Heterogeneous electron-transfer kinetics with synchrotron Fe Mössbauer spectroscopy

In the first known kinetic application of the technique, synchrotron ⁵⁷Fe-Mössbauer spectroscopy was used to follow the rate of heterogeneous electron transfer between aqueous reagents and a solid phase containing Fe. The solid, a synthetic ⁵⁷Fe-enriched Fe(III)-bearing pyroaurite-like phase having terephthalate (TA) in the interlayer [Mg₃Fe(OH)₈(TA)_0.5 · 2H₂O], was reduced by Na₂S₂O₄ and then reoxidized by K₂Cr₂O₇ by means of a novel flow-through cell. Synchrotron Mössbauer spectra were collected in the time domain at 30-s intervals. Integration of the intensity obtained during a selected time interval in the spectra allowed sensitive determination of Fe(II) content as a function of reaction time. Analysis of reaction end member specimens by both the synchrotron technique and conventional Mössbauer spectroscopy yielded comparable values for Mössbauer parameters such as center shift and Fe(II)/Fe(III) area ratios. Slight differences in quadrupole splitting values were observed, however. A reactive diffusion model was developed that fit the experimental Fe(II) kinetic data well and allowed the extraction of second-order rate constants for each reaction. Thus, in addition to rapidly collecting high quality Mössbauer data, the synchrotron technique seems well suited for aqueous rate experiments as a result of the penetrating power of 14.4 keV X-rays and high sensitivity to Fe valence state.     

Geochemistry of eucrites: genesis of basaltic eucrites, and Hf and Ta as petrogenetic indicators for altered antarctic eucrites

We performed instrumental neutron activation analysis on a large suite of antarctic and nonantarctic eucrites, including unbrecciated, brecciated, and polymict eucrites and cumulate and noncumulate eucrites. We evaluate the use of Hf and Ta, two highly incompatible elements, as sensitive indicators of partial melting or fractional crystallization processes. Comparison with rare earth element (REE) data from nonantarctic and antarctic eucrites shows that Hf and Ta are unaffected by the terrestrial alteration that has modified the REE contents and patterns of some antarctic eucrites. The major host phases for Hf and Ta—zircon, baddeleyite, ilmenite, and titanite—are much less susceptible to terrestrial alteration than the phosphate hosts of REEs. The host phases for Hf and Ta are minor or trace phases, so sample heterogeneity is a serious concern for obtaining representative compositions. The trace lithophile and siderophile element contents of noncumulate eucrites do not allow for a single, simple model for the petrogenesis of the howardite-eucrite-diogenite suite. Fractional crystallization models cannot reproduce the compositional relationship between eucrites of the main group-Nuevo Laredo trend and those of the Stannern trend. Equilibrium crystallization models cannot explain the trace element diversity observed among diogenites. Partial melting models cannot explain the W variations among eucrites, unless source regions had different metal contents. We suggest that slight variations in oxygen fugacity of eucrite source regions during partial melting can explain the W variations without requiring different metal contents. This hypothesis may fail to account for eucrite Co contents, however.     

Fluxes of Sr into the headwaters of the Ganges

Himalayan weathering is recognized as an important agent in modifying sea water chemistry, but there are significant uncertainties in our understanding of Himalayan riverine fluxes. This paper examines causes of the variability, including that of the seasons, by analysis of downstream variations in Sr, ⁸⁷Sr, and major ions in the mainstream, in relation to the composition of tributary streams from subcatchments with differing geologic substrates.Water samples were collected over four periods spanning the premonsoon, monsoon, and postmonsoon seasons. Uncertainties in the relative fluxes have been estimated, using Monte Carlo techniques, from the short-term variability of mainstream chemistry and the scatter of tributary compositions. The results show marked seasonal variations in the relative inputs related to high monsoon rainfall in the High and Lesser Himalaya, contrasting with the major contribution from glacial melt waters from the Tibetan Sedimentary Series (TSS) at times of low rainfall. Much of the spread in previously published estimates of the sources of Sr in Himalayan rivers may result from these seasonal variations in Sr fluxes.The annual fluxes of Sr into the headwaters of the Ganges are derived from the three main tectonic units in the proportions 35 ± 1% from the TSS, 27 ± 3% from the High Himalayan Crystalline Series (HHCS), and 38 ± 8% from the Lesser Himalaya. The particularly elevated ⁸⁷Sr/⁸⁶Sr ratios characteristic of the HHCS and the Lesser Himalaya enhance their influence on seawater Sr-isotope composition. The TSS contributes 13 ± 1%, the HHCS 30 ± 3%, and the Lesser Himalaya 57 ± 11% of the ⁸⁷Sr flux in excess of the seawater ⁸⁷Sr/⁸⁶Sr ratio of 0.709.     

