Phase relations inferred from field data for mn pyroxenes and pyroxenoids

Electron microprobe analysis of manganese silicates from Balmat, N.Y., has helped elucidate phase relations for Mn-bearing pyroxenes and pyroxenoids. A compilation of these data along with published and unpublished analyses for phases plotting on the CaSiO₃-MgSiO₃-MnSiO₃ and CaSiO₃-FeSiO₃-MnSiO₃ faces of the RSiO₃ tetrahedron has constrained the subsolidus phase relations. For the system CaSiO₃-FeSiO₃-MnSiO₃, the compositional gaps between bustamite/hedenbergite, bustamite/ rhodonite and rhodonite/pyroxmangite are constrained for middle-upper amphibolite facies conditions and extensive solid solutions limit possible three phase fields. For the CaSiO₃-MgSiO₃-MnSiO₃ system much less data are available but it is clear that the solid solutions are much more limited for the pyroxenoid structures and a continuum of compositions is inferred for clinopyroxenes from diopside to kanoite (MnMgSi₂O₆) for amphibolite facies conditions (T=650° C). At lower temperatures, Balmat kanoites are unstable and exsolve into C2/c calciumrich (Ca_0.68Mn_0.44Mg_0.88Si₂O₆) and C2/c calciumpoor (Ca_0.12Mn_1.02Mg_0.86Si₂O₆) phases. At temperatures of 300–400° C the calcium-poor phase subsequently has undergone a transformation to a P2₁/c structure; this exsolution-inversion relationship is analogous to that relating augites and pigeonites in the traditional pyroxene quadrilateral. Rhodonite coexisting with Mn-clinopyroxenes is compositionally restricted to Mn_0.75–0.95Mg_0.0–0.15Ca_0.05–0.13SiO₃. For the original pyroxene+rhodonite assemblage, the Mg and Ca contents of the rhodonite are fixed for a specific P (6kbars)-T (650° C)-X(H₂O)-X(CO₂) by the coexistence of talc+quartz and calcite+quartz respectively.Contribution No. 363, from the Mineralogical Laboratory, Department of Geological Sciences, The University of Michigan, Ann Arbor MI 48109, USA     

Seasonal oxygen depletion in Chesapeake Bay

The spring freshet increases density stratification in Chesapeake Bay and minimizes oxygen transfer from the surface to the deep layer so that waters below 10 m depth experiece oxygen depletion which may lead to anoxia during June to September. Respiration in the water of the deep layer is the major factor contributing to oxygen depletion. Benthic respiration seems secondary. Organic matter from the previous year which has settled into the deep layer during winter provides most of the oxygen demand but some new production in the surface layer may sink and thus supplement the organic matter accumulated in the deep layer.     

The thermodynamic properties and phase relations of some minerals in the system CaO-AI2O3-SiO2-H2O

The heat capacities of lawsonite, margante, prehnite and zoisite have been measured from 5 to 350 K with an adiabatic-shield calorimeter and from 320 to 999.9 K with a differential-scanning calorimeter. At 298.15 K, their heat capacities, corrected to end-member compositions, are 66.35, 77.30, 79.13 and 83.84 cal K^?1 mol^?1; their entropies are 54.98, 63.01, 69.97 and 70.71 cal K^?1 mol^?1, respectively. Their high-temperature heat capacities are described by the following equations (in calories, K, mol): Lawsonite (298–600 K): Cp° = 66.28 + 55.95 × 10^?3T ? 15.27 × 10⁵T^?2 Margarite (298–1000 K): Cp° = 101.83 + 24.17 × 10^?3T ? 30.24 × 10⁵T^?2 Prehnite (298–800 K): Cp° = 97.04 + 29.99 × 10^?3T ? 25.02 × 10⁵T^?2 Zoisite (298–730 K): Cp° = 98.92 + 36.36 × 10^?3T ? 24.08 × 10⁵T^?2 Calculated Clapeyron slopes for univariant equilibria in the CaO-Al₂O₃-SiO₂-H₂O system compare well with experimental results in most cases. However, the reaction zoisite + quartz = anorthite + grossular + H₂O and some reactions involving prehnite or margarite show disagreements between the experimentally determined and the calculated slopes which may possibly be due to disorder in experimental run products. A phase diagram, calculated from the measured thermodynamic values in conjunction with selected experimental results places strict limits on the stabilities of prehnite and assemblages such as prehnite + aragonite, grossular + lawsonite, grossular + quartz, zoisite + quartz, and zoisite + kyanite + quartz. The presence of this last assemblage in eclogites indicates that they were formed at moderate to high water pressure.     

