Thermodynamic data from redox reactions at high temperatures. II. The MnO-0Mn3O4 oxygen buffer,and implications for the thermodynamic properties of MnO and Mn3O4

The \(\mu _{O_2 } \) defined by the reaction 6 MnO+O₂ =2 Mn₃O₄ has been determined from 917 to 1,433 K using electrochemical cells (with calcia-stabilized zirconta, CSZ) of the type: Steady emfs were achieved rapidly at all temperatures on both increasing and decreasing temperature, indicating that the MnO-Mn₃O₄ oxygen buffer equilibrates relatively easily. It therefore makes a useful alternative choice in experimental petrology to Fe₂O₃-Fe₃O₄ for buffering oxygen potentials at oxidized values. The results are (in J/mol, temperature in K, reference pressure 1 bar); \(\mu _{O_2 } \) (±200)=-563,241+1,761.758T-220.490T inT+0.101819T ² with an uncertainty of ±200 J/mol. Third law analysis of these data, including a correction for the deviations in stoichiometry of MnO, impliesS _298.15 for Mn₃O₄ of 166.6 J/K · mol, which is 2.5 J/K · mol higher than the calorimetric determination of Robie and Hemingway (1985). The low value of the calorimetric entropy may be due to incomplete ordering of the magnetic spins. The third law value of Δ _r H _298.15 ⁰ is-450.09 kJ/mol, which is significantly different from the calorimetric value of-457.5±3.4 kJ/mol, calculated from Δ _f H _298.15 ⁰ of MnO and Mn₃O₄, implying a small error in one or both of these latter.     

Mass-radius relationships and constraints on the composition of Pluto,II

A new estimate of Pluto's mass within the range of possible masses considered in an earlier work has enabled us to refine our model of Pluto's interior.     

Resistive ballooning line-tied boundary conditions

Ideal and resistive ballooning modes are investigated for different ratios of a two-layer stratified density region representing a model for the photospheric/coronal boundary. Construction of the ballooning equations using a WKB approach is justified by comparison between the values of the growth rate obtained using Hain-Lüst and ballooning equations together with a WKB integral relation. Different values of the density ratio, radius, and resistivity are considered. Sausage-type and kink-type instabilities are found. One of these, depending on the value of r remained unstable for large density ratios. The other instability tended to marginal stability as the density ratio was increased, and allowed parallel and perpendicular flows across the boundary. This is contrary to the predictions of both the rigid-wall and flow-through conditions.     

Water vapor adsorption by sodium montmorillonite at −5°C

A large amount of interest has recently been expressed pertaining to the quantity of physically adsorbed water by the Martian regolith. Thermodynamic calculations based on experimentally determined adsorption and desorption isotherms and extrapolated to subzero temperatures indicate that physical adsorption of more than one or two monomolecular layers is highly unlikely under Martian conditions. Any additional water would find ice to be the state of lowest energy and therefore the most stable form. To test the validity of the thermodynamic calculations we have measured adsorption and desorption isotherms of sodium montmorillonite at ?5°C. To a first approximation it was found to be valid.     

The formation of saturn's satellites and rings,as influenced by saturn's contraction history

We have used Pollack et al.'s 1976 calculations of the quasi-equilibrium contraction of Saturn to study the influence of the planet's early high luminosity on the formation of its satellites and rings. Assuming that the condensation of ices ceased at the same time within Jupiter's and Saturn's primordial nebulae, and using limits for the time of cessation derived for Jupiter's system by Pollack and Reynolds (1974) and Cameron and Pollack (1975), we arrive at the following tentative conclusions. Titan is the innermost satellite at whose position a methane-containing ice could condense, a result consistent with the presence of methane in this satellite's atmosphere. Water ice may have been able to condense at the position of all the satellites, a result consistent with the occurrence of low-density satellites close to Saturn. The systematic decrease in the mass of Saturn's regular satellites with decreasing distance from Saturn may have been caused partially by the larger time intervals for the closer satellites between the start of contraction and the first condensation of ices at their positions and between the start of contraction and the time at which Saturn's radius became less than a satellite's orbital radius. Ammonia ices, principally NH₄SH, were able to condense at the positions of all but the innermost satellites.Water ice may bave been able to condense in the region of the rings close to the end of the condensation period. We speculate that the rings are unique to Saturn because on the one hand, temperatures within Jupiter's Roche limit never became cool enough for ice particles to form before the end of the condensation period and on the other hand, ice particles formed only very early within Uranus' and Neptune's Roche limits, and were eliminated by gas drag effects that caused them to spiral into the planet before the gas of these planets' nebula was eliminated. Gas drag would also have eliminated any rocky particles initially present inside the Roche limit.We also derive an independent estimate of several million years for the time between the start of the quasi-equilibrium contraction of Saturn and the cessation of condensation. This estimate is based on the density and mass characteristics of Saturn's satellites. Using this value rather than the one found for Jupiter's satellites, we find that the above conclusions about the rings and the condensation of methane-and ammonia-containing ices remain valid.     

