Distribution and fluxes of metals in the St. Lawrence River from the outflow of Lake Ontario to Québec City

Six anchor stations in the St. Lawrence River from the outflow of Lake Ontario to Quebec City, were occupied for ca. 24 hours in June 1987 during low flow conditions. Samples of water and suspended particulate matter were separated by continuous-flow centrifugation, and were collected every two hours.During this sampling period, fluxes of dissolved forms of zinc, copper and nickel increased in Lac St. François and downstream relative to the sum of the fluxes for the two upstream stations at the outflow of Lake Ontario. Increases in the flux of dissolved zinc and copper were pronounced below Montreal and above Lac St. Pierre. For particulate forms of metals, all five metals show that there are significant inputs in the section of the St. Lawrence River between Lac St. François and the station just above the entrance to Lac St. Pierre.The average concentrations of dissolved cadmium, lead, zinc, copper and nickel ranged from 7–23 ng/l; 9–35 ng/l; 0.434–0.939 g/l; 0.15–0.89 g/l and 0.58–1.12 g/l respectively.Regression analysis of the dissolved and particulate metal concentrations suggests that the concentration of dissolved cadmium, lead, zinc and nickel can be predicted from the regression equation and the determination of particulate metal concentration. This prediction appears to be independent of the suspended particulate matter concentration which varies from ca. 1 to 10 mg/l from the outflow of Lake Ontario to Québec City.     

The redox states of basic and silicic magmas: a reflection of their source regions?

At present the best estimates of the oxygen fugacity of spinel-lherzolites that could be the source material of basic magmas is about five log units below the Ni–NiO buffer to one above it. However partially glassy basic lavas, ranging from MORBs to minettes, all with olivine on their liquidus, cover a wider range, and may have oxygen fugacities that extend to four log units above NNO. Surprisingly the range of oxygen fugacities observed in silicic lavas and ashflows with quartz phenocrysts is smaller, despite a crustal dominated evolution. The peralkaline silicic lava type pantellerite is the most reduced, equivalent to MORBs, whereas the large volume ashflows with phenocrysts of hornblende and/or sphene are the most oxidised. As the concentration of water in the basic lavas is correlated with increase in their redox state, it would seem that water could be the agent of this increase. That this is unlikely is seen in the behavior of silicic ashflows and lavas, particularly those of Yellowstone. Here the silicic magmas of the last 2Ma contain about 2 wt% FeO_(total), and typically phenocrysts of fayalite, quartz and Fe–Ti oxides. Despite extensive exchange of the ¹⁸O of the magma with meteoric water after caldera collapse (Hildreth et al. 1984), there is no displacement of the redox equilibria. Thus the thermal dissociation of molecular H₂O to H₂, and its subsequent diffusive loss to cause oxidation must have been minimal. This could only be so if the activity of water was small, as it would be if H₂O reacted with the silicate liquid to form OH groups (Stolper 1982). The conclusion is that silicic magmas with small amounts of iron and large amounts of water do not have their redox states reset, which in turn presumably reflect their generation. By analogy basic magmas with large amounts of iron and far less water are even less likely to have their redox equilibria disturbed, so that their oxygen fugacities will also reflect their source regions. The effect of pressure on the ferric-ferrous equilibrium in basic magmas can be calculated from experimental measurements of the partial molar volumes of FeO and Fe₂O₃, and their pressure derivatives V/P, in silicate liquids. The effect of pressure is found to be about the same on the liquid as it is for various solid oxygen buffers. Accordingly there should be mantle source regions covering the same range of oxygen fugacity as that found in basic lavas, but so far samples of spinel-lherzolite of equivalent oxygen fugacity to minettes or other potassic lavas have not been found. Whether or not the redox state of phlogopite-pyroxenites is equivalent to these potassic lavas cannot be established without experiment.     

