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     

Intercomparison of Stratospheric Chemistry Models under Polar Vortex Conditions

Several stratospheric chemistry modules from box, 2-D or 3-D models, have been intercompared. The intercomparison was focused on the ozone loss and associated reactive species under the conditions found in the cold, wintertime Arctic and Antarctic vortices. Comparisons of both gas phase and heterogeneous chemistry modules show excellent agreement between the models under constrained conditions for photolysis and the microphysics of polar stratospheric clouds. While the mean integral ozone loss ranges from 4–80% for different 30–50 days long air parcel trajectories, the mean scatter of model results around these values is only about ±1.5%. In a case study, where the models employed their standard photolysis and microphysical schemes, the variation around the mean percentage ozone loss increases to about ±7%. This increased scatter of model results is mainly due to the different treatment of the PSC microphysics and heterogeneous chemistry in the models, whereby the most unrealistic assumptions about PSC processes consequently lead to the least representative ozone chemistry. Furthermore, for this case study the model results for the ozone mixing ratios at different altitudes were compared with a measured ozone profile to investigate the extent to which models reproduce the stratospheric ozone losses. It was found that mainly in the height range of strong ozone depletion all models underestimate the ozone loss by about a factor of two. This finding corroborates earlier studies and implies a general deficiency in our understanding of the stratospheric ozone loss chemistry rather than a specific problem related to a particular model simulation.     

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.     

A Case Study Of An On-Ice Air Flow Over The Arctic Marginal Sea-Ice Zone

A case study of warm air advection over the Arctic marginalsea-ice zone is presented, based on aircraft observations with direct flux measurements carriedout in early spring, 1998. A shallow atmospheric boundary layer (ABL) was observed, which wasgradually cooling with distance downwind of the ice edge. This process was mainly connected with astrong stable stratification and downward turbulent heat fluxes of about 10–20 W m^-2, but wasalso due to radiative cooling. Two mesoscale models, one hydrostatic and the other non-hydrostatic,having different turbulence closures, were applied. Despite these fundamental differences betweenthe models, the results of both agreed well with the observed data. Various closure assumptions had amore crucial influence on the results than the differences between the models.Such an assumption was, for example,the parameterization of the surface roughness for momentum (z₀) and heat (z_T). This stronglyaffected the wind and temperature fields not only close to the surface but also within and abovethe temperature inversion layer. The best results were achieved using a formulation for z₀ that took intoaccount the form drag effect of sea-ice ridges together withz_T = 0.1z₀. The stability within theelevated inversion strongly depended on the minimum eddy diffusivity K_min. A simple ad hocparameterization seems applicable, where K_min is calculated as 0.005 timesthe neutral eddy diffusivity. Although the longwave radiative cooling was largest within the ABL, theapplication of a radiation scheme was less important there than above the ABL. This was related to theinteraction of the turbulent and radiative fluxes. To reproduce the strong inversion, it wasnecessary to use vertical and horizontal resolutions higher than those applied in most regional andlarge-scale atmospheric models.     

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.