An electrochemical study of Ni2+, Co2+, and Zn2+ ions in melts of composition CaMgSi2O6

Cyclic voltammetry has been done for Ni²⁺, Co²⁺, and Zn²⁺ in melts of diopside composition in the temperature range 1425 to 1575°C. Voltammetric curves for all three ions excellently match theoretical curves for uncomplicated, reversible charge transfer at the Pt electrode. This implies that the neutral metal atoms remain dissolved in the melt. The reference electrode is a form of oxygen electrode. Relative to that reference assigned a reduction potential of 0.00 volt, the values of standard reduction potential for the ions are $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.32 ± .01}\text{V}$, $\text{E}{}^1\text{(}\text{Co}{}^{\mathrm{2+}}\text{Co}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.45 ± .02}\text{V}$, and $\text{E}{}^1\text{(}\text{Zn}{}^{\mathrm{2+}}\text{Zn}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.53 ± .01}\text{V}$. The electrode reactions are rapid, with first order rate constants of the order of 10^?2 cm/sec. Diffusion coefficients were found to be 2.6 × 10^?6 cm²/sec for Ni²⁺, 3.4 × 10^?6 cm²/sec for Co²⁺, and 3.8 × 10^?6 cm²/sec for Zn²⁺ at 1500°C. The value of $\text{E1}$ ($\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0$, diopside) is a linear function of temperature over the range studied, with values of ?0.35 V at 1425°C and ?0.29 V at 1575°C. At constant temperature the value of $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{, 1525°C}$) was not observed to vary with composition over the range CaO · MgO · 2SiO₂ to CaO·MgO·3SiO₂ or from 1.67 CaO·0.33MgO·2SiO₂ to 0.5 CaO·1.5MgO·2SiO₂. The value for the diffusion coefficient for Ni²⁺ decreased by an order of magnitude at 1525°C over the compositional range CaO · MgO · 1.25SiO₂ to CaO · MgO · 3SiO₂. This is consistent with a mechanism by which Ni²⁺ ions diffuse by moving from one octahedral coordination site to another in the melt, with the same Ni²⁺ species discharging at the cathode regardless of the SiO₂ concentration in the melt.     

The contribution of humic substances to the acidity of colored natural waters

An operationally defined carboxyl content of humic substances extracted from rivers, streams, lakes, wetlands, and groundwaters throughout the United States and Canada is reported. Despite the diversity of the samples, only small variations were observed in this humic carboxyl content. The dissociation behavior of two combined fulvic/humic acid extracts was studied and it was found that the dissociation of the humics varied in a predictable manner with pH. Using a carboxyl content of 10 μeq/ mg humic organic carbon, and mass action quotient calculated from sample pH, the ionic balances of three highly colored Nova Scotia rivers were estimated.     

The weathering of a late Tertiary volcanic ash: Importance of organic solutes

The weathering of a late Tertiary volcanic ash near Jackson, Wyoming, was studied by sampling water percolating through the ash with suction lysimeters, and by examination of the associated solid phases. Soluble organic compounds derived from vegetation control the release and transport of solutes by complexing Al and Fe, and by causing low pH values. The concentrations of Na, K, Ca, and Mg, as well as those of Al and Fe correlate with the dissolved organic carbon concentrations (DOC) and follow an annual cycle with a maximum in spring. DOC concentrations averaged 5O mg C per liter, and values as high as 260 mg/l were observed. Al and Fe concentrations ranged as high as 5 mg/l. The dissolved organic matter was largely in the form of humic acids, although minor amounts of oxalate, acetate, and formate were also present. The pH of the percolating waters ranged from 4.3 to 6.5 with a mean of 5.2.During laboratory weathering experiments with the same ash in the absence of dissolved organic compounds, pH values ranged from 7.3 to 9.5, dissolved Al and Fe concentrations were below the detection limit, and there was little resemblance between the compositions of the solutions and the compositions observed in the field. Any model attempting to describe weathering in a comparable setting must incorporate biological mechanisms as the dominant controls.     

