Partitioning of Fe and Mn between ilmenite and olivine at 1100 °C: constraints on the thermodynamic mixing properties of (Fe, Mn)TiO3 ilmenite solid solutions

The partitioning of Fe²⁺ and Mn²⁺ between (Fe, Mn)TiO₃ and (Fe, Mn)₂SiO₄ solid solutions in the system FeO-MnO-TiO₂-SiO₂ has been experimentally investigated at 1100 ^∘C and pressures of 1 bar and 25 kbar, over a wide range of Fe/Mn ratios, using electron microprobe analysis of quenched run products. The ilmenite solid solution in this system is within analytical uncertainty a simple binary between FeTiO₃ and MnTiO₃, but the olivine solid solution appears to contain up to 2.5 wt% TiO₂. The Fe-Mn partitioning results constrain precisely the difference in the thermodynamic mixing properties of the two solid solutions. If the mixing properties of (Fe, Mn)₂SiO₄ solid solutions are assumed to be ideal, as experimentally determined by Schwerdtfeger and Muan (1966), then the ilmenite is a regular, symmetric solution with W ^ilm _Fe-Mn=1.8±0.1 kJ mol⁻¹. The quoted uncertainty does not include the contribution from the uncertainty in the mixing properties of the olivine solution, which is estimated to be ±1.8 kJ mol⁻¹, and which therefore dominates the uncertainty in the present results. Nevertheless, this result is in good agreement with the previous experimental study of O'Neill et al. (1989), who obtained W ^ilm _Fe-Mn=2.2±0.3 kJ mol⁻¹ from an independent method. The results provide another item of empirical evidence supporting the proposition that solid solutions between isostructural end-members, in which order-disorder effects are not important, generally have simple thermodynamic mixing properties, with little asymmetry, modest excess entropies, and excess enthalpies approximately proportional to the difference in the molar volumes of the end-members. Received: 11 February 1998 / Accepted: 29 June 1998     

Geochemistry of silicic magmas in the Macolod Corridor, SW Luzon, Philippines: evidence of distinct, mantle-derived, crustal sources for silicic magmas

Silicic volcanic deposits (>65 wt% SiO₂), which occur as domes, lavas and pyroclastic deposits, are relatively abundant in the Macolod Corridor, SW Luzon, Philippines. At Makiling stratovolcano, silicic domes occur along the margins of the volcano and are chemically similar to the silicic lavas that comprise part of the volcano. Pyroclastic flows are associated with the Laguna de Bay Caldera and these are chemically distinct from the domes and lavas at Makiling stratovolcano. As a whole, samples from the Laguna de Bay Caldera contain lower concentrations of MgO and higher concentrations of Fe₂O_3(t) than the samples from domes and lavas. The Laguna de Bay samples are more enriched in incompatible trace elements. The silicic rocks from the domes, Makiling Volcano and Laguna de Bay Caldera all contain high alkalis and high K₂O/Na₂O ratios. Melting experiments of primitive basalts and andesites demonstrate that it is difficult to produce high K₂O/Na₂O silicic magmas by fractional crystallization or partial melting of a low K₂O/Na₂O source. However, recent melting experiments (Sisson et al., Contrib Mineral Petrol 148:635–661, 2005) demonstrate that extreme fractional crystallization or partial melting of K-rich basalts can produce these silicic magmas. Our model for the generation of the silicic magmas in the Macolod Corridor requires partial melting of mantle-derived, evolved, moderate to K-rich, crystallized calc-alkaline magmas that ponded and crystallized in the mid-crust. Major and trace element variations, along with oxygen isotopes and ages of the deposits, are consistent with this model. Electronic Supplementary Material Supplementary material is available for this article at     

Petrology,isotope characteristics,and K-Ar ages of the Maranhão,northern Brazil,Mesozoic basalt province

