphase carbonate-salt immiscibility in carbonatite melts: data on melt inclusions from the Krestovskiy massif minerals (Polar Siberia)

Minerals of olivine–melilite and olivine–monticellite rocks from the Krestovskiy massif contain primary silicate-salt, carbonate-salt, and salt melt inclusions. Silicate-salt inclusions are present in perovskite I and melilite. Thermometric experiments conducted on these inclusions at 1,230–1,250°C showed silicate–carbonate liquid immiscibility. Globules of composite carbonate-salt melt rich in alkalies, P, S, and Cl separated in silicate melt. Carbonate salt globules in some inclusions from perovskite II at 1,190–1,200°C separated into immiscible liquid phases of simpler composition. Carbonate-salt and salt inclusions occur in monticellite, melilite, and garnet and homogenize at close temperatures (980–780°C). They contain alkalies, Ca, P, SO₃, Cl, and CO₂. According to the ratio of these components and predominance of one of them, melt inclusions are divided into 6 types: I—hyperalkaline (CaO/(Na₂O+K₂O)≤1) carbonate melts; II—moderately alkaline (CaO/(Na₂O+K₂O)>1) carbonate melts; III—sulfate-alkaline melts; IV—phosphate-alkaline melts; V—alkali-chloridic melts, and VI—calc-carbonate melts. Joint occurrence of all the above types and their syngenetic character were established. Some inclusions demonstrated carbonate-salt immiscibility phenomena at 840–800°C. A conclusion in made that the origin of carbonate melts during the formation of intrusion rocks is related to silicate–carbonate immiscibility in parental alkali-ultrabasic magma. The separated carbonate melt had a complex alkaline composition. Under unstable conditions the melt began to decompose into simpler immiscible fractions. Different types of carbonate-salt and salt inclusions seem to reflect the composition of these spatially isolated immiscible fractions. Liquid carbonate-salt immiscibility took place in a wide temperature range from 1,200–1,190°C to 800°C. The occurrence of this kind of processes under macroconditions might, most likely, cause the appearance of different types of immiscible carbonate-salt melts and lead to the formation of different types of carbonatites: alkali-phosphatic, alkali-sulfatic, alkali-chloridic, and, most widespread, calcitic ones.     

Lamprophyres of the Tomtor Massif: A result of mixing between potassic and sodic alkaline mafic magmas

The paper presents data on inclusions in minerals of the least modified potassic lamprophyres in a series of strongly carbonatized potassic alkaline ultramafic porphyritic rocks. The rocks consist of diopside, kaersutite, analcime, apatite, and rare phlogopite and titanite phenocrysts and a groundmass, which is made up, along with these minerals, of potassic feldspar and calcite. The diopside and kaersutite phenocrysts display unsystematic multiple zoning. Chemically and mineralogically, the rock is ultramafic foidite and most likely corresponds to monchiquite. Primary and secondary melt inclusions were found in diopside, kaersutite, apatite, and titanite phenocrysts and are classified into three types: sodic silicate inclusions with analcime, potassic silicate inclusions with potassic feldspar, and carbonate inclusions, which are dominated by calcite. Heating and homogenization of the inclusions show that the potassic lamprophyres crystallized from a heterogeneous magma, with consisted of mixing mafic sodic and potassic alkaline magmas enriched in a carbonatite component. The composition of the magmas was close to nepheline and leucite melanephelinite. The minerals crystallized at 1150–1090°C from the sodic melts and at 1200–1250°C from the potassic ones. The sodic mafic melts were richer in Fe than the potassic ones, were the richest in Al, Mn, SO₃, Cl, and H₂O and poorer in Ti and P. The potassic mafic melts were not lamproitic, as follows from the presence of albite in the crystallized primary potassic melt inclusions. The diopside, the first mineral to crystallize in the rock, started to crystallize in the magmatic chamber from sodic mafic melt and ended to crystallize from mixed sodic–potassic melts. The potassic mafic melts were multiply replenished in the chamber in relation to tectonic motions. The ascent of the melts to the surface and rapidly varying P–T parameters of the magma were favorable for multiple separations of carbonatite melts from the alkaline mafic ones and their mixing and mingling.     