Does reactive surface area depend on grain size? Results from pH 3, 25 °C far-from-equilibrium flow-through dissolution experiments on anorthite and biotite

Laboratory determined mineral weathering rates need to be normalised to allow their extrapolation to natural systems. The principle normalisation terms used in the literature are mass, and geometric- and BET specific surface area (SSA). The purpose of this study was to determine how dissolution rates normalised to these terms vary with grain size. Different size fractions of anorthite and biotite ranging from 180-150 to 20-10 μm were dissolved in pH 3, HCl at 25 °C in flow through reactors under far from equilibrium conditions. Steady state dissolution rates after 5376 h (anorthite) and 4992 h (biotite) were calculated from Si concentrations and were normalised to initial- and final- mass and geometric-, geometric edge- (biotite), and BET SSA. For anorthite, rates normalised to initial- and final-BET SSA ranged from 0.33 to 2.77 × 10⁻¹⁰ mol_feldspar m⁻² s⁻¹, rates normalised to initial- and final-geometric SSA ranged from 5.74 to 8.88 × 10⁻¹⁰ mol_feldspar m⁻² s⁻¹ and rates normalised to initial- and final-mass ranged from 0.11 to 1.65 mol_feldspar g⁻¹ s⁻¹. For biotite, rates normalised to initial- and final-BET SSA ranged from 1.02 to 2.03 × 10⁻¹² mol_biotite m⁻² s⁻¹, rates normalised to initial- and final-geometric SSA ranged from 3.26 to 16.21 × 10⁻¹² mol_biotite m⁻² s⁻¹, rates normalised to initial- and final-geometric edge SSA ranged from 59.46 to 111.32 × 10⁻¹² mol_biotite m⁻² s⁻¹ and rates normalised to initial- and final-mass ranged from 0.81 to 6.93 × 10⁻¹² mol_biotite g⁻¹ s⁻¹. For all normalising terms rates varied significantly (p ? 0.05) with grain size. The normalising terms which gave least variation in dissolution rate between grain sizes for anorthite were initial BET SSA and initial- and final-geometric SSA. This is consistent with: (1) dissolution being dominated by the slower dissolving but area dominant non-etched surfaces of the grains and, (2) the walls of etch pits and other dissolution features being relatively unreactive. These steady state normalised dissolution rates are likely to be constant with time. Normalisation to final BET SSA did not give constant ratios across grain size due to a non-uniform distribution of dissolution features. After dissolution coarser grains had a greater density of dissolution features with BET-measurable but unreactive wall surface area than the finer grains. The normalising term which gave the least variation in dissolution rates between grain sizes for biotite was initial BET SSA. Initial- and final-geometric edge SSA and final BET SSA gave the next least varied rates. The basal surfaces dissolved sufficiently rapidly to influence bulk dissolution rate and prevent geometric edge SSA normalised dissolution rates showing the least variation. Simple modelling indicated that biotite grain edges dissolved 71-132 times faster than basal surfaces. In this experiment, initial BET SSA best integrated the different areas and reactivities of the edge and basal surfaces of biotite. Steady state dissolution rates are likely to vary with time as dissolution alters the ratio of edge to basal surface area. Therefore they would be more properly termed pseudo-steady state rates, only appearing constant because the time period over which they were measured (1512 h) was less than the time period over which they would change significantly.     

Search for nucleosynthetic and radiogenic tellurium isotope anomalies in carbonaceous chondrites

Tellurium isotope data acquired by multiple-collector inductively coupled plasma-mass spectrometry (MC-ICPMS) are presented for sequential acid leachates of the carbonaceous chondrites Orgueil, Murchison, and Allende. Tellurium isotopes are produced by a broad range of nucleosynthetic pathways and they are therefore of particular interest given the isotopic anomalies previously identified for other elements in these meteorites. In addition, the data provide new constraints on the initial solar system abundance of the r-process nuclide ¹²⁶Sn, which decays to ¹²⁶Te with a half-life of 234,500 years. The ¹²⁶Te/¹²⁸Te ratios of all leachates were found to be identical, within uncertainty, despite variations in ¹²⁴Sn/¹²⁸Te of between about 0.002 and 1.4. The data define a ¹²⁶Sn/¹²⁴Sn ratio of <7.7 × 10⁻⁵ at the time of last isotopic closure, consistent with the value of <18 × 10⁻⁵ previously reported for bulk carbonaceous chondrites. How close this is to the initial ¹²⁶Sn/¹²⁴Sn ratio of the solar system depends on when the investigated samples last experienced redistribution of Sn and Te. No clear evidence is found for nucleosynthetic anomalies in the abundances of p-, s-, and r-process nuclides. The largest effect detected in this study is a small excess of the r-process nuclide ¹³⁰Te in a nitric acid leachate of Murchison. This fraction displays an anomalous ε¹³⁰Te of +3.5 ± 2.5. Although barely resolvable given the analytical uncertainties, this is consistent with the presence of a small excess r-process component or an s-process deficit. The general absence of anomalies contrasts with previous results obtained for K, Cr, Zr, Mo, and Ba isotopes in similar leachates, which display nucleosynthetic anomalies of up to 3.8%. The reason for this discrepancy is unclear but it may reflect volatility and more efficient mixing of Te in the solar nebula.     