High pressure experimental calibration of the olivine-orthopyroxene-spinel oxygen geobarometer: implications for the oxidation state of the upper mantle

Synthetic spinel harzburgite and lherzolite assemblages were equilibrated between 1040 and 1300° C and 0.3 to 2.7 GPa, under controlled oxygen fugacity (f _{O 2}). f _{O 2} was buffered with conventional and open double-capsule techniques, using the Fe−FeO, WC-WO₂-C, Ni−NiO, and Fe₃O₄−Fe₂O₃ buffers, and graphite, olivine, and PdAg alloys as sample containers. Experiments were carried out in a piston-cylinder apparatus under fluid-excess conditions. Within the P-T-X range of the experiments, the redox ratio Fe³⁺/ΣFe in spinel is a linear function of f _{O 2} (0.02 at IW, 0.1 at WCO, 0.25 at NNO, and 0.75 at MH). It is independent of temperature at given Δlog(f _{O 2}), but decreases slightly with increasing Cr content in spinel. The Fe³⁺/ΣFe ratio falls with increasing pressure at given Δlog(f _{O 2}), consistent with a pressure correction based on partial molar volume data. At a specific temperature, degree of melting and bulk composition, the Cr/(Cr+Al) ratio of a spinel rises with increasing f _{O 2}. A linear least-squares fit to the experimental data gives the semi-empirical oxygen barometer in terms of divergence from the fayalite-magnetite-quartz (FMQ) buffer:

The effect of bulk rock composition on the stability of amphibole in the upper mantle: Implications for solidus positions and mantle metasomatism

Summary The stability of pargasitic amphibole in the upper mantle is a function of water content and bulk rock composition, and under water-undersaturated conditions, the stability of amphibole controls the solidus position. Experiments in the system Tinaquillo peridotite +0.2% H₂O, a refractory peridotite under water-undersaturated conditions, show that amphibole is stable to 1030°C and 26 kb. In contrast, pargasitic amphibole is stable to 1150°C and 30 kb in Hawaiian pyrolite, a more fertile peridotite composition. This indicates that under water-undersaturated conditions, the most fertile part of a crystallizing mantle diapir with an inhomogeneous composition will solidify first while a more refractory component will contain an alkali-rich melt which will have the ability to metasomatize adjacent regions. The relative stabilities of amphibole in refractory and fertile bulk compositions may result in increasing rather than diminishing chemical contrasts in high temperature lherzolite, i.e. a process of metamorphic differentiation. Ti, Fe, Al and Na metasomatism can therefore be considered a normal occurrence associated with the upward migration and solidification of an H₂O-bearing mantle diapir.

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Der Einfluß der Gesamtgesteins-Zusammensetzung auf die Stabilität von Amphibol im oberen Mantel: Bedeutung für Solidus-Positionen und Mantel-Metasomatose

Zusammenfassung Die Stabilität pargasitischer Amphibole im oberen Mantel ist eine Funktion von Wassergehalt und Gesamtgesteins-Zusammensetzung. Unter wasser-untersättigten Bedingungen, kontrolliert die Stabilität von Amphibol die Solidus-Position. Experimente in dem System Tinaquillo Peridotit +0,2% H₂O, einem refraktären Peridotit unter wasser-untersättigten Bedingungen, zeigen daß Amphibol bis 1030°C und 26 Kb stabil ist. Im Gegensatz dazu ist pargasitische Hornblende in einem Hawaii-Pyrolit, von mehr fertiler Peridotit-Zuammensetzung, bis 1150°C und 30 Kb stabil. Das zeigt, daß bei wasser-untersättigten Bedingungen der am meisten produktive Teil eines kristallisierenden Mantel-Diapirs mit inhomogener Zusammensetzung sich zuerst verfestigen wird, während eine mehr refraktäre Komponente eine alkali-reiche Schmelze enthalten wird, die wiederum die Fähigkeit hat, umliegende Bereiche metasomatisch zu beeinflussen. Die relativen Stabilitäten von Amphibol in refraktären und fertilen Gesamtzusammensetzungen können dazu führen, daß die chemischen Gegensätze in Hochtemperaturlherzoliten eher zunehmen als abnehmen, d. h. ein Prozeß metamorpher Differentiation. Ti, Fe, Al und Na Metasomatose können deshalb als ein verbreiteter Vorgang, der mit der Aufwärtsbewegung und Verfestigung eines H₂O-führenden Mantel-Diapirs assoziiert ist, betrachtet werden.