Characteristics of the atmospheric heat source and moisture sink over the Qinghai-Tibetan Plateau during the second TIPEX of summer 1998 and their impact on surrounding monsoon

Summary ?Using the data of 6 automatic heat balance observation (AWS) stations and a data set of 52 surface observation stations over the Qinghai-Tibetan Plateau (“the Plateau”) and surroundings, the horizontal distribution is studied of “apparent atmospheric heat sources” 〈Q ₁〉 and of “apparent atmospheric moisture sinks” 〈Q ₂〉. The AWS stations were established during the period May to August 1998 of the Tibetan Plateau Meteorological Experiment (second TIPEX) by a cooperation of China and Japan. For this period the Plateau mean of 〈Q ₁〉 is positive. Its value of 74 W/m² is a little greater than a climate value and than values from MONEX and the first TIPEX in 1979, respectively. Also the corresponding 〈Q ₂〉 is positive. Hence during that time the Plateau is a heat source and a moisture sink. A day-to-day change of 〈Q ₁〉 and 〈Q ₂〉 is more pronounced over the middle and east part of the Plateau than over the west part. Diagnostics accompanied by numerical simulations are used to study the daily relationship between 〈Q ₁〉 over the Plateau and the weather over China and Asia for this summer. The results suggest that 〈Q ₁〉 may affect precipitation over northern China and position of the west Pacific subtropical high. Abnormal southward retreat of this Pacific high seems to have caused the second flood over the middle and lower Yangtse river basin in July. Received May 20, 2001; revised February 2, 2002     

The Global Distribution of Secondary Particulate Matter in a 3-D Lagrangian Chemistry Transport Model

A global 3-D Lagrangian chemistry-transport model STOCHEM is used to describe the tropospheric distributions of four components of the secondary atmospheric aerosol: nitrate, sulphate, ammonium and organic compounds. The model describes the detailed chemistry of the formation of the acid precursors from the oxidation of SO₂, DMS, NO_x, NH₃ and terpenes and their uptake into the aerosol. Model results are compared in some detail with the available surface observations. Comparisons are made between the global budgets and burdens found in other modelling studies. The global distributions of the total mass of secondary aerosols have been estimated for the pre-industrial, present day and 2030 emissions and large changes have been estimated in the mass fractions of the different secondary aerosol components.     

The Vulnerability of the Australian Beef Industry to Impacts of the Cattle Tick (Boophilus microplus) under Climate Change

An integrated assessment is presented of the potential impacts of the cattle tick (Boophilus microplus Canestrini) on the Australian beefindustry under climate change. The project was carried out as a case study to test an impact assessment approach that was designed to integrate biological, production and socio-economic impacts on managed and natural systems. A climate-driven, tick population model was run for European, zebu and crossbred cattle breeds having different levels of resistance to cattle ticks. A geographical information system (GIS) was used to organise spatial data on climate scenarios and industry statistics and to undertake regional analyses.A comparison was made of the two available approaches to conducting impact assessments, namely a bottom-up approach using sensitivity analysis and a top-down approach using climate change scenarios from a global circulation model (GCM) (CSIRO, 1996). The output, in terms of the abundance of tick populations and reductions in cattle productivity for each breed showed significant expansions in potential geographical impacts. In the absence of any adaptation measures, the results indicated changes in the losses in live weight gain of cattle tick ranging from 7780 tonnes per year by 2030 to 21637 tonnes per year by 2100, in comparison with estimates for current losses of 6594 tonnes per year.The principal adaptation options available to the beef industry are to switch to breeds that are more resistant to cattle ticks, or to increase the frequency of treatments with various tick control products. In this paper we focus on switching breeds as an adaptive measure when appropriate damage thresholds are triggered under the climate change scenarios. When adaptation measures were put in place, the losses ranged from 4962 tonnes in 2030 to 5619 tonnes in 2100 compared with 2636 tonnes at present if all producers adopted the optimal breed structure. Optimal breed structure was defined as one that would prevent tick numbers per animal exceeding 100 ticks per animal for European and 700 ticks per animal for crossbred breeds of cattle in any week of the year under a tick control strategy that was suitable for present climatic conditions. The lower threshold for European breeds reflects their vulnerability to explosive increases in numbers because of their low resistance to ticks. The results of the analyses using the GCM scenarios were used in an economic model to calculate costs of lost live-weight gain for 2030, 2070 and 2100. The greatest increases in costs were incurred in the southern parts of the current distribution in Queensland and potentially in northern New South Wales if the present quarantine barrier failed.Given the great uncertainty of the nature of possible regional changes in climate, analyses of the sensitivity of losses in live weight gain to changes in climatic variables were also undertaken. The analyses included a measure of likely impacts of cattle tick on the beef cattle industry, in the absence of adaptation measures, as a baseline measure of sensitivity. The likely impacts on crossbred cattle were insensitive to the climatic variables.When adaptive breed changes were allowed, the economic impacts on the industry were insensitive to the GCM scenarios. This suggests that, at least in this instance, reducing the uncertainties in climate change scenarios is not a priority if the adaptation strategies can be implemented in a cost-effective manner. Finally we made a qualitative assessment of the sustainability and robustness of alternative approaches to adaptation and assessed regional vulnerability to cattle tick under climate change. The conclusions were so strongly dependent on assumptions about the future of other global changes, in particular the ability to maintain quarantine barriers and to retain effective acaricides at comparable costs to the present, that we strongly recommend that risk assessments of climate change extend to all relevant variables in involved in global change where possible.     