碳酸岩岩浆作用过程的包裹体研究

碳酸岩是一种富含碳酸盐矿物(方解石，白云石，铁白云石等＞50％以上)的火成岩。通常以侵入的方式，与超基性岩和碱性岩共生，位于环状侵人体的中心部位；或以喷出的方式，与碱性岩等构成环状杂岩体。碳酸岩在喷出或侵入过程中，与上部地壳围岩发生以富含碱质(钠或钾)为主的蚀变作用，形成特征性的蚀变岩石——霓长岩。通过对碳酸岩中的包裹体研究，可以获得包括成岩成矿时的温度、压力、密度、流体组分、流体演化等大量信息。碳酸岩矿物中包裹体的研究已取得很大进展，并为了解碳酸岩岩浆演化性质和特征提供了许多重要的信息：(1)碳酸岩可以形成于流体和熔体两种介质条件下；(2)碳酸岩矿物中包裹体富含CO2；(3)在碳酸岩的起源和演化过程中伴随有岩浆的不混溶作用发生；(4)碳酸岩岩浆具有的较低的粘度和密度。为了保证对从碳酸岩中获得的包裹体资料的合理解释，在研究过程中必须结合碳酸岩产出的大地构造背景、典型岩石组合、典型蚀变岩石(霓长岩)、赋存的矿产特征等方面的资料。虽然目前在包裹体研究方面尚有许多不足，但作为自然界唯一能够保存有原始成岩成矿流体的地质样品，包裹体的研究具有其他方法不可替代的作用。     

The role of carbonate-fluoride melt immiscibility in shallow REE deposit evolution

The Lugiin Gol nepheline syenite intrusion, Mongolia, hosts a range of carbonatite dikes mineralized in rare-earth elements(REE). Both carbonatites and nepheline syenite-fluorite-calcite veinlets are host to a previously unreported macroscale texture involving pseudo-graphic intergrowths of fluorite and calcite. The inclusions within calcite occur as either pure fluorite, with associated REE minerals within the surrounding calcite, or as mixed calcite-fluorite inclusions, with associated zirconosilicate minerals. Consideration of the nature of the texture, and the proportions of fluorite and calcite present(～29 and 71 mol%,respectively), indicates that these textures most likely formed either through the immiscible separation of carbonate and fluoride melts, or from cotectic crystallization of a carbonatefluoride melt. Laser ablation ICP-MS analyses show the pure fluorite inclusions to be depleted in REE relative to the calcite. A model is proposed, in which a carbonate-fluoride melt phase enriched in Zr and the REE, separated from a phonolitic melt, and then either unmixed or underwent cotectic crystallization to generate an REE-rich carbonate melt and an REE-poor fluoride phase. The separation of the fluoride phase(either solid or melt) may have contributed to the enrichment of the carbonate melt in REE, and ultimately its saturation with REE minerals. Previous data have suggested that carbonate melts separated from silicate melts are relatively depleted in the REE, and thus melt immiscibility cannot result in the formation of REE-enriched carbonatites. The observations presented here provide a mechanism by which this could occur, as under either model the textures imply initial separation of a mixed carbonate-fluoride melt from a silicate magma. The separation of an REEenriched carbonate-fluoride melt from phonolitic magma is a hitherto unrecognized mechanism for REE-enrichment in carbonatites, and may play an important role in the formation of shallow magmatic REE deposits.     

Rare earth partitioning between immiscible carbonate and silicate liquids and CO2 vapor: Results and implications for the formation of light rare earth-enriched rocks

Melting relations at 5 and 20 kbar on the composition join sanidine-potassium carbonate are dominated by a two-liquid region that covers over 60% of the join at 1,300 ° C. At this temperature, the silicate melt contains approximately 19 wt% carbonate component at 5 kbar and 32 wt% carbonate component at 20 kbar. The conjugate carbonate melt contains less than 5 wt% silicate component, and it varies less as a function of temperature than does the silicate melt.Partition coefficients for Ce, Sm, and Tm between the immiscible carbonate and silicate melts at 1,200 ° and 1,300 ° C at 5 and 20 kbar are in favor of the carbonate melt by a factor of 2–3 for light REE and 5–8 for heavy REE. The effect of pressure on partitioning cannot be evaluated independently because of complementary changes in melt compositions.Minimum REE partition coefficients for CO₂ vapor/carbonate melt and CO₂ vapor/silicate melt can be calculated from the carbonate melt/silicate melt partition coefficients, the known proportions of melt, and maximum estimates of the proportion of CO₂ vapor. The vapor phase is enriched in light REE relative to both melts at 20 kbar and enriched in all REE, especially the light elements, at 5 kbar. The enrichment of REE in CO₂ vapor relative to both melts is 3–4 orders of magnitude in excess of that in water vapor (Mysen, 1979) at 5 kbar and is approximately the same as that in water vapor at 20 kbar.Mantle metasomatism by a CO₂-rich vapor enriched in light REE, occurring as a precursor to magma genesis, may explain the enhanced REE contents and light REE enrichment of carbonatites, alkali-rich silicate melts, and kimberlites. Light REE enrichment in fenites and the granular suite of nodules from kimberlites attests to the mobility of REE in CO₂-rich fluids under both mantle and crustal conditions.     

