Time-dependent geochemistry of clinopyroxene from the Alban Hills (Central Italy): Clues to the source and evolution of ultrapotassic magmas

We investigated chemical and isotopic compositions of clinopyroxene crystals from well age-constrained juvenile scoria clasts, lava flows, and hypoabyssal magmatic ejecta representative of the whole eruptive history of the Alban Hills Volcanic District. The Alban Hills is a Quaternary ultra-potassic district that was emplaced into thick limestone units along the Tyrrhenian margin of Italy. Alban Hills volcanic products, even the most differentiated, are characterised by low SiO₂ content. We suggest that the low silica activity in evolving magmas can be ultimately due to a decarbonation process occurring at the magma/limestone interface. According to the liquid line of descent we propose, the differentiation process is driven by crystallisation of clinopyroxene + leucite ± apatite ± magnetite coupled with assimilation of a small amount of calcite and/or with interaction with crustal CO₂. By combining age, chemical data, strontium and oxygen isotopic compositions, and REE content of clinopyroxene, we give insights into the evolution of primitive ultrapotassic magmas of the Alban Hills Volcanic District over an elapsed period of about 600 kyr. Geochemical features of clinopyroxene crystals, consistent with data coming from other Italian ultrapotassic magmas, indicate that Alban Hills primary magmas were generated from a metasomatized lithospheric mantle source. In addition, our study shows that the ⁸⁷Sr / ⁸⁶Sr and LREE/HREE of Alban Hills magmas continuously diminished during the 600–35 ka time interval of the Alban Hills eruptive history, possibly reflecting the progressive depletion of the metasomatized mantle source of magmas.     

Oxygen isotope fractionation during the dolomitization of calcium carbonate

The oxygen isotope fractionation accompanying the hydrothermal dolomitization of CaCO₃ between 252 and 295°C has been investigated. Dolomitization (which occurs via the crystallization of one or more intermediate magnesian calcite phases) is characterised by a progressive lowering in δ⁸O, which smoothly correlates with the change in the Mg/(Mg + Ca) and the $\text{Sr}\text{(Mg + Ca)}$ ratios and with the sequential phase formation. The data support the proposals of Katz and Matthews (1977) that (a) all reaction occurs by solution and reprecipitation, (b) intermediate phases and dolomite form sequentially and (c) the intermediate phases form within limited solution zones surrounding the dissolving precursor. Calculated volumes of the solution zone for the aragonite → low magnesian calcite transformation are within the range 3.7–6.7 × 10^?5 liters (out of 5 × 10^?3 liters, the volume of the bulk solution used in the present study), and agree well with those calculated from strontium and magnesium partitioning data. Dolomite precipitates in apparent isotopic equilibrium with the bulk solution. The temperature dependence of the fractionation is defined by the equation 1000 Inα_D-H2O = 3.06 × 10⁶T^?2 ? 3.24 Dolomite-water fractionations from this equation are significantly lower than those obtained by extrapolation of the Northrop And Clayton (1966) calibration. The reaction zone model can be applied to explain near zero dolomite-calcite oxygen isotope fractionations reported by Epsteinet al. (1964).     

Oxygen, carbon, and strontium isotope geochemistry of diamond-bearing carbonate rocks from Kumdy-Kol, Kokchetav Massif, Kazakhstan

Diamond-bearing carbonate rocks from Kumdy-Kol, Kokchetav massif, Kazakhstan, were strongly altered by fluids flowing through fractures and infiltrating along grain boundaries during exhumation. Alteration includes retrogradation of high-grade silicate assemblages by hydrous minerals, replacement of diamond by graphite and of dolomite by calcite. Diamond-bearing carbonate rocks are among the most intensely altered isotopically with δ¹⁸O_VSMOW values as low as +9‰, δ¹³C_VPDB=−9‰, and ⁸⁷Sr/⁸⁶Sr as high as 0.8050. Evidence of isotopic equilibration between coexisting dolomite and high-Mg calcite during ultrahigh-pressure metamorphism (UHPM) is preserved only rarely in samples isolated from infiltrating fluids by distance from fractures. Isotopic heterogeneity and isotopic disequilibrium are widespread on a hand-specimen scale. Because of this lack of homogeneity, bulk analyses cannot provide definitive measurements of ¹³C/¹²C fractionation between coexisting diamond and carbonate. Our study adequately documents alteration on a scale commensurate with observed vein structures. But, testing the hypothesis of metamorphic origin of microdiamonds has not fully succeeded because our analytical spatial resolution, limited to 0.5 mm, is not small enough to measure individual dolomite inclusions or individual diamond crystals.     