Understanding Climatic Impacts, Vulnerabilities, and Adaptation in the United States: Building a Capacity for Assessment

Based on the experience of the U.S. National Assessment, we propose a program of research and analysis to advance capability for assessment of climate impacts, vulnerabilities, and adaptation options. We identify specific priorities for scientific research on the responses of ecological and socioeconomic systems to climate and other stresses; for improvement in the climatic inputs to impact assessments; and for further development of assessment methods to improve their practical utility to decision-makers. Finally, we propose a new institutional model for assessment, based principally on regional efforts that integrate observations, research, data, applications, and assessment on climate and linked environmental-change issues. The proposed program will require effective collaboration between scientists, resource managers, and other stakeholders, all of whose expertise is needed to define and prioritize key regional issues, characterize relevant uncertainties, and assess potential responses. While both scientifically and organizationally challenging, such an integrated program holds the best promise of advancing our capacity to manage resources and the economy adaptively under a changing climate.     

Meso-gamma scale forecasts using the nonhydrostatic model LM

Summary ?The nonhydrostatic model LM was developed for small scale operational predictions. Advances in computer development will give the possibility of operational models of a rather fine scale, which will cover the meso-gamma scale. The LM is currently applied at a scale of 7 km and an increase of the operational resolution to 2.5 km is planned for the next few years. Predictions of such high resolution require to abandon the hydrostatic assumption, which is used with most current operational weather prediction models. The LM was designed to cover all resolutions from 50 m to 50 km with an efficiency making it suitable for operational use. It is a fully elastic model, using second order centred finite differences. The time integration is done using the Klemp–Wilhelmson method, treating the slow modes by a larger time step than the fast modes. The vertical propagation of the fast waves is done implicitly. After describing the design of the LM, this paper gives examples of model predictions at the meso-γ scale. Some results of the current operational application at the resolution 7 km are presented. Deficiencies in the localisation of model generated precipitation are investigated using an idealised bell shaped mountain and applying different resolutions. In this way the convergence to the correct solution can be investigated. From these results it is concluded, that orographic filtering is necessary and the effect of such filtering on precipitation forecasts is investigated. Finally, the prediction of a squall line over northern Germany is shown in order to demonstrate the potential of the model in forecasting the meso-γ scale. Received May 15, 2001; revised September 21, 2001     

Climate Dangers and Atoll Countries

Climate change-induced sea-level rise, sea-surface warming, and increased frequency and intensity of extreme weather events puts the long-term ability of humans to inhabit atolls at risk. We argue that this risk constitutes a dangerous level of climatic change to atoll countries by potentially undermining their national sovereignty. We outline the novel challenges this presents to both climate change research and policy. For research, the challenge is to identify the critical thresholds of change beyond which atoll social-ecological systems may collapse. We explain how thresholds may be behaviorally driven as well as ecologically driven through the role of expectations in resource management. The challenge for the international policy process, centred on the UN Framework Convention on Climate Change (UNFCCC), is to recognize the particular vulnerability of atoll countries by operationalising international norms of justice, sovereignty, and human and national security in the regime.