Basalts of unusual composition from the Chyulu Hills,Kenya

Five Ne-normative basalts are unusually rich in Cr, to a lesser degree in Co, and have very high La/Lu ratios and high contents of several excluded trace elements resembling kimberlites in these and other aspects. They seem to represent mantle-derived magmas, only slightly modified by shallow level crystal/liquid fractionation. Cr was apparently excluded from the crystalline phases in equilibrium with these magmas in the upper mantle.The Chyulu rocks differ in several respects from other Gregory Rift basalts, but closely resemble those from Jan Mayen Island near the Mid-Atlantic ridge. The generation of these unusual basalts is therefore not related simply to mantle composition or tectonic setting, but may reflect unusually high-T (1450°C), low-P (15–29 kbars) environments in the zones of last effective equilibration of these magmas with mantle rocks.     

Structure energies of the alkali feldspars

Structural energetics of the alkali feldspars have been studied using a “lattice” or structure energy model. Electrostatic energies, U _e,for 20 well-refined, non-intergrown alkali feldspars were calculated using Bertaut's (1952) summation procedure and average about ?13,400 kcal/mol; the repulsive energies of the alkali site in each structure (～15 kcal/mol) were calculated using repulsive parameters for K-O and Na-O interactions estimated from bulk modulus data for NaF and KF and the exponential form of the repulsive potential. Using a procedure in which the position of the alkali cation was varied while the oxygen cage was kept fixed, structure energy gradients for the alkali sites of high albite and a hypersolvus Ab₄₂Or₅₈ structure were computed. In both cases, a broad structure energy well, elongated approximately parallel to c and subparallel to the observed split Na positions, was found. In both structures there is a single energy minimum corresponding closely with the observed single alkali positions. Comparison of U _e values for the alkali feldspars with different K/Na ratios shows that intermediate compositions are predicted to be less “stable” than either endmember and that the potassic end-member is predicted to be less “stable” than the sodic one, assuming that all other factors contributiong to the free energies of each phase are approximately the same. Comparison of U _e values for the high albite and low sanidine structures with different Al/Si distributions and a fixed tetrahedral framework indicates that the ordered charge distributions are 63.0 and 54.8 kcal/mol, respectively, more “stable” than the disordered distributions. Smaller, more realistic energy differences were obtained by using U _evalues averaged from four separate calculations with a +3 charge on a different T site in each and with +4 charges on the other T sites. If, in addition, the charges on cations and oxygen are reduced to half their nominal formal charges, in agreement with Pauling's electroneutrality principle and the results of recent molecular orbital calculations on silicates, the predicted electrostatic energy differences are reduced to 3.6 and 1.6 kcal/mol, respectively. These calculations also indicate that the T₁O site in the high albite structure energetically favors Al and that the Al/Si distribution determines the Na position within the alkali site.     

Atmospheric effects in the remote sensing of phytoplankton pigments

We investigate the accuracy with which relevant atmospheric parameters must be estimated to derive phytoplankton pigment concentrations (chlorophyll a plus phaeophytin a ) of a given accuracy from measurements of the ocean's apparent spectral radiance at satellite altitudes. The analysis is limited to an instrument having the characteristics of the Coastal Zone Color Scanner scheduled to orbit the Earth on NIMBUS-G. A phytoplankton pigment algorithm is developed which relates the pigment concentration (C) to the three ratios of upwelling radiance just beneath the sea surface which can be formed from the wavelengths () 440, 520 and 550 nm. The pigment algorithm explains from 94 to 98% of the variance in log₁₀ C over three orders of magnitude in pigment concentration. This is combined with solutions to the radiative transfer equation to simulate the ocean's apparent spectral radiance at satellite altitudes as a function of C and the optical properties of the aerosol, the optical depth of which is assumed to be proportioned to ^-n . A specific atmospheric correction algorithm, based on the assumption that the ocean is totally absorbing at 670 nm, is then applied to the simulated spectral radiance, from which the pigment concentration is derived. Comparison between the true and derived values of C show that: (1) n is considerably more important than the actual aerosol optical thickness; (2) for C 0299-1 0.2 g l^-1 acceptable concentrations can be determined as long as n is not overestimated; (3) as C increases, the accuracy with which n must be estimated, for a given relative accuracy in C, also increases; and (4) for C greater than about 0.5 g 1^-1, the radiance at 440 nm becomes essentially useless in determining C. The computations also suggest that if separate pigment algorithms are used for C 1gl^-1 and C 1 gl^-1, accuracies considerably better than ±± in log C can be obtained for C 1 g l^-1 with only a coarse estimate of n, while for C 10 gl^-1, this accuracy can be achieved only with very good estimates of n.Contribution No. 387 from the NOAA/ERL Pacific Environmental Laboratory.On leave from Department of Physics, University of Miami, Coral Gables, Florida.     