Carbon isotope geochemistry of the Precambrian Lomagundi carbonate province,Rhodesia

Carbon isotope measurements carried out on 67 dolomite samples from the Middle Precambrian Lomagundi Group (Rhodesia) have yielded a δ¹³C mean of +8.2 ± 2.6%. vs PDB. With the outcrop of these dolomites extending over a distance of almost 300 km, the Lomagundi dolomite faces is likely to represent the largest isotopically anomalous sedimentary carbonate province ever recorded. It is concluded that the anomalous carbonates formed in a closed basin whose δ¹³C level had been substantially increased as a result of a preferential removal (within sedimentary organics) of the light carbon isotope.     

The role of fluorine in the evolution of ultrapotassic magmas

Summary The distribution of F and, to a lesser extent, Cl between phlogopite, amphibole, apatite, and glass in kamafugites from the West Eifel, Germany, and South-West Uganda, and from lamprophyres (minettes) from Hopi-Navajo, Arizona has been determined. In addition, these elements have been analyzed in the same phases from mantle-derived xenoliths from the kamafugitic rocks. All halogen determinations were made using a JEOL 8600 electron microprobe. The F contents and trends in the minerals and glass in the kamafugites and lamprophyres are very similar to those reported for lamproites (Edgar and Charbonneau, 1991). The results indicate that F in the minerals of ultrapotassic magmas is much greater then that found in the xenoliths that are believed to represent likely source regions for such magmas. Chlorine is present in much lower amounts and in the same phases. The discrepancy between F in the xenoliths and in the lavas, and the preference for F to be incorporated in solid phases suggest that F is insufficient to account for the F found in ultrapotassic magmas or to provide for the reduced fluid conditions proposed by Foley (1988) for the genesis of such magmas. Based on these results, the genesis of ultrapotassic magmas may occur if they are partial melts of a mantle source that has been further enriched in F by repeated partial melting of mantle-derived xenoliths such as those of southwest Uganda. Alternatively the slightly higher Cl in the minerals of the xenoliths relative to the magmas suggests that Cl has been lost during degassing of the ascending magma. This may enrich the magmas in F by a dilution effect that may take place prior to the formation of phenocrystal F-rich phlogopites that are often present in ultrapotassic magmas.

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Die Rolle von fluor in der evolution ultrapotassischer magmen

Zusammenfassung Die Verteilung von Fluor and untergeordnet von Chlor zwischen Phlogopit, Amphibol, Apatit and Glas wurde an Kamafugiten aus der westlichen Eifel, Deutschland and aus Südwest-Uganda sowie an Lamprophyren (Minetten) aus Hopi-Navajo, Arizona bestimmt. Außerdem wurde der Gehalt an diesen Elementen in den gleichen Mineralphasen von Mantel-Xenolithen aus kamafugitischen Gesteinen analysiert. Die Halogenbestimmungen wurden an einer JEOL 8600 Mikrosonde durchgeführt. Die Gehalte und Verteilungstrends von Fluor in den Mineralphasen und im Glas der Kamafugite und Lamprophyre sind vergleichbar mit jenen aus Lamproiten (Edgar und Charbonneau, 1991). Die Resultate deuten an, daß der Fluorgehalt in Mineralen ultrapotassischer Magmen viel höher ist als in Xenolithen, die als Repräsentanten der Herkunftsregion derartiger Magmen gelten. Chlor tritt in den selben Mineralphasen in viel geringeren Mengen auf. Das unterschiedliche Auftreten von Fluor in den Xenolithen und in den Laven sowie der bevorzugte Einbau von Fluor in feste Mineralphasen lassen vermuten, daß dieser Gehalt an Fluor nicht ausreicht, um den hohen Fluorgehalt in ultrapotassischen Magmen und die reduzierenden Fluida-Bedingungen, wie sie von Foley (1988) für die Genese von solchen Magmen angenommen worden sind, zu erklären. Auf der Basis dieser Ergebnisse können ultrapotassische Magmen nur dann entstehen, wenn das Mantelmaterial als Herkunft für die partielle Schmelze zum Beispiel durch wiederholtes Teilaufschmelzen von Mantelxenolithen wie jenen aus Südwest-Uganda an Fluor angereichert worden ist. Als Alternative wird angenommen, daß die leicht höheren Chlorgehalte in den Mineralen der Xenolithe verglichen mit dem der Magmen durch Chlorverlust während Entgasung beim Aufstieg des Magmas zustande gekommen sind. Dadurch kam es zu einem Verdünnungseffekt, der zu einer Anreicherung von Fluor führt, vor der Bildung von F-reichem Phlogopit als Phenokristall, Kristalle, die häufig in ultrapotassischen Magmen auftreten.

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With 9 Figures     

Oxygen and carbon isotope measurements of land snail shell carbonate

δ¹³C and δ¹⁸O analyses have been performed on the aragonite shells of a variety of modern land snails from a number of different geographic and climatic locales. The δ¹⁸O values of the waters assumed to be in isotopic equilibrium with the shell carbonate were calculated. These calculated δ¹⁸O values are more positive than the δ¹⁸O values of the average meteoric waters in the locales in which the snails lived. The ¹⁸O enrichment appears to be linearly related to the reciprocal of the local relative humidity, which is consistent with the notion that these ambient waters have undergone isotopic steady-state evaporation. Measurements of the δ¹⁸O values of ancient land snail shells from the excavation of Sudden Shelter (42SV6) at Ivie Creek, Utah, suggest that the climate at this site was probably warmer and/or drier around 7100–7800 BP than at present.     

