An experimental investigation of the partitioning of REE between garnet and liquid with reference to the role of defect equilibria

The partitioning of samarium and thulium between garnets and melts in the systems Mg₃Al₂-Si₃O₁₂-H₂O and Ca₃Al₂Si₃O₁₂-H₂O has been studied as a function of REE concentration in the garnets at 30 kbar pressure. Synthesis experiments of variable time under constant P, T conditions indicate that garnet initially crystallizes rapidly to produce apparent values of D _Sm (D _Sm=concentration of Sm in garnet/concentration of Sm in liquid) which are too large in the case of pyrope and too small in the case of grossular. As the experiment proceeds, Sm diffuses out of or into the garnet and the equilibrium value of D _Sm is approached. Approximate values of diffusion coefficients for Sm in pyrope garnet obtained by this method are 6 × 10^–13 cm² s^–1 at 1,300 ° C and 2 × 10^–12 cm² s^–1 at 1,500 ° C, and for grossular, 8.3 × 10^–12 cm² s^–1 at 1,200 ° C and 4.6 × 10^–11 cm² s^–1 at 1,300 ° C. The equilibrium values of D _Sm have been reversed by experiments with Sm-free pyrope and Sm-bearing glass, and with Sm-bearing grossular and Sm-free glass.Between 12 ppm and 1,000 ppm Sm in pyrope at 1,300 ° C and between 80 ppm and >2 wt.% Tm in pyrope at 1,500 ° C, partition coefficients are constant and independent of REE concentration. Above 100 ppm of Sm in garnet at 1,500 ° C, partition coefficients are independent of Sm concentration. At lower concentrations, however, D _Sm is dependent upon the Sm content of the garnet. The two regions may be interpreted in terms of charge-balanced substitution of Sm₃Al₅O₁₂ in the garnet at high Sm concentrations and defect equilibria involving cation vacancies at low concentrations. At very low REE concentrations (< 1 ppm Tm in grossular at 1,300 ° C) D_REE garnet/liquid again becomes constant with an apparent Henry's Law value greater than that at high concentrations. This may be interpreted in terms of a large abundance of cation vacancies relative to the number of REE ions.The importance of defects in the low concentration region has been confirmed by adding other REE (at 80 ppm level) to the system Mg₃Al₂Si₃O₁₂-H₂O at low Sm concentrations. These change D _Sm in the defect region, demonstrating their role in the production of vacancies.Experiments on a natural pyropic garnet indicate that defect equilibria are of importance to REE partitioning within the concentration ranges found in nature.     

The solubility of alumina in orthopyroxene coexisting with garnet

The solubility of alumina in complex orthopyroxenes crystallised in equilibrium with garnet has been determined over the pressure-temperature range 8–30 Kb and 800–1250° C. The results are in good agreement with predictions made using the simple thermodynamic model of Wood and Banno (1973). The model has been refined using a combination of the new data on orthopyroxenes of about En₆₀Fs₄₀ (with variable calcium content) and previously published data on more magnesian systems. Given analyses of coexisting Orthopyroxene and garnet in natural assemblages it is possible to calculate a P-T curve for the rock which should, in most cases, be accurate to within 2 or 3 kbar.     

Widespread occurrence of magnesiocummingtonite in ultramafic schists,Cima di Gagnone,Ticino, Switzerland

Abundant magnesiocummingtonite (space group P2₁/m) with Mg/(Mg+Fe) ratios between 0.85 and 0.89 occurs in lenses of schistose metaperidotite enclosed in kyanite-zone rocks of the Lepontine Alps, Ticino, Switzerland. It forms prisms and needles that extend homoaxially from cores of tremolite. Coexisting magnesian phases are olivine, orthopyroxene, talc, magnesite, and chlorite. Except for γ∶z, optical and structural properties of one example fall on extrapolations of existing determinative curves. Analogous to synthetic F-clinoamphiboles, zz∶z has a maximum at approximately 0.7 Mg/(Mg+Fe). Anthophyllite, of almost identical composition, occurs in the same region, often intergrown with cummingtonite along lamellae ‖(010) and ‖(100). Cummingtonite is believed to have partially inverted to anthophyllite during cooling.     

Quantitative geography: Revolution or counter-revolution?Quantitative geographie: Revolution oder konterrevolution?La géographie quantitative: Révolution ou contre-révolution?

There has been a crisis of the so-called “quantitative geography” for a few years. It is partly due to a poor use of mathematics, often presented for its own sake. There are also deeper reasons: refusal of rational formalization; and more emphasis on social and political studies.This paper tries to snow that a formal language (i.e., vocabulary and syntax) is necessary. Linguistics show how a language can be perverted by ideology into a myth. This has happened with traditional geography and is still present in some recent radical studies.     

De L'opportunité d'utiliser les coefficients de corrélation en météorologie forestière

Résumé En complément d'une étude précédente, les auteurs ont examiné si les coefficients de corrélation pouvaient s'utiliser avec profit pour résoudre les problèmes écologiques et plus spécialement de météorologie forestière. Pour cela ils ont calculé les coefficients résultant de la comparaison de l'accroissement forestier avec 12 grandeurs météorologiques. Afin d'obtenir des coefficients plus élévés ils ont considéré ensuite la courbe d'accroissement sur la base de sa droite de régression au lieu de sa moyenne. Ils ont enfin calculé diverses corrélations partielles en tenant compte d'une seconde grandeur météorologique. Il ressort de l'important matérial ainsi rassemblé, qu'il n'existe pas de corrélation entre les éléments météorologiques et l'accroissement forestier, du moins pas au sens mathématique du terme. Comme cette conclusion est en contradiction avec l'expérience pratique, on en déduit que cette méthode est inutilisable dans le cas particulier. Cette déduction est en outre étayée par des considérations d'ordre physiologique.