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With 4 Figures     

Evaluation of ferrous and ferric Mössbauer fractions

The Mössbauer fractions f for various ferrous- and/or ferric-containing oxides and oxyhydroxides, silicates and carbonates were evaluated from the experimental temperature dependence of their center shifts, using the Debye approximation for the second-order Doppler shift. It is concluded that ferrous ions exhibit a lower fraction as compared to ferric ions. Using standard mixtures of -Fe₂O₃ with selected Fe²⁺ or Fe³⁺ compounds, it is found that the calculated Fe³⁺ f values are somewhat overestimated with respect to those of Fe²⁺. Possible explanations for this shortcoming are discussed and it is suggested that a different temperature dependence of the intrinsic isomer shift is the most likely reason. This suggestion is corroborated by analyses of hematite and hedenbergite data which are available for temperatures up to 900 K and 800 K respectively.     

Littoral '92

Reports

Littoral '92     

An internal variable model for the creep of rocksalt

Summary The creep strain rate of rocksalt, like that of other ductile crystalline materials, can be described by a power law equation of the type ( ) ⁿ , where the active stress is the difference between the total deviatoric applied stress and an internal stress _i . In this paper, the origin and the nature of this internal stress, which develops during inelastic deformation of the material, are discussed. It is shown that this internal stress can serve as an internal (or state) variable in the constitutive model of rocksalt, which reflects the microstructure evolution of the material under the competitive action of hardening and recovery mechanisms.An analysis of experimental data, both our own and those taken from the literature, demonstrates that such a law is able to correctly reproduce rocksalt creep test results in the steady-state domain. The proposed model is in accordance with the macroscopic and microscopic behavior of salt, and with direct measurements of the internal stresses made by others on this material.     

Geochemistry of Gneiss-Granulite transformation in the “incipient charnockite” zones of southern India

Summary Upper amphibolite facies gneisses in the southern Indian Shield show local transformation into veins, clots and patches of orthopyroxene-bearing dry granulites (incipient charnockites). Depending upon the protolith composition, these desiccated zones are classified into ortho- and para-charnockites and have developed within rocks of distinct mineralogy and chemistry at different time intervals through the structurally-controlled influx of carbon dioxide-rich fluids. Our geochemical investigations at five critical quarry sections indicate that the incipient charnockites have undepleted chemistry and very low K/Rb values. In the paracharnockite localities, where granulite formation is characterized by consumption of garnet, biotite and quartz to produce orthopyroxene, loss of Rb and Ba and enrichment of Ti are observed. In contrast, the orthocharnockite localities show marked LILE enrichment with gain of K, Rb and Ba and loss of CaO, suggesting extensive replacement of plagioclase in the gneisses by K-feldspar in the charnockite through K-Na-Ca exchange reactions with influxing carbonic fluids. The marked depletion in Fe, Mg, Ti and P in these rocks correlates with progressive dissolution of hornblende, biotite, magnetite and accessory apatite. Our study indicates that gneiss to granulite transformation, even if on a local scale, is not an isochemical phenomenon, but attended by distinct element mobilities, although they are contrastingly different from the geochemical trends in some regional high grade terrains.

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Geochemie von Gneiss-Granulit-Übergängen in den Incipient Charnockite Zonen von Süd-Indien

