Evaluation of In Situ Heterogeneity of Elements in Solids: Implications for Analytical Geochemistry

A general method for the evaluation of in situ heterogeneity of geochemical materials is described and the significance of the results discussed, by using three case studies and earlier data sets. The heterogeneity of Pb in soil (expressed as RSD due to sampling, RSD_samp) varies from < 5 to > 100% between different sites, in a way that relates to the mode of deposition of the element. The heterogeneity of an element also varies systematically as a function of the distance scale at some sites. This variation can be modelled using linear regression, accounting for over 90% of the experimental variance, at seven scales over three orders of magnitude. Variation in heterogeneity between elements at the same site, seems to be somewhat diagnostic of the origin of the element, lithogenic being less than anthropogenic, although the later is also being modified by the mode of deposition. Where the heterogeneity is large (RSD > 30%), it is proposed that it can be expressed more accurately as a heterogeneity factor (10^GSDsamp), to reflect its frequency distribution, which is positively skewed towards higher concentration values.     

Limitations of single-basket trading: lessons from the Montreal Protocol for climate policy

Numerous policy options exist to reduce future greenhouse gas emissions. A single-basket approach, which controls aggregate emissions, was adopted by the Kyoto Protocol. Such an approach allows emissions reductions of one gas to be traded with those of other gases in the “basket”, with the trade “price” determined by some weighting metric like the Global Warming Potential. To reduce stratospheric ozone depletion, the Montreal Protocol also dealt with controlling many compounds, but did so employing an alternative, multi-basket scheme. Trading was allowed within each basket, but not among baskets. While the Montreal Protocol has been highly successful using this approach, we show that if a single-basket approach had been adopted the short-term success could have been at risk due to the non-unique relationship between controls and environmental impacts when using a single basket. Using climate policy as an example, and without considering technological and economic constraints, we further show that the magnitude of the ambiguities in impacts associated with a single-basket approach depends on the rapidity of the emission phaseout. Fast phaseouts lead to less ambiguity than do slow ones. These results suggest that for each set of greenhouse gas control policies considered, the benefit of additional flexibility associated with a single-basket approach should be weighed against the associated increased uncertainties in the impacts to ascertain whether a single- or a multi-basket approach has the greater chance of successfully mitigating climate change.     

On the interpretation of seasonal variations of stratospheric ozone

Insight into the causes of the annual and semi-annual ozone oscillations may be gained from the analysis of photochemical model behavior. In this paper, the monthly variations of the ozone mixing ratio computed by the two-dimensional photochemical model of Garcia and Solomon (1983, J. geophys. Res. 88, 1379) are Fourier-analyzed and compared with SBUV observations of ozone mixing ratio. Remarkably good qualitative agreement between the model calculations and the observations is found. Analysis of computed transport and chemical production and destruction rates reveals the causes of the modelled seasonal ozone variations.

It will be shown that at high latitudes and low altitudes, modelled ozone abundances increase in the winter due to transport and decrease in the summer due to chemical destruction. In the middle stratosphere, the calculated annual ozone variation is largely due to the annual variation in the odd-oxygen production rate, and in the upper stratosphere, the computed annual ozone variation is caused by the large calculated annual oscillation in temperature. Comparison between the model and observations suggests that the equatorial semi-annual oscillation above 10 mb is caused mainly by the semi-annual temperature and wind oscillation (SAO). Below 10 mb the computed equatorial ozone variation is caused by the increased rates of odd-oxygen production associated with the semi-annual zenith crossings of the Sun. Finally, the calculated polar semi-annual ozone oscillations are found to be caused by modulation of the radiatively driven middle-stratospheric ozone variation by temperature dependent chemical destruction processes.     

THE SEARCH FOR OIL: FACTORS INFLUENCING US INVESTMENT IN FOREIGN PETROLEUM EXPLORATION AND DEVELOPMENT*

Determinants of foreign exploration and development spending by US oil companies are examined with multiple regression analysis. Since major US oil companies earn higher profits abroad, I test the role of profit rate surrogates and cash flow in a petroleum investment model. A high income tax rate is shown to discourage foreign oil investment, a finding that should be recognized by foreign governments. Institutional factors also appear to limit the flow of investment funds out of the United States, despite attractive foreign profit rates.     