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Summary The present paper is a complement to an earlier work. It's purpose is to investigate the utility of correlation calculus with regard to ecological problema especially of the forest-meteorological kind. The authors computed, first of all, the direct correlation between treegrowth and each of 12 meteorological quantities. They tried then to improve the results by referring the annual treegrowth to it's regression line instead of the mean. Finally, they examined partial correlation taking into account two meteorological influences at the same time. The results seem to indicate, that there is no statistical evidence for any significant correlation between treegrowth and meteorological data. This is of course contrary to practical experience, whence the authors infer, that correlation calculus is an inadequate tool for handling their problem and similar ecological researches. This conclusion is supported by physiological considerations.

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Zusammenfassung In Ergänzung zu einer früheren Arbeit untersuchen die Autoren, ob Korrelationskoeffizienten in oekologischen, speziell forstmeteorologischen Aufgaben sinnvoll angewendet werden können. Zuerst werden die direkten Korrelationen zwischen dem jährlichen Holzzuwachs und je einer von 12 meteorologischen Grössen berechnet; dann wird zur Erzielung höherer Koeffizienten die Kurve des Holzzuwachses auf ihre zeitliche Regressionsgerade statt auf den Mittelwert bezogen, und schiesslich werden verschiedene partielle Korrelationen unter Berücksichtigung von je einer zweiten meteorologischen Grösse angegeben. Aus dem ziemlich unfangreichen Zahlenmaterial scheint hervorzugehen, dass zwischen Holzzuwachs und Witterung kaum ein statistischer Zusammenhang im mathematischen Sinne besteht. Da dieses Ergebnis der praktischen Erfahrung widerspricht, muss geschlossen werden, dass die Korrelationsrechnung der vorliegenden Aufgabe nicht angemessen ist, eine Folgerung, die durch Ueberlegungen physiologischer Natur gestützt und eingehend begründet ist.

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Riassunto A complemento di un precedente lavoro, gli autori studiano se abbia un senso l'impiego di coefficienti di correlazione in problemi ecologici e in particolare in quelli meteorologici-forestali. Dapprima vengono calcolate le correlazioni dirette tra la crescita annua del legno e ciascuna di 12 grandezze meteorologiche; in seguito, allo scopo di raggiungere coefficienti più elevati la curva della crescita del legno vien riferita alla sua retta di regressione del tempo invece che al valore medio; in ultimo vengono rese note diverse correlazioni parziali ottenute considerando anche una seconda grandezza meteorologica. Dal materiale assai abbondante utilizzato, sembra potersi dedurre che tra crescita del legno e condizioni meteorologiche non esiste una relazione statistica in senso matematico. Siccome questo risultato è in contrasto con l'esperienza pratica, bisogna dedurre che il calcolo del coefficiente di correlazione non è adatto per il problema in questione. E' questa una conseguenza che può appoggiarsi su ragionamenti di natura fisiologica ed essere minuziosamente motivata.

     

The Calcium Isotope Composition of Modern Seawater Determined by Thermal Ionisation Mass Spectrometry

The Ca isotopic composition of modern seawater has been determined using a ⁴³Ca-⁴⁸Ca double spike, which was calibrated using a ⁴²Ca/⁴⁴Ca seawater ratio of 0.30587 ± 0.00026. This ratio was determined from a total evaporation experiment in which the ion beam was measured from the beginning to the end of the emission. With integration of the peak intensities, the fractionation effects can be minimised, since total evaporation of the reservoir cancels out the effect of vapour enrichment in the light isotopes. This experiment avoids the gravimetric uncertainty inherent in the double spike calibration. This calibration allows the precise redetermination of the seawater isotopic composition of Ca. A mean ⁴⁰Ca/⁴⁴Ca ratio for two Atlantic water samples of 45.143 (2s_mean= 0.003) was found. The good reproducibility of the Ca isotope ratios in present seawater and the very strong isotopic homogeneity of Ca in the oceans illustrate the advantage of using seawater as the common standard, with the advantage of decreasing interlaboratory bias.     

A Compilation of Silicon and Thirty One Trace Elements Measured in the Natural River Water Reference Material SLRS-4 (NRC-CNRC)

The natural river water certified reference material SLRS-4 (NRC-CNRC, National Research Council-Conseil National de Recherches Canada) has been routinely analysed for major and trace elements by six French laboratories. Most measurements were made using inductively coupled plasma-mass spectrometry. For silicon and thirty one trace elements (rare earth elements, Ag, B, Br, Cs, Ga, Ge, Li, P, Pd, Rb, Se, Th, Ti, Tl, W, Y and Zr), no certified values are assigned by NRC-CNRC. We propose some compilation values and related uncertainties according to the results obtained by the different laboratories.     

The 1987–88 Alaskan Bight tsunamis: Deep ocean data and model comparisons

Excellent deep ocean records have been obtained of two tsunamis recently generated in the Alaskan Bight on 30 November 1987 and 6 March 1988, providing the best available data set to date for comparison with tsunami generation/propagation models. Simulations have been performed with SWAN, a nonlinear shallow water numerical model, using source terms estimated by a seafloor deformation model based on the rectangular fault plane formalism. The tsunami waveform obtained from the model is quite sensitive to the specific source assumed. Significant differences were found between the computations and observations of the 30 November 1987 tsunami, suggesting inadequate knowledge of the source characteristics. Fair agreement was found between the data and the model for the first few waves of the 6 March 1988 tsunami. Model estimates of the seismic moment and total slip along the fault plane are also in fair agreement with those derived from the published Harvard centroid solution for the 6 March 1988 event, implying that the computed seafloor deformation does bear some similarity to the actual source.