Zusammenfassung Gneise der oberen Amphibolit-Fazies im Südteil des Indischen Schildes zeigen lokal Umwandlungen in Adern, and unregelmäßigen Bereichen von orthopyroxen-führenden trockenen Granuliten (Incipient Charnockites). In Abhängigkeit von der Zusammensetzung des Ausgangsgesteins werden diese Zonen in Ortho- und Paracharnockite eingeteilt. Sie entwickelten sich in Gesteinen von charakteristischer mineralogischer und chemischer Zusammensetzung zu verschiedenen Zeit-Intervallen durch die tektonisch kontrollierte Zufuhr von kohlendioxid-reichen Fluiden. Unsere geochemischen Untersuchungen an fünf strategisch ausgewählten Steinbruchen zeigen, daß die Incipient Charnockite eine nicht verarmte chemische Zusammensetzung und sehr niedrige K/Rb Werte haben. In den Paracharnockit-Lokalitäten, wo Granulitbildung charakterisiert wird durch das Verschwinden von Granat, Biotit und Quartz, aus denen Orthopyroxene gebildet werden, ist Verlust von Rb und Ba und Anreicherung an Ti zu beobachten. Im Gegensatz dazu zeigen die Orthocharnockite eindeutige LILE Anreicherung mit Zunahme von K, Rb, und Ba und Verlust von Ca0. Dies weist auf extensiven Ersatz von Plagioklas in den Gneisen durch K-Feldspat in den Charnockiten durch K-Na-Ca Austausch-Reaktionen mit zugeführten C0₂-Fluiden hin. Die deutliche Verarmung an Fe, Mg, Ti und P in diesen Gesteinen wird mit zunehmender Auflösung von Hornblende, Biotit, Magnetit und akzessorischem Apatit erKlärt. Unsere Untersuchungen zeigen, daß die Gneis-Granulit Transformation auch im lokalen Maßstab nicht ein isochemisches Phänomen ist, sondern durch charakteristische Elementtransporte charakterisiert wird. Diese unterscheiden sich jedoch deutlich von den geochemischen Trends, die in einigen regional-metamorphen high grade terrains zu beobachten sind.[/p]

     

New compositional and optical data for antimonian and bismuthian varieties of hemusite from Japan

Summary New compositional and optical data are reported for antimonian and antimonianbismuthian varieties of hemusite from epithermal Au-Ag-Cu deposits in Japan. The empirical formula for the antimonian variety, from the Iriki mine is: (Cu_5.83Fe_0.14Ag_0.01)_5.98Mo_1.03(Sn_0.54Sb_0.41Te_0.03Bi_0.02)_1.00(S_7.85Se_0.15)_8.00, and that of the Sb-Bi variety from the Kawazu mine is: (Cu_5.84Fe_0.14Ag_0.01)_5.99Mo_1.03(Sn_0.82Sb_0.11Bi_0.l0Te_0.04)_1.07(S_7.80Se_0.12)_7.92. The theoretical formula of hemusite is Cu⁺ ₄Cu²⁺ ₂MO⁴⁺Sn⁴⁺S₈, whilst the most probable formula of the Iriki hemusite is Cu⁺ _4.5CU²⁺ _1.5Mo⁴⁺Sn⁴⁺ _0.5Sb⁵⁺ _0.5S₈, with Sb⁵⁺ substituting for Sn⁴⁺ and forming (SbS₄)^3– tetrahedra as might be expected, given that the metal to sulphur ratio is 1, and given the sphalerite-like structure of the mineral. However Bi³⁺ cannot be so accommodated, resulting in a deficiency in (S + Se) for Kawazu hemusite. Reflectance spectra for both are compared with those of the tungsten analogue (compositional) of hemusite, kiddcreekite. The relationship between hemusitesensu stricto and these newly reported varieties is discussed in terms of simple and coupled chemical substitutions, and inferences are drawn on the valency of Sb, Bi, Mo and Cu in the hemusite structure.

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Neue chemische und optische Daten für antimon- und bismuthführende Varietäten von Hemusit aus Japan