Northern Brazil contains remnants of Mesozoic flood basalts and hypabyssal rocks that were apparently emplaced during tectonism related to opening of the Atlantic Ocean. Analyses and new K-Ar ages reveal that this 700x250 km Maranhão province (5°–8°S) has low-Ti basalts (1.1 wt% TiO₂) in the western part that range about 160 to 190 Ma, and high-Ti basalts (3.4–4.4 wt% TiO₂) in the eastern part about 115–122 Ma. Low-Ti basalt compositions are less evolved and have a smaller range, Mg# 62-56, than the high-Ti basalts, Mg# 44–33. General characteristics of the least evolved members of low- and high-Ti groups include, respectively, Zr 100 and 250 ppm, Sr 225 and 475 ppm, Ba 200 and 500 ppm, Nb 10 and 26 ppm, Y 29 and 36 ppm, La/Yb_(n) 4.2 and 8.8, where La_(n) is 30 and 90. Overall compositions resemble the low- and high-Ti basaltic rocks of the Mesozoic Serra Geral (Paraná) province in southern Brazil. The Maranhão low-Ti basalts have more radiogenic Sr and Pb and higher ¹⁸O than the high-Ti basalts. Respectively, low- vs high-Ti: _Sr26–54 vs 15–18; ²⁰⁶Pb/²⁰⁴Pb=18.25–.78 vs 18.22–.24; and ¹⁸O 8.9–12.6 vs 6.5–8.6. Nd isotopes overlap: _Nd–1.6 to –3.8 vs –2.1 to –3. Ages, compositions, and isotopes indicate that the low- and high-Ti groups had independent parentages from enriched subcontinental mantle. However, both groups can be modeled from one source composition if low-Ti basalt isotopes reflect crustal contamination, and if the parentages for each group were picritic liquids that represent either higher (for low-Ti) or lower (for high-Ti) percentages of melting of that single source. When comparing Pb isotopes of Maranhão and Serra Geral high-Ti basalts (uncontaminated) to evaluate the DUPAL anomaly, Maranhão has Pb 7/4=4.6–11, and Pb 8/4=72–87; Serra Geral has Pb 7/4=10–13, and Pb 8/4=95–125. The small difference is not enough to conform to DUPAL contours, and is inconsistent with large-scale isotopic heterogeneity of mantle beneath Brazil prior to rifting of South America from Africa. Maranhão low-Ti magmas probably relate to the opening of central North Atlantic, and high-Ti magmas to the opening of equatorial Atlantic. The proposed greater percentage of source melting for low-Ti basalts may reflect a Triassic-Jurassic hotspot, while lesser melting for high-Ti magmas may relate to Cretaceous decompressional (rifting) melting.     

Sectoral Composition and Spatial Distribution of Department of Defense Services Procurement*

The purpose of this research is to analyze the composition and distribution of Department of Defense (DOD) services procurement. The results indicate producer services comprise 53% of DOD services outlays. Defense expenditures for services are particularly important in the Washington, D.C., region and in states that either produce weapons or house defense-related R&D facilities. Defense expenditures are providing impetus to service sector growth in Virginia and, simultaneously, are providing the initial stimulus for development of producer services in states such as New Mexico.     

Observations of polar patches generated by solar wind Alfvén wave coupling to the dayside magnetosphere