Application of the trace element and isotope geochemistry of strontium to studies of carbonate diagenesis

Carbonate rocks and natural waters exhibit a wide range in the concentration and isotopic composition of strontium. This wide range and the quantifiable covariation of these parameters can provide diagnostic tools for understanding processes of fluid-rock interaction. Careful consideration of the uncertainties associated with trace element partitioning, sample heterogeneity and fluid-rock interaction mechanisms is required to advance the application of the trace element and isotope geochemistry of strontium to studies of diagenesis, goundwater evolution, ancient seawater chemistry and isotope stratigraphy. A principal uncertainty involved in the application of Sr concentration variations to carbonate systems is the large range of experimental and empirical results for trace element partitioning of Sr between mineral and solution. This variation may be a function of precipitation rate, mineral stoichiometry, crystal growth mechanism, fluid composition and temperature. Calcite and dolomite in ancient limestones commonly have significantly lower Sr concentrations (20–70 p.p.m.) than would be expected from published trace element distribution coefficient values and Sr/Ca ratios of most modern sedimentary pore waters. This discrepancy probably reflects the uncertainties associated with determining distribution coefficient values. As techniques improve for the analytical measurement and theoretical modelling of Sr concentration and isotopic variations, the petrological analysis of carbonate samples becomes increasingly important. The presence of even small percentages of non-carbonate phases with high Rb concentrations and high ⁸⁷ Sr⁸⁶ Sr values, such as clay minerals, can have significant effects on the measured ⁸⁷ Sr/⁸⁶ Sr values of carbonate rocks, due to the decay of ⁸⁷Rb to ⁸⁷ Sr. For example, a Permian marine limestone with 50 p.p.m. Sr and 1 p.p.m. Rb will have a present-day ⁸⁷ Sr/⁸⁶ Sr value that is >2 × 10^?4 higher than its original value. This difference is an order of magnitude greater than the analytical uncertainty, and illustrates the importance of assessing the need for and accuracy of such corrections. A quantitative evaluation of the effects of water-rock interaction on Sr concentrations and isotope compositions in carbonates strengthens the application of these geochemical tracers. Geochemical modelling that combines the use of trace elements and isotopes can be used to distinguish between different mechanisms of water-rock interaction, including diffusive and advective transport of diagenetic constituents in meteoric pore fluids during the recrystallization of carbonate minerals. Quantitative modelling may also be used to construct diagnostic fluid-rock interaction trends that are independent of distribution coefficient values, and to distinguish between mixing of mineral end-members and fluid-rock interaction.     

Oxygen isotope partitioning between phosphate and carbonate in mammalian apatite

The oxygen isotope compositions of phosphate and structural carbonate in mammalian enamel and bone apatite are linked to that of body water at constant body temperature near 37°C, but the isotope systematics of oxygen in structural carbonate are not well understood. Using coupled measurements of the oxygen isotope composition of structural carbonate and phosphate from horse tooth enamel, the apparent oxygen isotope fractionation factor between structural carbonate and body water is estimated to be 1.0263 ± 0.0014. These estimates provide a quantitative basis for using the oxygen isotope composition of structural carbonate in mammalian biogenic apatite for ecological, climatological, and physiological reconstruction.     

Oxygen isotope geochemistry of the Mesozoic volcanics of the Etendeka Formation,Namibia

The Etendeka Formation volcanics consist of a bimodal association of basalts and quartz latites. Forty three new whole rock oxygen isotope analyses are reported for all the major magma types. All the rocks except a minor suite of dolerites have higher ¹⁸O values than normal mantle. The basic rocks (average of 29=8.8) have significantly different ¹⁸O to the acid rocks (average of 10=14.4) These data are apparently consistent with previously published petrogenetic models, which propose that the basalts were affected by crustal contamination and that the quartz latites are crustally derived. However, mineral oxygen data show that there is significant oxygen isotopic disequilibrium between phenocryst and whole rock, the latter being significantly higher in most cases. One of the basic magma types (the Tafelberg basalts) shows mutual positive correlations between ¹⁸O, SiO₂ and _Sr. If these correlations are due to crustal contamination, then as much as 45% contamination is required by material having a ¹⁸O value of 15 which is the maximum observed value in the Damaran basement rocks. In the absence of pyroxene phenocryst ¹⁸O data for the high _Sr Tafelberg basalts (they are aphyric), it is not possible to confirm that contamination has taken place. An alternative explanation is that the correlation between _Sr and SiO₂ resulted from assimilation coupled with fractional crystallization (AFC) (before emplacement). Post-eruption alteration resulted in a correlation between SiO₂ ¹⁸O because the material with the most Si-O bonds was able to concentrate ¹⁸O more effectively. The limited mineral data for the quartz latites suggests that there is some source heterogeneity. A pyroxene ¹⁸O value of 10% for a southern Etendeka quartz latite is consistent with a crustal source.     