Uncertainty in Coal Property Valuation in West Virginia: A Case Study

Interpolated grids of coal bed thickness are being considered for use in a proposed method for taxation of coal in the state of West Virginia (United States). To assess the origin and magnitude of possible inaccuracies in calculated coal tonnage, we used conditional simulation to generate equiprobable realizations of net coal thickness for two coals on a 7 min topographic quadrangle, and a third coal in a second quadrangle. Coals differed in average thickness and proportion of original coal that had been removed by erosion; all three coals crop out in the study area. Coal tonnage was calculated for each realization and for each interpolated grid for actual and artificial property parcels, and differences were summarized as graphs of percent difference between tonnage calculated from the grid and average tonnage from simulations. Coal in individual parcels was considered minable for valuation purposes if average thickness in each parcel exceeded 30 inches. Results of this study show that over 75% of the parcels are classified correctly as minable or unminable based on interpolation grids of coal bed thickness. Although between 80 and 90% of the tonnages differ by less than 20% between interpolated values and simulated values, a nonlinear conditional bias might exist in estimation of coal tonnage from interpolated thickness, such that tonnage is underestimated where coal is thin, and overestimated where coal is thick. The largest percent differences occur for parcels that are small in area, although because of the small quantities of coal in question, bias is small on an absolute scale for these parcels. For a given parcel size, maximum apparent overestimation of coal tonnage occurs in parcels with an average coal bed thickness near the minable cutoff of 30 in. Conditional bias in tonnage for parcels having a coal thickness exceeding the cutoff by 10 in. or more is constant for two of the three coals studied, and increases slightly with average thickness for the third coal.     

Inverted-polarity electrical structures in thunderstorms in the Severe Thunderstorm Electrification and Precipitation Study (STEPS)

Balloon-borne electric field soundings and lightning mapping data have been analyzed for three of the storms that occurred in the Severe Thunderstorm Electrification and Precipitation Study field program in 2000 to determine if the storms had inverted-polarity electrical structures. The polarities of all or some of the vertically stacked charge regions in such storms are opposite to the polarities observed at comparable heights in normal storms. Analyses compared the charge structures inferred from electric field soundings in the storms with charges inferred from three-dimensional lightning mapping data. Charge structures were inferred from electric field profiles by combining the one-dimensional approximation of Gauss's law with additional information from three-dimensional patterns in the electric field vectors. The three different ways of inferring the charge structure in the storms were found to complement each other and to be consistent overall. Charge deposition by lightning possibly occurred and increased the charge complexity of one of the storms.Many of the cloud flashes in each case were inverted-polarity flashes. Two storms produced ground flash activity comprised predominantly of positive ground flashes. One storm, which was an isolated thunderstorm, produced inverted-polarity cloud flashes, but no flashes to ground. The positive and negative thunderstorm charge regions were found at altitudes where, respectively, negative and positive charge would be found in normal-polarity storms. Thus, we conclude that these storms had anomalous and inverted-polarity electrical structures. Collectively, these three cases (along with the limited cases in the refereed literature) provide additional evidence that thunderstorms can have inverted-polarity electrical structures.     

Examining the C1-P1 Pseudorange Bias

Use of GPS tracking data from different dual-frequency receiver types (cross-correlating vs. codeless) has revealed satellite-dependent biases in pseudorange observables P1 (Y-code) and C1 (C/A, Clear Acquisition code). These biases can have a direct effect on clock estimates, carrier phase bias fixing, and other parameters estimated in GPS data processing. A set of satellite-specific compensatory pseudorange offsets is calculated, and each is applied to a wee of daily global network analyses in which satlellite, receiver, atmospheric, and Earth rotation parameters are estimated. Results from these analyses are then compared to those from corresponding baseline cases in which no biases were applied. There is also some evidence that suggests that the pseudorange biases differ even among codeless receiver models. Hence, a second set of offsets is computed on a different basis, and compared with the baseline model in a similar manner. A preliminary examination of C1-P1 variations over time is presented. Finally, recommendations are made for the use of the calculated offsets, and consideration is given to a future dissemination of updates to these values as necessary. ? 2001 John Wiley & Sons, Inc.     