Zusammenfassung Neue chemische und optische Daten für antimon- und bismuthführende Hemusite auf epithermalen Au-Ag-Cu Lagerstätten in Japan werden vorgelegt. Die empirische Formel für die antimon-führende Varietät aus der Iriki-Mine ist: (Cu_5.83Fe_0.14Ag_0.01)_5.98Mo_1.03(Sn_0.54Sb_0.41Te_0.03Bi_0.02)_1.00 (S_7.85Se_0.15)_8.00, und die der Sb-Bi Varietät aus der Kawazu Mine ist: (Cu_5.84Fe_0.14Ag_0.01)_5.99M0_1.03(Sn_0.82Sb_0.11Bi_0.l0Te_0.04)_1.07 (S_7.80Se_0.12)_7.92. Die theoretische Formel von Hemusit ist Cu⁺ ₄Cu²⁺ ₂Mo⁴⁺Sn⁴⁺S₈, während die wahrscheinlichere Formel für den Hemusit von Iriki Cu⁺ ₄Cu²⁺ _1.5Mo⁴⁺Sn⁴⁺ _0.5Sb⁵⁺ _0.5S₈, mit Sb⁵⁺ an der Stelle von Sn⁴⁺, das(SbS₄)^3– Tetraeder bildet, wie zu erwarten ist, unter der Voraussetzung, da das Metall zu Schwefelverhältnis 1 und die Struktur sphaleritähnlich ist. Bi³⁺ kann jedoch nicht in dieser Weise untergebracht werden, und das führt zu einem Mangel an (S + Se) für den Hemusit von Kawazu. Die Reflektions-Spektren beider Minerale werden mit denen des Wolfram-Equivalents von Hemusit (Kiddcreekit) verglichen. Die Beziehung zwischen Hemusitsensu stricto und diesen jetzt beschriebenen Varietäten wird auf der Basis einfacher und gekoppelter chemischer Substitution diskutiert. Auf dieser Basis werden Schlüsse auf die Valenz von Sb, Bi Mo und Cu in der Hemusit-Struktur gezogen.

     

Ongonite from Ongon Khairkhan,Mongolia

Summary Albite-topaz kerotophyres, termed ongonites, were discovered byV. I. Kovalenko and coworkers at Ongon Khairkhan in Mongolia in 1970. The type area was revisited, described, resampled, the new data is compared with the earlier data and that from similar rocks elsewhere (Beauvoir and Cinovec granites; Macusani glass).Ongonites are fluorine-rich peraluminous sodic two feldspar granitoids with orthoclase and albite phenocrysts, high modal and normative albite content and the presence of topaz as common accessory mineral. They contain variable amounts of lithium micas or muscovite. Chemically, ongonite is similar to highly fractionated S-type or ilmenite series granitoids. In the type area, F-rich water-poor ongonite melts have intruded to a high crustal level.Ongonite displays a long history of subsolidus reactions and hydrothermal alteration. The hydrothermal alteration may be linked to a spatially associated quartz-wolframite stockwork not genetically related to ongonite. Ongonite has a low W content and an elevated Sn content despite a lack of association with Sn deposits.

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Ongonite von Ongon Khairkhan, Mongolei

Zusammenfassung Albit-Topas-Keratophyre, auch als Ongonite bezeichnet, wurden 1970 von V. E. Kowalenko und Mitarbeitern bei Ongon Khairkhan in der Mongolei entdeckt. Die TypLokalität wurde beschrieben und beprobt und die neuen Daten werden mit den früher erhaltenen, und denen von ähnlichen Gesteinen in anderen Bereichen (die Granite von Beauvoir und Cinovec, das Glas von Macusani) verglichen.Ongonite sind Fluor- und Aluminiumreiche (Peraluminous), zwei-Feldspat-Natriumgranitoide mit idiomorphen Orthoklasen und Albit, hohem modalem und normativem Albitgehalt, und Topas als verbreitetem Nebenmineral. Sie führen wechselnde Gehalte von Lithiumglimmern oder Muskovit. Chemisch sind Ongonite stark fraktionierten S-Typ Granitoiden vergleichbar oder auch Granitoiden der Ilmenit-Serie. Im Gebiet der Typlokalität sind fluorreiche wasserarme Ongonit-Schmelzen in ein hohes Krustenniveau intrudiert worden.Ongonite zeigen eine lange Geschichte von Subsolidusreaktionen und hydrothermaler Umwandlung. Die hydrothermale Umwandlung kann mit einem räumlich assoziiertem Quarz-Wolframit Stockwerk in Beziehung gesetzt werden, das genetisch nicht mit den Ongoniten zusammenhängt. Ongonit hat einen niedrigen Wolframgehalt und einen erhöhten Zinngehalt, obwohl keine Assoziation mit Zinnlagerstätten zu beobachten ist.