Oxygen isotope geochemistry of hydrothermally-altered synmetamorphic granitic rocks from South-Central Maine,USA

Hydrothermally-altered mesozonal synmetamorphic granitic rocks from Maine have whole-rock ¹⁸O (SMOW) values 10.7 to 13.8. Constituent quartz, feldspar, and muscovite have ¹⁸O in the range 12.4 to 15.2, 10.0 to 13.2, and 11.1 to 12.0, respectively. Mean values of _Q–F ( ¹⁸O_quartz– ¹⁸O_feldspar)=2.4 and _Q–M ( ¹⁸O_quartz– ¹⁸O_muscovite)=3.3 are remarkably uniform (standard deviations of both are 0.2). Measured _Q–F and _Q–M values demonstrate that the isotopic compositions of the minerals are altered from primary magmatic ¹⁸O values but that the minerals closely approached oxygen isotope exchange equilibrium at subsolidus temperatures. Analyzed muscovites have D (SMOW) values in the range –65 to –82.Feldspars in the granitic rocks are mineralogically altered to either (a) muscovite+calcite, (b) muscovite+calcite+epidote, (c) muscovite+epidote, or (d) muscovite only. A consistent relation exists between the assemblage of secondary minerals and the oxygen isotope composition of whole rocks, quartz, and feldspar. Rocks with assemblage (a) have whole-rock ¹⁸O>12.1 and contain quartz and feldspar with ¹⁸O>13.8 and >11.4, respectively. Rocks with assemblages (b), (c), and (d) have whole-rock ¹⁸O<11.4 and contain quartz and feldspar with ¹⁸O< 13.1 and <11.0, respectively. The correlation suggests that the mineralogical alteration of the rocks was closely coupled to their isotopic alteration.Three mineral thermometers in altered granite suggest that the hydrothermal event occurred in the temperature range 400°–150° C, 100°–150° C below the peak metamorphic temperature inferred for country rocks immediately adjacent to the plutons. Calculations of mineral-fluid equilibria indicate that samples with assemblage (a) coexisted during the event with CO₂-H₂O fluids of and ¹⁸O=10.8 to 12.2 while samples with assemblages (b), (c), or (d) coexisted with fluids of and ¹⁸O=9.4 to 10.1. Compositional variations of the hydrothermal fluids were highly correlated: fluids enriched in CO₂ were also enriched in ¹⁸O. Because CO₂ was added to the granites during hydrothermal alteration and because fluids enriched in CO₂ were enriched in ¹⁸O, some or all of the variation in ¹⁸O of altered granites may have been caused by addition of ¹⁸O to the rocks during the hydrothermal event. The source of both the CO₂ and ¹⁸O could have been high-¹⁸O metasedimentary country rocks. The inferred change in isotopic composition of the granites is consistent with depletion of the metacarbonate rocks in ¹⁸O close to the plutons and with large volumes of fluid that were inferred from petrologic data to have infiltrated the metacarbonate rocks during metamorphism.A close approach of minerals to oxygen isotope exchange equilibrium in altered mesozonal rocks from Maine is in marked contrast to hydrothermally-altered epizonal granites whose mineral commonly show large departures from oxygen isotope exchange equilibrium. The difference in oxygen isotope systematics between altered epizonal granites and altered mesozonal granites closely parallels a differences between their mineralogical systematics. Both differences demonstrate the important control that depth exerts on the products of hydrothermal alteration. Deeper hydrothermal events occur at higher temperature and are longer-lived. Minerals and fluid have sufficient time to closely approach both isotope exchange and heterogeneous chemical equilibrium. Shallower hydrothermal events occur at lower temperatures and are shorter-lived. Generally there is insufficient time for fluid to closely approach equilibrium with all minerals.     

铁氧化物氧同位素示踪原理及其在铁矿成因研究中的应用

铁氧化物(以磁铁矿和赤铁矿最为常见)是铁矿床中最主要的含铁矿物,其氧同位素地球化学对于铁矿的成因研究具有重要意义。本文在总结了铁氧化物氧同位素分馏理论、不同成因类型铁矿形成过程的基础上,对世界主要类型铁矿铁氧化物的氧同位素组成特征和分馏规律进行了总结,并以新疆智博、查岗诺尔、备战海相火山岩型铁矿为例,开展了磁铁矿氧同位素地球化学研究。结果发现,这些铁矿中磁铁矿氧同位素组成δ18OSMOW集中在1‰～3‰之间,表明其形成于岩浆作用主导的高温岩浆/岩浆-热液环境,后期低温热液作用对铁的成矿作用影响有限。     