中国南京与美国德克萨斯稻田甲烷排放的比较

Field measurements of methane emission from rice paddies were made in Nanjing, China and in Texas, USA, respectively. Soil temperature at approximately 10 cm depth of the flooded soils was automatically recorded. Aboveground biomass of rice crop was measured approximately every 10 days in Nanjing and every other week in Texas. Seasonal variation of soil temperature in Nanjing was quite wide with a magnitude of 15.3℃ and that in Texas was narrow with a magnitude of 2.9℃. Analysis of methane emission fluxes against soil temperature and rice biomass production demonstrated that the seasonal course of methane emission in Nanjing was mostly attributed to soil temperature changes, while that in Texas was mainly related to rice biomass production. We concluded that under the permanent flooding condition, the seasonal trend of methane emission would be determined by the soil temperature where there was a wide variation of soil temperature, and the seasonal trend would be mainly determined by rice biomass production if there are no additional organic matter inputs and the variation of soil temperature over the rice growing season is small.     

Efficacy of minnow traps for sampling mummichogs in tidal marshes

We evaluated two types of wire-mesh minnow traps for sampling mummichogs (Fundulus heteroclitus) from intertidal rivulets on the surface of a salt marsh. In field trials, mean catch (no. of fish trap⁻¹) did not differ significantly between trap types nor across soak times ranging from 30 to 240 min. Catch rate (no. of fish trap⁻¹ min⁻¹) was significantly (K-W ANOVA on ranked data, H_4df=24.79; p<0.001) greater at shorter soak times, and larger size classes (>45 mm TL) of fish were relatively more abundant (Kolmogorov-Smirnov test, p<0.0001) in collections from double-funnel cylindrical traps (volume=10,330 cm³) compared to rectangular traps having about twice the volume and a single funnel cylindrical traps (volume=10,330 cm³) compared to rectangular traps having about twice the volume and a single funnel opening. We estimated entry and escape rates by adding marked fish to traps at initial densities of 30, 60, and 120 trap⁻¹ and measuring changes in the numbers of marked and unmarked fish in each trap type at soak times ranging from 15 to 120 min during the flood stage of the tidal cycle. Escape rate was almost, twice as great from the two-funnel cylindrical traps (0.77 fish min⁻¹) than from the single-funnel rectangular type (0.42 fish min⁻¹) but entry rates did not differ significantly (K-W ANOVA, H_4df=0.06; p=0.813) between trap types. Escape rate increased and entry rate decreased as fish density within traps was increased. Escape rates were highest immediately following immersion of the traps, but approached a constant value after 30 min. Trap-specific rates of entry and escape can be affected by a variety of factors including physical characteristics of different trap types, method and timing of trap deployment, and fish behavior. Catch data from minnow traps are unlikely to be useful in measuring relative abundance of mummichogs among habitats unless very short soak times (≤60 min) are used and calibration tests are performed. Use of longer soak times virtually ignores the dynamics involved in determining catch, and is unlikely to provide accurate information on either abundance or size distribution of mummichogs from tidal marsh habitats.     

Aircraft wind measurement considering lift-induced upwash

Flow distortion is a universal consideration in the measurement of wind. Usually the distortion results from deflection of the flow by the support. Instruments mounted on airplanes, however, experience an additional deflection associated with lift, which changes rapidly and continuously during flight. In front of the airplane, this deflection appears as upwash. Characteristic upwash contamination ranges from 0.5 to 2.5 m s^-1, depending on wing loading, flight speed, and forward distance from the wing to the measurement location. On pressure-radome installations the distance from the wing is usually small and the potential for upwash contamination large. Sensors mounted at the end of long probes attached to smaller airplanes with light wing loading are less susceptible to upwash contamination. Since wing loading also depends on the local vertical wind velocity the upwash velocity is directly correlated with vertical wind velocity. Generally, empirical corrections are derived from flight tests. We develop a simple method from principles of aerodynamics which explains these corrections in terms of upwash. The applicability of our approach to moderate upwash is demonstrated with data collected from the NOAA Long-EZ research airplane. More severe upwash conditions require a more sophisticated correction beyond the scope of this paper, but basically derived from the same principles.Oak Ridge Associated Universities, assigned to NOAA/ATDD