Experimental evaluation of biases associated with sampling estuarine fishes with seines

Beach seines are widely used to estimate the density and species richness of fishes in estuaries. We evaluated the causes and extent of bias in estimates from seines using a series of field experiments in small estuaries in southern California, USA. Seining in spatially paired areas that were either enclosed by block nets or not, revealed that seines used without block nets und erestimated density by more than 4-fold and species richness by more than 2-fold relative to blocked areas. Seining in paired blocked areas with seines of two lengths revealed that net length affected estimates of density, but not species richness; a 7.6-m long seine produced 1.6-fold higher estimates of total density than did a 15.2-m long seine due to increased catches of demersal fishes, but not midwater species. Paired sampling in blocked areas also revealed that many fishes initially evaded capture by the seine. Estimates of density but not species richness were significantly higher in areas through which a seine was swept 5 times compared to once. This was due to higher catches of demersal fishes but not midwater fishes in areas seined 5 times. Repeated seining through blocked areas revealed that the vast majority (90% or more) of species and individuals of midwater fishes were captured within the first 5 sweeps, compared to only about 50% of the individuals of demersal species. A mark-recapture study in blocked areas revealed lower probabilities of capture for demersal species relative to midwater species.     

Sampling characteristics and biases of enclosure traps for sampling fishes in estuaries

We evaluated the sampling characteristics of enclosure traps in estuaries in southern California, USA. Using enclosure traps that sampled 0.25, 0.5, and 1-m² footprints, we found that enclosure trap size significantly affected estimates of fish density and the precision of these estimates. The highest estimates were produced by the 0.5-m² trap and the lowest by the 0.25-m² trap. Precision of the density estimates improved with increasing trap size, while the proportion of zero values in the data sets decreased and estimates of species richness increased. The largest trap was difficult to use in the field and often did not function properly; thus we concluded that intermediate enclosure trap sizes offered the best compromise between statistical and logistical considerations. By examination of burrows in sediment cores taken in fished out enclosure traps, we found no evidence to support the widely held view that burrow-dwelling fishes evaded capture by hiding in burrows. We also used mark-recapture techniques to estimate recovery efficiency in 0.43-m² enclosure traps. Recovery efficiency averaged 91% and did not differ significantly among estuaries or sampling stations within estuaries. Based on extensive netting within enclosure traps, we determined that in areas with dense fish populations (>90 fish 0.43-m⁻²), netting could be ceased after the first sweep that captured no fish with only a trivial effect on the estimate of density. In more sparsely populated areas, netting had to continue until 2–3 sweeps had captured no fish in order to obtain estimates of density that were within 90% of the actual values present. Overall, we found enclosure traps to be effective tools for sampling small, abundant fishes in shallow estuaries in southern California, but we recommend that care be taken when choosing trap size and sampling (netting) effort within traps in order to optimize their sampling characteristics.     

Relative effects of physical and biological processes on nutrient and phytoplankton dynamics in a shallow estuary after a storm event

The effects of advection, dispersion, and biological processes on nitrogen and phytoplankton dynamics after a storm event in December 2002 are investigated in an estuary located on the northern New South Wales coast, Australia. Salinity observations for 16 d after the storm are used to estimate hydrodynamic transports for a one-dimensional box model. A biological model with nitrogen limited phytoplankton growth, mussel grazing, and a phytoplankton mortality term is forced by the calculated transports. The model captured important aspects of the temporal and spatial dynamics of the bloom. A quantitative analysis of hydrodynamic and biological processes shows that increased phytoplankton biomass due to elevated nitrogen loads after the storm was not primarily regulated by advection or dispersion in spite of an increase in river flow from <1 to 928×10³ m³ d⁻¹. Of the dissolved nitrogen that entered the surface layer of the estuary in the 16 d following the storm event, the model estimated that 28% was lost through exchange with the ocean or bottom layers, while 15% was removed by the grazing of just one mussel species,Xenostrobus securis, on phytoplankton, and 50% was lost through other biological phytoplankton loss processes.X. securis grazing remained an important loss process even when the estimated biological parameters in the model were varied by factors of ± 2. The intertidal mangrove pneumatophore habitat ofX. securis allows filtering of the upper water column from the lateral boundaries when the water column is vertically stratified, exerting top-down control on phytoplankton biomass.