Trace Elements in Alkaline Lamprophyres,Clinopyroxene, and Amphibole of the Tomtor Massif and the Ore Potential of the Melts

Data obtained on lamprophyres from the carbonatite–volcanic unit in the lower horizon of the Tomtor Massif indicate that the rocks and zoned diopside and kaersutite phenocrysts in them are enriched in incompatible elements more significantly than is typical of alkaline ultramafic rocks of the Maymecha–Kotui and Kola provinces. The concentrations of these elements and their indicator ratios in the cores and intermediate zones of the diopside and kaersutite phenocrysts significantly vary, and this suggests that the minerals might have crystallized from different melts. This is consistent with the earlier conclusions, which were derived from studying melt inclusions, that the phenocrysts crystallized from mixing alkaline mafic melts of sodic and potassic types and different Mg–number which were enriched in the carbonatite component. The cores of the diopside phenocrysts started to crystallize from sodic mafic magma in a magmatic chamber, while the intermediate and outermost zones of this mineral crystallized from mixed sodic–potassic mafic melts. The carbonatite component was separated from the sodic mafic melt at high temperature (>1150°C) during diopside core crystallization. The bulk compositions of the alkaline lamprophyres and of the diopside and kaersutite phenocrysts contain lower normalized concentrations of HREE than LREE. This led us to conclude that the parental sodic and potassic mafic melts were derived from an enriched mantle source material under garnet–facies parameters, as is typical of continental rifts. It is noteworthy that the potassic mafic melt was derived at greater depths and lower degrees of melting of the mantle source than the sodic melt. The iron–rich sodic melt from which the cores of the diopside phenocrysts started to crystallize was enriched in V, REE, Y, and volatile components (H₂O, CO₂, F, Cl, and S). The onset of carbonate–silicate liquid immiscibility was marked by the redistribution of REE and Y into the carbonatite melt. The potassic, more Mg–rich mafic melt from which the intermediate and outermost zones of the diopside phenocrysts crystallized was enriched in Ti, Nb, Zr, and REE and always remained homogeneous when this mineral crystallized.     

Origin of carbonatite magma during the evolution of ultrapotassic basite magma

Clinopyroxene phenocrysts in fergusite from a diatreme in the Dunkel’dyk potassic alkaline complex in the southeastern Pamirs, Tajikistan, and from carbonate veinlets cutting across this rock contain syngenetic carbonate, silicate, and complex melt inclusions. The homogenization of the silicate and carbonate material of the inclusions with the complete dissolution of daughter crystalline phases and fluid in each of them occur simultaneously at 1150?1180°C. The pressures estimated using fluid inclusions and mineral geobarometers were 0.5–0.7 GPa. The behavior of the inclusions during their heating and their geochemistry are in good agreement with the origin of carbonate melts via liquid immiscibility. Carbonatite magma was segregated at the preservation of volatile components (H₂O, CO₂, F, Cl, and S) in the melt, and this resulted in the crystallization of H₂O-rich minerals and carbonates and testifies that the magma was not intensely degassed during its ascent to the surface. The silicate melts are rich in alkalis (up to 4 wt % Na₂O and 12 wt % K₂O), H₂O, F, Cl, and REE (up to 1000 ppm), LREE, Ba, Th, U, Li, B, and Be. The diagrams of the concentrations of incompatible elements of these rocks typically show deep Nb, Ta, and Ti minima, a fact making them similar to the unusual type of ultrapotassic magmas: lamproites of the Mediterranean type. These magmas are thought to be generated in relation to subduction processes, first of all, the fluid transport of various components from a down-going continental crustal slab into overlying levels of the mantle wedge, from which ultrapotassic magmas are presumably derived.