Applications of a total dissolved gas pressure probe in ground water studies

Measurements of dissolved gases have numerous applications in ground water hydrology, and it is now possible to measure the total dissolved gas pressure in situ using a probe. Dissolved gas pressure is measured by submerging a headspace volume with a gas-permeable membrane, allowing dissolved gases in the water to equilibrate with gases in the headspace, then measuring the pressure in the headspace with a pressure transducer. Total dissolved gas pressure (TGP) probes have many potential uses in ground water studies employing dissolved gases, including: (1) determining approximate excess air levels, which may provide information about the time and location of recharge; (2) screening wells for air contamination, which can compromise the accuracy of dissolved gas tracer techniques: (3) detecting a trapped gas phase, which can significantly reduce hydraulic conductivity and impede the transport of dissolved solutes and gases; (4) enabling the use of gas-filled passive diffusion samplers for determining accurate dissolved gas concentrations; and (5) determining relative concentrations of CH4 and CO2 when they are known to be highly abundant. Although TGP probes designed for surface water have been available for several years, TGP probes suitable for ground water applications have only recently become available. Herein we present what are, to our knowledge, the first reported ground water dissolved gas data collected using a TGP probe. We also explain the basic operating principles of these probes and discuss the potential applications listed.     

Modeling Dynamic Vegetation Response to Rapid Climate Change Using Bioclimatic Classification

Modeling potential global redistribution of terrestrial vegetation frequently is based on bioclimatic classifications which relate static regional vegetation zones (biomes) to a set of static climate parameters. The equilibrium character of the relationships limits our confidence in their application to scenarios of rapidly changing climate. Such assessments could be improved if vegetation migration and succession would be incorporated as response variables in model simulations. We developed the model MOVE (Migration Of VEgetation), to simulate the geographical implications of different rates of plant extirpation and in-migration. We used the model to study the potential impact on terrestrial carbon stocks of climate shifts hypothesized from a doubling of atmospheric greenhouse gas concentration. The model indicates that the terrestrial vegetation and soil could release carbon; the amount of this carbon pulse depends on the rate of migration relative to the rate of climate change. New temperate and boreal biomes, not found on the landscape today, increase rapidly in area during the first 100 years of simulated response to climate change. Their presence for several centuries and their gradual disappearance after the climate ceases to change adds uncertainty in calculating future terrestrial carbon fluxes.     

The global distribution of pyroclastic deposits on Mercury: The view from MESSENGER flybys 1–3

We present a global survey of candidate pyroclastic deposits on Mercury, derived from images obtained during MESSENGER flybys 1–3 that provided near-global coverage at resolutions between 5 and 0.5 km/pixel. Thirty-five deposits were identified and characterized and are located principally on the floors of craters, along rims of craters, and along the edge of the Caloris basin. Deposits are commonly centered on rimless, often irregularly shaped pits, mostly between 5 and 45 km in diameter. The deposits identified are generally similar in morphology and absolute reflectance to lunar pyroclastic deposits. Spectrally the deposits appear brighter and redder than background Mercury terrain. On the basis of the available coverage, the candidate pyroclastic deposits appear to be essentially globally distributed. The diameters of the deposits, when mapped to lunar gravity conditions, are larger than their lunar counterparts, implying that more abundant volatiles were present during the typical eruptive process than on the Moon. These observations indicate that if these deposits resulted from hawaiian-style eruptions, the volatile contents required would be between ～1600 and 16,000 ppm CO or an equivalent value of H₂O, CO₂, SO₂, or H₂S (for a more oxidizing interior), or N₂, S₂, CS₂, S₂Cl, Cl, Cl₂, or COS (for a more reducing interior). These abundances are much greater than those predicted by existing models for Mercury's formation. An apparent lack of small deposits, compared with the Moon, may be due to resolution effects, a topic that can be further assessed during the orbital phase of the MESSENGER mission. These results provide a framework within which orbital observations by MESSENGER and the future BepiColombo mission can be analyzed.