An analytical electron microscopic study of a pyroxene-amphibole intergrowth

Samples of a garnet granulite from the mafic border units of the Lake Chatuge, Georgia alpine peridotite body were found to contain lamellar intergrowths of a pargastic amphibole in augite having the typical appearance of an exsolution feature. Single crystal X-ray diffraction, optical, electron microprobe and conventional and analytical electron microscopic studies have provided data limiting the compositions and structures of the coexisting phases. Individual lamellae of both materials are from 0.5 to 2.0 m in width with the lamellar interface parallel to {0 1 0}. The formulae of the minerals, as determined by a combination of electron microprobe and analytical electron microscopy, are (Na_0.1Ca_1.0Mg_0.6Fe³⁺ _0.3)(Si_1.8Al_0.2)O₆ for the pyroxene and Na_0.7Ca_1.9(Mg_2.1Fe²⁺ _1.4Fe³⁺ _0.5Ti_0.1Cr_0.1Al_0.8)(Si_5.9Al_2.1) O₂₂(OH)₂ for the amphibole. Several other studies have described intergrowths similar to those observed in this work, in general favoring exsolution as the formation mechanism for the intergrowths. In the Lake Chatuge samples however, replacement of pyroxene by amphibole is in part indicated by continuous gradation of amphibole lamellae into amphiboles rimming the clinopyroxenes.Contribution No. 368 from the Mineralogical Laboratory, Department of Geological Sciences, The University of Michigan, Ann Arbor, Michigan     

Petrogenetic model for the origin of carbonatites

The petrological significance and distribution of igneous carbonatites is discussed. Particular attention is paid to the relationship that exists between carbonatites and volcanism in East Africa. Using a simple model of a carbonatite-nephelinite-ijolite volcanic complex it was discovered that all the peralkaline and carbonatitic rocks found in such a complex could be derived from a single primary nephelinitic magma. The origin of such a primary magma, and the subsequent evolution carbonatitic sub-magmas, is examined.     

Mössbauer spectra of synthetic Ca-Fe pyroxenoids and lunar pyroxferroite

Resolution of the iron sites in the Mössbauer spectra of Ca-Fe pyroxenoids is only partial, two doublets being apparent in each case, whereas there are up to nine cation sites in each structure. Thus the inner and outer doublets represent, respectively: two sites and two sites in Ca_0.5Fe_0.5SiO₃ (ferrobustamite); five sites and two sites in Ca_0.15Fe_0.85SiO₃ (pyroxferroite); and five sites and four sites in FeSiO₃ (ferrosolite III). Disorder of iron and calcium which exists in the two calcium-bearing pyroxenoids is not readily apparent in the spectra.Publication authorized by the Director, U. S. Geological Survey.     

Evolution of volcanic islands

It is shown that there is no significant correlation between the chemistry of volcanic islands and their distance from the axes of oceanic rises. The composition and the distribution of those oceanic volcanic islands that are not associated with subduction zones is considered to be related to the distribution of a series of thermal plumes that originated either within the upper mantle or at the coremantle interface.     

