Solution of H2O in diopside melts: a thermodynamic model

Structural similarities between dry diopside melt and superhydrous albite melt (X _w >0.5) — both lack three-dimensional silicate units — suggest that thermodynamic relations may be similar. A model based on that assumption successfully predicts diopside melting relations and H₂O solubilities. For the model, the three partial differential equations describing solution of H₂O in albite melt for X _w >0.5 have been integrated for diopside melt from X _w =0 to X _w at least as large as 0.76, with two exceptions: an alternative partial differential equation for Henrian solution of H₂O in dilute melts was applied for X _w <0.20, and an alternative differential equation for the pressure dependence of a _w at pressures below 2 kbar was developed. The latter alternative equation yields relatively small ¯V_w's at low pressures rather than the large ¯V_w's calculated from the equation from the albite system. Available experimental solubility data are not precise enough to offer a choice between the small-¯V_w and large-¯V_w equations. Integration of all the partial differential equations was constrained solely by the P and T of a single experimentally-determined point on the H₂O-saturated solidus.Solubilities calculated by a Henrian-analogue solution model (a _di=X _di ² ) from the experimental H₂O saturated solidus lie outside experimental solubility constraints for dilute melts. On the other hand, a Henrian model (a _di=X_di) successfully predicts solubilities in dilute melts. The formulation of the Henrian model and magnitudes of model molar entropies of solution are consistent with the hypothesis that H₂O dissolves in diopside melt as an essentially undissociated species with little ordering on melt structural sites. That species could in turn be consistently, if not uniquely, interpreted to be molecular H₂O or a hydroxylation (OH^–) complex formed from nonbridging oxygens.     

Determination of Boron in 35 International Geochemical Reference Materials by Thermal Neutron Capture Prompt Gamma-ray Spectrometry

Concentrations of boron in 35 silicate reference materials are measured by thermal neutron capture gamma-ray spectrometry. Results are compared for NBS, USGS, and CCRMP reference materials with values from the literature. The use of two prompt gamma facilities at Los Alamos are discussed.     

Distribution and mode of occurrence of zinc and lead in glacial soils

The distribution and mode of occurrence of zinc and lead have been examined in glacial soils developed over a complex Precambrian marble-paragneiss terrain in the Adirondack Mountains of New York. Based on distribution within the soil profiles, zinc is enriched in the B₁ horizon of soils sampled over marble and lead is generally enriched in the A horizon, particularly in soils developed over paragneiss. Contrast is calculated using

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, where is the mean of n_A anomalous and n_B background samples, and S_p is the pooled standard deviation) for zinc, lead and cold-extractable heavy metals in soils sampled over marble and paragneiss. The t-values indicate that the B₁, soil horizon is the most suitable for sampling on a regular basis, even though lead is most concentrated in the A horizon.The distribution of zinc and lead among exchangeable, organic, iron-manganese oxide, clay, silt and sand fractions of B₁ horizons from two anomalous and one background soil indicates that both zinc and lead are tied up principally in iron and manganese oxides. The anomalous samples exhibit zinc enrichment in the Fe-oxide digestion and high Mn/Fe ratios for the Mn-oxide digestion (as well as the total analysis). In terms of total contribution to the sample, significant proportions of zinc in the clastic fraction can be attributed to zinc substitution into clays plus the ineffective removal of Fe-oxides by the ammonium oxalate extraction procedure. Lead, on the other hand, occurs in significant concentrations in clay, silt and sand as well as Fe- and Mn-oxides, probably as a trace constituent in feldspars or adsorbed onto clay surfaces.     