Crystallization conditions of leucite-bearing magmas and their implications on the magmatological evolution of ultrapotassic magmas: the Vico Volcano, Central Italy

Summary Mineral compositions in leucite-bearing and leucite-free rocks from Vico volcano are reported. FeO/MgO partitioning (Kd_ol/liq) between olivine and latite (0.14–0.22), and between olivine and trachyte (0.06–0.10) indicates a lack of equilibrium between mineral and host rock. This suggests that mingling and/or mixing between magmas was a leading process during magmatic differentiation. In addition, a phono-tephrite olivine population with high (0.84) and equilibrium (0.23–0.29) Kd_ol/liq values has been produced by the interaction of differently evolved magmas. Zoning in clinopyroxene and plagioclase from these rocks recorded the same processes. In addition, resorbed quartz xenocrysts with coronas of clinopyroxene microlites indicate that digestion of crustal rocks occurred during the residence of magma in a shallow level reservoir. Increasing Fe coupled with decreasing Ca in diopside crystals from some phonolites, together with the petrographic and trace element data, indicate that polybaric fractional crystallisation also may be involved in the genesis of magmas of the second period of Vico activity. Leucite-free trachybasalts erupted in a late stage contain highly forsteritic olivine phenocrysts (forsterite 84–88 mol.%) in-equilibrium (Kd_ol/liq = 0.24–0.35) with the host rock, which indicate that they did not suffer chemical modification at low pressure. Received November 28, 2000; revised version accepted September 27, 2001     

Oxygen and carbon isotope geochemistry of the Krivoy rog iron formation,Ukranian SSR

Oxygen and carbon isotope analyses of samples from three mines in the Krivoy Rog iron formation, Ukranian SSR, are reported here. Maximum and minimum quartz-magnetite fractionation values ($\text{Δ}{}_{\mathrm{<mtext>QM</mtext>}}$) and inferred temperature range in degrees centrigrade for each mine are:

     

15.

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

F. Barberi  H. Bizouard  J. Varet 《Contributions to Mineralogy and Petrology》1971,33(2):93-107

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.     

16.

Sulphur isotope geochemistry of carbonatites     

Roger H. Mitchell  H.Roy Krouse 《Geochimica et cosmochimica acta》1975,39(11):1505-1513

Sulphur isotopic data for sulphides and barite from several carbonatites (Mountain Pass, Oka, Magnet Cove, Bearpaw Mountains, Phalabora) show that individual carbonatites have different mean sulphide or barite isotopic compositions which deviate from the meteoritic mean $\text{δ}{}^{34}\text{S(0‰)}$.Classification of carbonatites in terms of T,?O₂ and pH during formation of the sulphur-bearing assemblages indicates that with decreasing T and increasing relative ?O₂ the mean δ³⁴S sulphide becomes increasing negative relative to the mean magma δ³⁴S. Only barite-free high temperature carbonatites (Phalabora) in which the mean δ^34S sulphide approaches the mean magmaδ³⁴S as a consequence of the paucity of oxidized anionic sulphur species in the magma can be used to directly estimate the mean isotopic composition of the source material.Barites from the Mountain Pass carbonatite show an increase in δ³⁴S with sequence of intrusion of the carbonatite units; dolomitic carbonatite (mean δ³⁴S, + 5.4‰), calcitic carbonatite (+ 4.8%.), silicified carbonatite (+ 6.9‰), tabular carbonatite dikes (+ 8.7‰), mineralized shear zones (+ 9.5‰). Within each of these units a spread of 6.8%. is evident. Isotopic trends in this low temperature (300°C) carbonatite are evaluated by treating the system as a hydrothermal fluid. The observed isotopic variations can be explained by removal of large amounts of sulphur from a fluid whose mean δ³⁴S is 0 to + 1‰     

17.

Dependence of clinopyroxene composition on cooling rate in basaltic magmas: Implications for thermobarometry     

Silvio Mollo  Pierdomenico Del Gaudio  Guido Ventura  Gianluca Iezzi  Piergiorgio Scarlato 《Lithos》2010,118(3-4):302-312