Polymerization of silicate and aluminate tetrahedra in glasses,melts, and aqueous solutions—I. Electronic structure of H6Si2O7, H6AlSiO71−, and H6Al2O72−

As part of a study of the effect of geologically common network modifiers on polymerization in silicate melts, glasses, and silica-rich aqueous solutions, we have studied the energies, electronic structures, and inferred chemical properties of ^IVT-O-^IVT linkages in the tetrahedral dimers H₆,Si₂O₇, H₆AlSiO₇^1?, and H₆Al₂O₇^2? using semi-empirical molecular orbital theory (CNDO/2). Our results indicate that the electron donating character of the bridging oxygen, O(br), linking two tetrahedra increases with increasing T-O(br) bond length but decreases with decreasing T-O(br)-T angles and increasing O-T-O(br) angles. This increase or decrease of the donor character of O(br) coincides with an increase or decrease of the affinity of O(br) for hard acceptors. The calculated electronic structure for the H₆Si₂O₇ molecule is compared with the observed X-ray emission, absorption, and photoelectron spectra of quartz and vitreous silica; the reasonable match between calculated and observed oxygen Kα emission spectra of vitreous silica supports our assertion that non-bonded O(br) electron density energetically at the top of the valence band controls the chemical reactivity of ^IVT-O-^IVT linkages in polymerized tetrahedral environments.     

Cenozoic latitudinal shift of the Hawaiian hotspot and its implications for true polar wander

Pacific plate equatorial sediment facies provide estimates of the northward motion of the Pacific plate that are independent of paleomagnetic data and hotspot tracks. Analyses of equatorial sediment facies consistently indicate less northward motion than analyses of the dated volcanic edifices of the Hawaiian-Emperor chain. The discrepancy is largest 60–70 Ma B.P.; the 60- to 70-Ma equatorial sediment facies data agree with recent paleomagnetic results from deep-sea drilling on Suiko seamount [1] and from a northern Pacific piston core [2]. Equatorial sediment facies data and paleomagnetic data, combined with K-Ar age dates along the Emperor chain [3], indicate a position of the spin axis at 65 Ma B.P. of 82°N, 205°E in the reference frame in which the Pacific Ocean hotspots are fixed. This pole agrees well with the position of the spin axis in the reference frame in which the Atlantic Ocean hotspots and the Indian Ocean hotspots are fixed [4,5], supporting the joint hypotheses that (1) the Pacific Ocean hotspots are fixed with respect to the hotspots in other oceans, (2) the hotspots have shifted coherently with respect to the spin axis, and (3) the time average of the earth's magnetic field 65 Ma B.P. was an axial geocentric dipole. Global Neogene paleomagnetic data suggest that a shift of the mantle relative to the spin axis has been occurring during the Neogene in the same direction as the shift between 65 Ma B.P. and the present. All data are consistent with a model in which the hotspots (and by inference the mantle) have shifted with respect to the spin axis about a fixed Euler pole at a constant rate of rotation for the last 65 Ma.     

Compositions of Formosan basalts and aspects of their petrogeneses

Twenty-three basalts from northwestern Formosa were analyzed for Si, Ti, Al, Fe, Mg, Ca, Na, K, Rb, Sr, Hf, Co, Sc, Cr, Th, and 7 REE. Formosan alkalic basalts are generally similar to most alkalic basalts, and Formosan tholeiites are somewhat similar to island arc and continental tholeiites in terms of trends in K/Rb, Rb/Sr, K/Sr, and Ca/Sr ratios. Compared to most submarine tholeiites, Formosan tholeiites are enriched in Rb relative to K and Sr, and enriched in Sr relative to K and Ca. Both types of Formosan basalts show, relative to chondritic proportions, enrichments in light REE which smoothly decrease through the heavy REE. Their REE patterns are similar to those observed in Dogo-Oki alkalic basalts, Hawaiian basalts, and Deccan Plateau basalt, but differ strikingly from those of Japanese tholeiites and oceanic ridge basalts. These relationships and contrasts suggest that Formosan basalts originated in a plagioclase-free portion of the upper mantle and at greater depths that did Japanese tholeiites and oceanic ridge basalts.     

Some constraints on the origin of phonolites from the Gregory Rift,Kenya, and inferences concerning basaltic magmas in the Rift System

Plateau-type phonolites of the Gregory Rift represent magmas with densities of about 2.3 g/cm³. These magmas must have erupted soon after their formation. The average depth of the bases of the approximately 100 to 300 magma chambers from which they erupted was between about 10 and about 24 km. The average vertical extent of the magma chambers was between about 3 and about 8 km. The aggregate volume of phonolitic magma formed beneath the Rift in Miocene times probably lies in the range of 0.5 to 1×10⁵ km³. Both the crystal fractionation model and the anatectic model for formation of this volume of phonolitic magma require the presence of a large reservoir of basaltic magma, probably picritic in character, with a volume of at least 5×10⁵ km³ and perhaps as much as 20×10⁵ km³. This reservoir presumably is now part of the dense basic intrusive complex along the Rift axis. The Miocene and Pliocene episodes of basaltic volcanism in this region may be related to eruption of evolved liquids from this reservoir.