Temperature dependence of calcite dissolution kinetics between 1 and 62°C at pH 2.7 to 8.4 in aqueous solutions

The kinetics of calcite dissolution in aqueous KCl-solutions far from equilibrium, between 1 and 62°C in the pH-range 2.7 to 8.4 have been investigated using a rotating disc apparatus. At neutral and alkaline pH in the mixed kinetic regime the empirical apparent activation energy (EAAE) for the surface chemical reaction rate constant is 54 ± 4 kJ mole^?1 for Carrara marble and 46 ± 4 kJ mole^?1 for Iceland spar. Under similar conditions the EAAE of the transport rate constant increases with decreasing temperature, but has a mean value of 27 ± 2 kJ mole^?1. The corresponding diffusion coefficient has a mean EAAE of 37 ± 3 kJ mole^?1 and this high EAAE is consistent with transport dependence on product diffusion in this H⁺-independent regime.In contrast, in acid solutions, where the rate approaches end-member transport control, the EAAE of the diffusion coefficient is 16 kJ mole^?1, also decreasing with increasing temperature. This is compatible with H⁺-diffusion to the surface being rate-controlling.In inhibitor-free natural systems, calcite dissolution kinetics far from equilibrium can be described in terms of three regimes: an H⁺-dependent regime (pH < 4 at 25°C), a transition regime (4 < pH < 5.5 at 25°C) and an H⁺-independent regime (pH > 5.5 at 25°C). At lower temperatures these boundaries move to higher pH values. The presence of inhibitors in natural systems may enhance surface controlled kinetics.     

Analysis of dislocations in some naturally deformed plagioclase feldspars

Dislocations in intermediate plagioclase feldspars, which were deformed under granulite facies conditions, have been analysed. The study reveals extensive ductile deformation by intracrystalline slip and by twinning. Six out of the seven possible Burgers vectors were identified: \(b = \left[ {001} \right],\tfrac{1}{2}\left[ {110} \right],\tfrac{1}{2}\left[ {1\bar 10} \right],\left[ {101} \right],\tfrac{1}{2}\left[ {112} \right]and\tfrac{1}{2}\left[ {1\bar 12} \right]\) . Most, perhaps all, dislocations are dissociated by up to 200 Å. The microstructure is dominated by [001] screw dislocations, most of which appear to be dissociated in (010). The dominant slip system appears to be (010) [001]. Large grain-to-grain variations in the density of free dislocations indicate that the plastic strain in individual grains depended upon the Schmid factor for (010) [001]. The microstructure suggests that the rate-controlling step for high-temperature creep of plagioclase is cross-slip of extended [001] screw dislocations. The rheological contrast between feldspar and quartz is partly due to a difference in stacking fault energy.     

Late Quaternary sapropel sediments in the eastern Mediterranean Sea: Faunal variations and chronology

Distinctive planktonic foraminiferal assemblages which characterize particular late Quaternary sapropel layers in deep basin sediments from the eastern Mediterranean Sea have been identified using cluster analysis. Three distinct clusters allow for identification and intercore correlation of the nine sapropels deposited during the last 250,000 yr. Cluster 1, representing sapropel layers S1 and S9, exhibits low abundances of Neogloboquadrina dutertrei and high abundances of Globigerinoides ruber; Cluster 2, which groups S3, S5, and S7, contains high abundances of G. ruber, N. dutertrei, and Globigerina bulloides, and Cluster 3, which includes samples from S4, S6, and S8, is marked by extremely abundant N. dutertrei and G. bulloides, and rare G. ruber. Analysis of sedimentation rates in 14 cores reveals the following approximate ages for the sapropel layers: S2 = 52,000 yr B.P.; S3 = 81,000–78,000 yr B.P.; S4 = 100,000–98,000 yr B.P.; and S5 = 125,000–116,000 yr B.P. As previously suggested, sedimentation rates on the Mediterranean Ridge were determined to be relatively constant during the last 127,000 yr. In contrast, basin sedimentation rates have fluctuated markedly from lower rates during interglacial stage 5 to higher rates during the last glacial episode. These glacial/interglacial differences are most pronounced in the northern Ionian Basin, because of increased terrigenous sediment deposition during glacial episodes. Unusually high biogenic sedimentation rates occurred in an arc south of Crete during the deposition of sapropel S5, probably due to higher productivity in this region.     