A long series of polar patches was observed by ionosondes and an all-sky imager during a disturbed period (K_p = 7- and IMF B_z <0). The ionosondes measured electron densities of up to 9 × 10¹¹ m⁻³ in the patch center, an increase above the density minimum between patches by a factor of ≈4.5. Bands of F-region irregularities generated at the equatorward edge of the patches were tracked by HF radars. The backscatter bands were swept northward and eastward across the polar cap in a fan-like formation as the afternoon convection cell expanded due to the IMF B_y > 0. Near the north magnetic pole, an all-sky imager observed the 630-nm emission patches of a distinctly band-like shape drifting northeastward to eastward. The 630-nm emission patches were associated with the density patches and backscatter bands. The patches originated in, or near, the cusp footprint where they were formed by convection bursts (flow channel events, FCEs) structuring the solar EUV-produced photoionization and the particle-produced auroral/cusp ionization by segmenting it into elongated patches. Just equatorward of the cusp footprint Pc5 field line resonances (FLRs) were observed by magnetometers, riometers and VHF/HF radars. The AC electric field associated with the FLRs resulted in a poleward-progressing zonal flow pattern and backscatter bands. The VHF radar Doppler spectra indicated the presence of steep electron density gradients which, through the gradient drift instability, can lead to the generation of the ionospheric irregularities found in patches. The FLRs and FCEs were associated with poleward-progressing DPY currents (Hall currents modulated by the IMF B_y) and riometer absorption enhancements. The temporal and spatial characteristics of the VHF backscatter and associated riometer absorptions closely resembled those of poleward moving auroral forms (PMAFs). In the solar wind, IMP 8 observed large amplitude Alfvén waves that were correlated with Pc5 pulsations observed by the ground magnetometers, riometers and radars. It is concluded that the FLRs and FCEs that produced patches were driven by solar wind Alfvén waves coupling to the dayside magnetosphere. During a period of southward IMF the dawn-dusk electric field associated with the Alfvén waves modulated the subsolar magnetic reconnection into pulses that resulted in convection flow bursts mapping to the ionospheric footprint of the cusp.     

A study of internal solitary waves observed on the continental shelf in the northwestern South China Sea

Based on in-situ time series data from the acoustic Doppler current profiler (ADCP) and thermistor chain in Wenchang area, a sequence of internal solitary wave (ISW) packets was observed in September 2005, propagating northwest on the continental shelf of the northwestern South China Sea (SCS). Corresponding to different stratification of the water column and tidal condition, both elevation and depression ISWs were observed at the same mooring location with amplitude of 35 m and 25 m respectively in different days. Regular arrival of the remarkable ISW packets at approximately the diurnal tidal period and the dominance of diurnal internal waves in the study area, strongly suggest that the main energy source of the waves is the diurnal tide. Notice that the wave packets were all riding on the troughs and shoulders of the internal tides, they were probably generated locally from the shelf break by the evolution of the internal tides due to nonlinear and dispersive effects.     

THREE-WAY METHODS FOR THE CALIBRATION OF CHROMATOGRAPHIC SYSTEMS:COMPARING PARAFAC AND THREE-WAY PLS

For the calibration of chromatographic systems,different methods can be used.One class of methodsutilizes three-way approaches.The calibration problem is stated in such a way that the decompositionof a three-way array can serve for the prediction of retention on new stationary phases.Two three-way approaches are presented:the Unfold-PCA and PARAFAC models.The theory ofboth methods is presented and the differences are highlighted,the main difference being that PARAFACis a trilinear decomposition whereas Unfold-PCA is not.Both three-way methods are evaluated on asmall data set consisting of retention measurements of eight solutes at six mobile phase compositions onsix stationary phases.The differences in performance of the two models are minor,For calibration purposes,two variants of the methods are discussed:three-way PLS and an extensionof PARAFAC.Again the theory and differences between the two methods are explained.The predictiveperformance of the two methods is compared using the same data set as earlier.The differences inpredictive performance,however,are minor.Both methods are capable of predicting 98% of thevariation in the test sets.Yet,there are other considerations when comparing methods than predictiveperformance,e.g.the quality of the predictions.     