The compositional variation of clinopyroxene and the partitioning of major elements between clinopyroxene and melt are estimated as a function of the cooling rate. Clinopyroxenes were crystallized under variable cooling regimes (15, 9.4, 3, 2.1, and 0.5 °C/min from 1250 down to 1000 °C) and at isothermal conditions of 1000 °C from a basaltic composition at a pressure of 500 MPa under anhydrous and hydrous (H₂O = 1.3 wt.%) conditions. The clinopyroxene chemistry shows that, as the cooling rate increases, crystals are progressively depleted in Ca, Mg, Fe²⁺ and Si and enriched in Na, Fe³⁺, Al (mainly Al^IV), and Ti. Di and Hd versus CaTs and CaFeTs form a continuous binary solid solution characterized by higher amounts of tschermakitic components with increasing cooling rate. Two parameters (DH = Di + Hd and TE = CaTs + CaFeTs + En) are calculated to describe the effect of cooling rate on the clinopyroxene composition. The variation of DH/TE with increasing cooling rate evidences the kinetic process induced by rapid cooling in basic rocks under hydrous and anhydrous conditions.Dynamic crystallization conditions affect the partitioning of major elements between clinopyroxene and melt; with increasing cooling rate, the value of crystal–melt partition coefficient departs from that obtained at the isothermal condition. However, in spite of these variations, the values of ^cpx–meltKd_Fe–Mg remain almost constant. Therefore, the Fe²–Mg exchange between clinopyroxene and melt is not suitable to prove the (dis)equilibrium conditions in basaltic cooling magmas, giving rise to possible mismatches in the application of thermobarometers. The results of our study are consistent with that observed at the margin of dikes or in the exterior portions of lavas, where the cooling rate is maximized and disequilibrium compositions of clinopyroxene have been found.     

18.

Major, trace element and isotope geochemistry (Sr-Nd-Pb) of interplinian magmas from Mt. Somma-Vesuvius (Southern Italy)     

R. Somma  R. A. Ayuso  B. De Vivo  G. Rolandi 《Mineralogy and Petrology》2001,73(1-3):121-143

Summary Major, trace element and isotopic (Sr, Nd, Pb) data are reported for representative samples of interplinian (Protohistoric, Ancient Historic and Medieval Formations) activity of Mt. Somma-Vesuvius volcano during the last 3500 years. Tephra and lavas exhibit significant major, trace element and isotopic variations. Integration of these data with those obtained by previous studies on the older Somma suites and on the latest activity, allows to better trace a complete petrological and geochemical evolution of the Mt. Somma-Vesuvius magmatism. Three main groups of rocks are recognized. A first group is older than 12.000 yrs, and includes effusive-explosive activity of Mt. Somma. The second group (8000–2700 yrs B.P.) includes the products emitted by the Ottaviano (8000 yrs. B.P.) and Avellino (3550 yrs B.P.) plinian eruptions and the interplinian activity associated with the Protohistoric Formation. Ancient Historic Formation (79–472 A.D.), Medieval Formation (472–1139 A.D.) and Recent interplinian activity (1631–1944 A.D.) belong to the third group of activity (79–1944 A.D.). The three groups of rocks display distinct positive trends of alkalis vs. silica, which become increasingly steeper with age. In the first group there is an increase in silica and alkalis with time, whereas an opposite tendency is observed in the two younger groups. Systematic variations are also evident among the incompatible (Pb, Zr, Hf, Ta, Th, U, Nb, Rb, Cs, Ba) and compatible elements (Sr, Co, Cr). REE document variable degrees of fractionation, with recent activity displaying higher La/Yb ratios than Medieval and Ancient Historic products with the same degree of evolution. N-MORB normalized multi-element diagrams for interplinian rocks show enrichment in Rb, Th, Nb, Zr and Sm (> ^*10 N-MORB). Sr isotope ratios are variable, with Protohistoric rocks displaying ⁸⁷Sr/⁸⁶Sr =  0.70711–0.70810, Ancient Historic ⁸⁷Sr/⁸⁶Sr = 0.70665–0.70729, and Medieval ⁸⁷Sr/⁸⁶Sr = 0.70685–0.70803. Neodymium isotopic compositions in the interplinian rocks show a tendency to become slightly more radiogenic with age, from the Protohistoric (¹⁴³Nd/¹⁴⁴Nd = 0.51240–0.51247) to Ancient Historic (¹⁴³Nd/¹⁴⁴Nd = 0.51245–0.51251). Medieval interplinian activity (¹⁴³Nd/¹⁴⁴Nd: 0.51250–0.51241) lacks meaningful internal trends. All the interplinian rocks have virtually homogeneous compositions of ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb in acid-leached residues (²⁰⁷Pb/²⁰⁴Pb ∼15.633 to 15.687, ²⁰⁸Pb/²⁰⁴Pb ∼38.947 to 39.181). Values of ²⁰⁶Pb/²⁰⁴Pb are very distinctive, however, and discriminate among the three interplinian cycles of activity (Protohistoric: 18.929–18.971, Ancient Historic: 19.018–19.088, Medieval: 18.964–19.053). Compositional trends of major, trace element and isotopic compositions clearly demonstrate strong temporal variations of the magma types feeding the Somma-Vesuvius activity. These different trends are unlikely to be related only to low pressure evolutionary processes, and reveal variations of parental melt composition. Geochemical data suggest a three component mixing scheme for the interplinian activity. These involve HIMU-type and DMM-type mantle and Calabrian-type lower crust. Interaction between these components has taken place in the source; however, additional quantitative constraints must be acquired in order to better discriminate between magma characteristics inherited from the sources and those acquired during shallow level evolution. Received May 5, 2000; revised version accepted June 19, 2001     

19.