On the onset of entrainment instability over the ocean

The marine atmospheric boundary layer is characterized by cool temperatures and high humidity. Clouds are observed over most of the oceans. It is generally accepted that these overcast cloud decks break up into scattered fragments due to cloud-top entrainment instability. That is, if the air above the boundary layer is sufficiently cool and dry relative to cloud top, the buoyancy flux will be directed upwards and entrainment can occur freely.A boundary-layer model is used to test the sensitivity of the model atmosphere to the various processes which promote the onset of cloud-top entrainment instability. It is found that the transition from a solid cloud deck to scattered cumulus clouds depends on a rate process. The cloud cover is sensitive to mesoscale variations in sea surface temperature only if the cloud-top inversion is sufficiently weak.     

Volatile contents of phlogopite micas from South African kimberlite

Phlogopite micas from nodules in South African kimberlites were analyzed for major elements with the electron microprobe and for volatile contents by high temperature mass spectrometry. The micas are from primary- (deformed) and secondary- (undeformed) textured grains in perodotite xenoliths, glimmerites, MARID (mica-amphibole-rutile-ilmenite-diopside) suite nodules and a mica megacryst. The major element and volatile contents of micas exhibiting these modes of occurrence overlap to a greater extent than indicated in previous studies. Concentrations of volatile species occupying structurally defined crystallographic sites (H₂O, F, Cl) are greater for many of the micas than predicted on the basis of the mica formula, particularly for the glimmerite and MARID suite samples. A correlation exists between micas with tetrahedral and octahedral cation deficiencies and those with excess H₂O, F and Cl. Substitution of H⁺ for tetrahedral and possibly octahedral cations may be responsible for the excess H₂O in these micas. Except for one sample, the major element and volatile data for the peridotite, glimmerite and MARID suite micas indicate that they crystallized at oxygen fugacities below the quartz-fayalite-magnetite buffer. F and K₂O are in the correct proportion in the micas to provide the source for these elements in alkali basalts, but not in mid-ocean ridge basalts. Kaersutite amphibole is a more likely source of potassium and fluorine in mid-ocean ridge basalts.     

Multiple scattering of seismic waves in fractured media: Velocity and effective attenuation of the coherent components ofP waves andS waves

We show that the multiple scattering by small fractures of seismic waves with wavelengths long compared to the fracture size and fracture spacing is indistinguishable from multiple-scattering effects produced by regular porosity, except for an orientation factor due to fracture alignment. The fractures reduce theP-wave andS-wave velocities and produce an effective attenuation of the coherent component of the seismic waves. The attenuation corresponds to 1000/Q of about unity for a Gaussian spectrum of fractures, and it varies with frequencyf asf ³. For a Kolmogorov spectrum of fractures of spectral index the attenuation is an order of magnitude or so larger and varies with frequency asf ^3-v The precise degree of attenuation depends upon the matrix properties, the fracture porosity, the degree of fracture anisotropy, the type of fluid filling the fractures, and the incidence angle of the wave.For fracture porosities less than about 15% theP-wave andS-wave velocities are decreased by the order of 5–10% with a lesser dependence on the type of fluid filling the fractures (gas, oil, or brine) and with a dependence on both the degree of anisotropy and the incident angle made by the wave. The tendency of fractures to occur perpendicularly to bedding suggests that the best way to measure seismically fractured rock behavior in situ is by using the travel-time delay and reflection amplitude. As both the offset and the azimuth of receivers vary from a shot, the travel-time delay and reflection amplitude should both show an elliptical pattern of behavior—the travel-time delay in response to the varying seismic speed, and the reflection amplitude in response to angular variations in the multiple scattering. Observations of attenuation at several frequencies should permit (a) determination of the spectrum of fractures (Gaussian versus Kolmogorovian) and (b) determination of the contribution of viscous damping to the effective attenuation.