Evolution of La Palma,Canary archipelago

La Palma is the northwestern island in the Canary archipelago. The island is volcanically active and in recent years there have been two eruptions (1949 and 1971). The oldest rocks that crop out on the island are altered spilitic lavas and they are intruded by numerous dykes and a number of mafic and ultramafic plutonic rocks. These rocks form part of the floor of the huge Caldera de Taburiente. In the walls of the Caldera one finds a 1000 metres thick unit that is composed of lavas and tephra. The rocks are called the El Time formation; and they together with the rocks of the Cumbre Vieja ridge are mainly composed of accumulative mafic rocks, basanites, hawaiites, benmoreites and phonolitic trachytes. These sodarich alkalic rocks are considered to have evolved by fractional crystallization of a basanitic magma in a near surface environment.It is proposed that La Palma developed on a relatively cold section of a plate of oceanic lithosphere that was over 100 m.y. old. During the Alpine-Atlas orogeny this section of the African plate was disrupted and a basanitic magma was extruded onto the sea floor. The volcanic focus of this eruption became established as a local centre for the degassing of the mantle and as a result this area has experienced a long series of eruptions.During the first phase in the evolution of La Palma the submarine edifice of the island was constructed and the rocks of the Caldera Floor formation were emplaced. After a period of marine erosion the huge old volcano Taburiente developed in the northern half of the island. During the final phase in the evolution of the island the southern section of the volcanic edifice subsided and formed the El Paso tectonic basin and the volcanic rift zone along which the many smaller volcanoes of the Cumbre Vieja ridge have developed.     

Evidence for sulfurization and the origin of some sudbury-type ores

The suggestion that Sudbury-type ores may be formed by the introduction of country rock sulfur into still hot intrusions (i.e., sulfurization) suffers from a reputed lack of field evidence. Permissive evidence for sulfurization includes the epigenetic nature of many Sudbury-type ores and that many Sudbury-type ores crystallized from sulfide melts. Visual evidence exists for sulfurization of a gabbro in Zambia. The lead isotopic composition of ore minerals at Sudbury implies that at least some of the metals were derived from the erruptive. Published sulfur isotopic data from several Sudbury-type ores differ from and do not exhibit a common pattern of isotopic enrichment with respect to sulfides within associated intrusions. Evidently the sulfur was derived from the country rocks. Sudbury-type ores exhibiting magmatic textures commonly occur within more siliceous dikes than the host intrusions. Inorganic reduction of sulfate occurs only above 600° C. Reduction of sulfate with resultant sulfurization of ferrous iron and traces of other metals originally present in the still hot parental intrusive rock would make the rock more siliceous. Above 1100° C the silicate-residue and newly formed sulfides would form immiscible magmas. Therefore, ore magmas within and near mafic intrusives can be epigenetic. The processes by which sulfur is introduced into intrusions are still speculative.

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Zusammenfassung Für die Annahme, daß Erze vom Sudbury-Typus sich durch Zuführung von Nebengesteinsschwefel in noch heiße Intrusionen bilden können (sulfurization), fehlt es angeblich an Feldunterlagen. Folgende Tatsachen lassen sich mit einer Schwefelung (sulfurization) vereinigen: der epigenetische Charakter vieler Erze vom Sudbury-Typ; auch sind viele Erze von Sudbury-Typus aus sulfidischen Schmelzen kristallisiert. In einem Gabbro in Zambia ist der Beweis für Schwefelung (sulfurization) direkt sichtbar. Die Isotopen-Zusammensetzung von Blei in Erzmineralien in Sudbury zeigt, daß mindestens einige der Metalle aus dem Eruptivgestein stammen. Schwefelisotop-Daten, die für mehrere Lagerstätten von Sudbury-Typen veröffentlicht worden sind, haben hinsichtlich der Isotop-Anreicherung keine gemeinsamen Züge. Offensichtlich stammt der Schwefel aus dem Nebengestein. Erze vom Sudbury-Typ mit magmatischem Gefüge finden sich oft in Gängen, die saurer sind als das Wirtsgestein. Anorganische Reduktion von Sulfat findet nur oberhalb 600°C statt. Reduktion von Sulfat und die entstehende Schwefelung (sulfurization) von zweiwertigem Eisen und Spuren anderer Metalle, die ursprünglich in dem noch heiß eruptiven Gestein anwesend sind, machen das Gestein noch saurer. Oberhalb 1100°C würden der Silicat-Rest und die neugeformten Sulfide nicht mischbare Magmen bilden. Deshalb können sich sulfidische Schmelzen innerhalb und in der Nähe von Mafic-Intrusionen später gebildet haben. Die Prozesse, durch die Schwefel in Intrusionen eingeführt wird, sind noch unbekannt.