Oxygen isotope and REE geochemistry of metamorphic veins within the Zhoutan Group,central Jiangxi Province     

Gongren Hu  Congqiang Liu  Ruilian Yu  Weihe Yu  Yue Liu 《中国地球化学学报》2011,30(4):422-429

Geochemical studies on REE, trace elements and oxygen isotopes from metamorphic veins and their host metasedimentary rocks in the Zhoutan Group at two localities, Xiangshan and Yihuang, in central Jiangxi Province have been conducted in this paper. The results show that the metamorphic quartz veins inherited the REE and oxygen isotope geochemical characteristics from their host rocks, suggesting that the vein-forming fluids were derived from the host rocks. Additionally, fractionation degrees of the trace element pairs Zr-Hf, Nb-Ta, Y-Ho and U-Th in the veins are different from those of their host rocks. It is also indicated that the veins are the products of the fluids. The metamorphic veins within the Zhoutan Group metasedimentary rocks were formed principally as a result of lateral diffusion of the metamorphic fluids.     

20.

Oxygen and hydrogen isotope geochemistry of Cretaceous bentonites and shales from the Disturbed Belt,Montana     

《Geochimica et cosmochimica acta》1986,50(1):59-68

     

Mine	$\text{Δ}{}_{\mathrm{<mtext>QM</mtext>}}$	Corresponding temperature
Sevgok	9.4 to 14.2	475° to 320°C
Ugok	10.0 to 12.7	450° to 355°C
Annovsky	10.5 to 12.6	430° to 360°C

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.     

Sulphur isotope geochemistry of carbonatites

Sulphur isotopic data for sulphides and barite from several carbonatites (Mountain Pass, Oka, Magnet Cove, Bearpaw Mountains, Phalabora) show that individual carbonatites have different mean sulphide or barite isotopic compositions which deviate from the meteoritic mean $\text{δ}{}^{34}\text{S(0‰)}$.Classification of carbonatites in terms of T,?O₂ and pH during formation of the sulphur-bearing assemblages indicates that with decreasing T and increasing relative ?O₂ the mean δ³⁴S sulphide becomes increasing negative relative to the mean magma δ³⁴S. Only barite-free high temperature carbonatites (Phalabora) in which the mean δ^34S sulphide approaches the mean magmaδ³⁴S as a consequence of the paucity of oxidized anionic sulphur species in the magma can be used to directly estimate the mean isotopic composition of the source material.Barites from the Mountain Pass carbonatite show an increase in δ³⁴S with sequence of intrusion of the carbonatite units; dolomitic carbonatite (mean δ³⁴S, + 5.4‰), calcitic carbonatite (+ 4.8%.), silicified carbonatite (+ 6.9‰), tabular carbonatite dikes (+ 8.7‰), mineralized shear zones (+ 9.5‰). Within each of these units a spread of 6.8%. is evident. Isotopic trends in this low temperature (300°C) carbonatite are evaluated by treating the system as a hydrothermal fluid. The observed isotopic variations can be explained by removal of large amounts of sulphur from a fluid whose mean δ³⁴S is 0 to + 1‰     

Dependence of clinopyroxene composition on cooling rate in basaltic magmas: Implications for thermobarometry

The compositional variation of clinopyroxene and the partitioning of major elements between clinopyroxene and melt are estimated as a function of the cooling rate. Clinopyroxenes were crystallized under variable cooling regimes (15, 9.4, 3, 2.1, and 0.5 °C/min from 1250 down to 1000 °C) and at isothermal conditions of 1000 °C from a basaltic composition at a pressure of 500 MPa under anhydrous and hydrous (H₂O = 1.3 wt.%) conditions. The clinopyroxene chemistry shows that, as the cooling rate increases, crystals are progressively depleted in Ca, Mg, Fe²⁺ and Si and enriched in Na, Fe³⁺, Al (mainly Al^IV), and Ti. Di and Hd versus CaTs and CaFeTs form a continuous binary solid solution characterized by higher amounts of tschermakitic components with increasing cooling rate. Two parameters (DH = Di + Hd and TE = CaTs + CaFeTs + En) are calculated to describe the effect of cooling rate on the clinopyroxene composition. The variation of DH/TE with increasing cooling rate evidences the kinetic process induced by rapid cooling in basic rocks under hydrous and anhydrous conditions.Dynamic crystallization conditions affect the partitioning of major elements between clinopyroxene and melt; with increasing cooling rate, the value of crystal–melt partition coefficient departs from that obtained at the isothermal condition. However, in spite of these variations, the values of ^cpx–meltKd_Fe–Mg remain almost constant. Therefore, the Fe²–Mg exchange between clinopyroxene and melt is not suitable to prove the (dis)equilibrium conditions in basaltic cooling magmas, giving rise to possible mismatches in the application of thermobarometers. The results of our study are consistent with that observed at the margin of dikes or in the exterior portions of lavas, where the cooling rate is maximized and disequilibrium compositions of clinopyroxene have been found.     