A comparison of early juvenile red drum densities among various habitat types in Galveston Bay, Texas

Seagrass meadows are often cited as important nursery areas for newly settled red drum even though many estuaries, such as Galveston Bay, Texas, support large numbers of red drum and have limited seagrass cover, suggesting the use of alternate nursery areas. We examined patterns of habitat use for newly settled red drum at six sampling areas in Galveston Bay; two areas had seagrass beds and four areas had no seagrass. We measured densities in different habitat types using epibenthic sleds and enclosure samplers. Peak recruitment of young red drum to the estuary occurred during September through December. Highest densities of new settlers were found in seagrass meadows (primarilyHalodule wrightii), but when seagrass was absent, the highest densities of red drum occurred along theSpartina alterniflora marsh edge interface. Densities were relatively low on nonvegetated bottom away from the marsh edge. We also examined density patterns in other habitat types at selected sampling areas and found no red drum within marsh vegetation away from the marsh edge interface (5 and 10 m into the marsh interior). Oyster reefCrassostrea virginica was sampled using lift nets, and we found no red drum using this habitat, although adjacent seagrass and marsh interface habitats were used. Even though red drum densities in marsh edge were low relative to seagrass, the large areal extent of marshes in the bay complex probably makes marsh edge the most important nursery habitat for red drum in Galveston Bay.     

Lithology-dependent seismic anisotropic amplitude variation with offset correction in transversely isotropic media

Analysis of amplitude variation with offset is an essential step for reservoir characterization. For an accurate reservoir characterization, the amplitude obtained with an isotropic assumption of the reservoir must be corrected for the anisotropic effects. The objective is seismic anisotropic amplitude correction in an effective medium, and, to this end, values and signs of anisotropic parameter differences (Δδ and Δε) across the reflection interfaces are needed. These parameters can be identified by seismic and well log data. A new technique for anisotropic amplitude correction was developed to modify amplitude changes in seismic data in transversely isotropic media with a vertical axis of symmetry. The results show that characteristics of pre-stack seismic data, that is, amplitude variation with offset gradient, can be potentially related to the sign of anisotropic parameter differences (Δδ and Δε) between two layers of the reflection boundary. The proposed methodology is designed to attain a proper fit between modelled and observed amplitude variation with offset responses, after anisotropic correction, for all possible lithofacies at the reservoir boundary. We first estimate anisotropic parameters, that is, δ and ε, away from the wells through Backus averaging of elastic properties resulted from the first pass of isotropic pre-stack seismic inversion, on input data with no amplitude correction. Next, we estimate the anisotropic parameter differences at reflection interfaces (values and signs of Δδ and Δε). We then generate seismic angle gather data after anisotropic amplitude correction using Rüger's equation for the P-P reflection coefficient. The second pass of isotropic pre-stack seismic inversion is then performed on the amplitude-corrected data, and elastic properties are estimated. Final outcome demonstrates how introduced methodology helps to reduce the uncertainty of elastic property prediction. Pre-stack seismic inversion on amplitude-corrected seismic data results in more accurate elastic property prediction than what can be obtained from non-corrected data. Moreover, a new anisotropy attribute (ν) is presented for improvement of lithology identification.     

Fossil midge associations and the historical status of fish in acidified lakes

Chaoborid and chironomid (Diptera) fossils were examined in sediment cores form nine Ontario Precambrian Shield lakes that were fishless in 1979. An abundance of Chaoborus americamus (intolerant of predation by fish) throughout cores from four lakes indicated that they were fishless historically. Occurrence of Chaoborus punctipennis and C. flavicans and absence of C. americanus in cores, except near the surface in two cases, indicated that four other lakes were inhabited by fish historically. One of these was probably periodically fishless as suggested by fluctuations among these Chaoborus species. The ninth lake was not suitable for Chaoborus; only one specimen of C. trivittatus was found in this core. Chironomid fossil associations were substantially different in historically fishless and inhabited lakes. Fishless lakes had chironomids typical of eutrophic conditions indicating that seasonal oxygen depletion likely was inimical to fish. Chironomid associations of oligotrophic waters occurred in lakes historically inhabited by fish. Both good water quality and accessibility were required for long-term habitation by fish. Partial recovery of alkalinity and rise in pH were accompanied by substantial re-invasion by fish in two lakes which had been inhabited historically by fish. Diptera associations provide valuable information on the historical suitability of lakes for fish and the presence/absence of fish in regions where acidification of surface waters has occurred.