Major, trace element and isotope geochemistry (Sr-Nd-Pb) of interplinian magmas from Mt. Somma-Vesuvius (Southern Italy)

Summary Major, trace element and isotopic (Sr, Nd, Pb) data are reported for representative samples of interplinian (Protohistoric, Ancient Historic and Medieval Formations) activity of Mt. Somma-Vesuvius volcano during the last 3500 years. Tephra and lavas exhibit significant major, trace element and isotopic variations. Integration of these data with those obtained by previous studies on the older Somma suites and on the latest activity, allows to better trace a complete petrological and geochemical evolution of the Mt. Somma-Vesuvius magmatism. Three main groups of rocks are recognized. A first group is older than 12.000 yrs, and includes effusive-explosive activity of Mt. Somma. The second group (8000–2700 yrs B.P.) includes the products emitted by the Ottaviano (8000 yrs. B.P.) and Avellino (3550 yrs B.P.) plinian eruptions and the interplinian activity associated with the Protohistoric Formation. Ancient Historic Formation (79–472 A.D.), Medieval Formation (472–1139 A.D.) and Recent interplinian activity (1631–1944 A.D.) belong to the third group of activity (79–1944 A.D.). The three groups of rocks display distinct positive trends of alkalis vs. silica, which become increasingly steeper with age. In the first group there is an increase in silica and alkalis with time, whereas an opposite tendency is observed in the two younger groups. Systematic variations are also evident among the incompatible (Pb, Zr, Hf, Ta, Th, U, Nb, Rb, Cs, Ba) and compatible elements (Sr, Co, Cr). REE document variable degrees of fractionation, with recent activity displaying higher La/Yb ratios than Medieval and Ancient Historic products with the same degree of evolution. N-MORB normalized multi-element diagrams for interplinian rocks show enrichment in Rb, Th, Nb, Zr and Sm (> ^*10 N-MORB). Sr isotope ratios are variable, with Protohistoric rocks displaying ⁸⁷Sr/⁸⁶Sr =  0.70711–0.70810, Ancient Historic ⁸⁷Sr/⁸⁶Sr = 0.70665–0.70729, and Medieval ⁸⁷Sr/⁸⁶Sr = 0.70685–0.70803. Neodymium isotopic compositions in the interplinian rocks show a tendency to become slightly more radiogenic with age, from the Protohistoric (¹⁴³Nd/¹⁴⁴Nd = 0.51240–0.51247) to Ancient Historic (¹⁴³Nd/¹⁴⁴Nd = 0.51245–0.51251). Medieval interplinian activity (¹⁴³Nd/¹⁴⁴Nd: 0.51250–0.51241) lacks meaningful internal trends. All the interplinian rocks have virtually homogeneous compositions of ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb in acid-leached residues (²⁰⁷Pb/²⁰⁴Pb ∼15.633 to 15.687, ²⁰⁸Pb/²⁰⁴Pb ∼38.947 to 39.181). Values of ²⁰⁶Pb/²⁰⁴Pb are very distinctive, however, and discriminate among the three interplinian cycles of activity (Protohistoric: 18.929–18.971, Ancient Historic: 19.018–19.088, Medieval: 18.964–19.053). Compositional trends of major, trace element and isotopic compositions clearly demonstrate strong temporal variations of the magma types feeding the Somma-Vesuvius activity. These different trends are unlikely to be related only to low pressure evolutionary processes, and reveal variations of parental melt composition. Geochemical data suggest a three component mixing scheme for the interplinian activity. These involve HIMU-type and DMM-type mantle and Calabrian-type lower crust. Interaction between these components has taken place in the source; however, additional quantitative constraints must be acquired in order to better discriminate between magma characteristics inherited from the sources and those acquired during shallow level evolution. Received May 5, 2000; revised version accepted June 19, 2001     

Oxygen isotope and REE geochemistry of metamorphic veins within the Zhoutan Group,central Jiangxi Province

Geochemical studies on REE, trace elements and oxygen isotopes from metamorphic veins and their host metasedimentary rocks in the Zhoutan Group at two localities, Xiangshan and Yihuang, in central Jiangxi Province have been conducted in this paper. The results show that the metamorphic quartz veins inherited the REE and oxygen isotope geochemical characteristics from their host rocks, suggesting that the vein-forming fluids were derived from the host rocks. Additionally, fractionation degrees of the trace element pairs Zr-Hf, Nb-Ta, Y-Ho and U-Th in the veins are different from those of their host rocks. It is also indicated that the veins are the products of the fluids. The metamorphic veins within the Zhoutan Group metasedimentary rocks were formed principally as a result of lateral diffusion of the metamorphic fluids.