Kinetics and Mechanism of Trithionate and Tetrathionate Oxidation at Low pH by Hydroxyl Radicals

The oxidation kinetics of trithionate (S₃O₆^2- ) and tetrathionate (S₄O ₆ ^2- ) with hydroxyl radicals (OH^*) have been investigated in systems analogous to acid mine drainage (AMD) environments. The discovery of hydroxyl radical (OH^*) formation on pyrite surfaces (Borda et al., 2003) suggests hydroxyl radicals may affect the oxidation kinetics of intermediate sulfur species such as tetrathionate. Cyclic voltammetry experiments in acidic solutions indicate that the reaction of S₄O ₆ ^2- with OH^* goes through an unknown intermediate, tentatively assigned as S₃O ₄ ^n- . An outer-sphere electron transfer mechanism for the reaction of S₄O ₆ ^2- with OH^* to form S₃O ₄ ^n- is proposed based on experimental results. Oxidation rates for trithionate and tetrathionate in the presence of Fenton's reagent (which forms hydroxyl radicals) are too fast to be directly measured using UV-Vis spectrophotometry, electrochemical, or stop-flow spectrophotometry methods. Competitive reaction kinetics within the context of the Haber—Weiss mechanism suggests that the rate constant for the oxidation of trithionate and tetrathionate with OH^* is in excess of 10⁸ M^-1 sec^-1.     

Strontium isotope evolution of Late Permian and Triassic seawater

The ⁸⁷Sr/⁸⁶Sr values based on brachiopods and conodonts define a nearly continuous record for the Late Permian and Triassic intervals. Minor gaps in measurements exist only for the uppermost Brahmanian, lower part of the Upper Olenekian, and Middle Norian, and only sparse data are available for the Late Permian. These 219 measurements include 67 brachiopods and 114 conodont samples from the Tethyan realm as well as 37 brachiopods and one conodont sample from the mid-European Middle Triassic Muschelkalk Sea. The Late Permian/Lower Triassic interval is characterized by a steep 1.3 × 10⁻³ rise, from 0.7070 at the base of the Dzhulfian to 0.7082 in the late Olenekian, a rate of change comparable to that in the Cenozoic. In the mid-Triassic (Anisian and Ladinian), the isotope values fall to 0.7075, followed again by a rise to 0.7081 in the Middle/Late Norian. The ⁸⁷Sr/⁸⁶Sr values decline again in the Late Norian (Sevatian) and Rhaetian to 0.7076.The sharp rise in the ⁸⁷Sr/⁸⁶Sr values during the Late Permian/Early Triassic was coincident with widespread clastic sedimentation. Because of the paucity of tectonic uplifts, the enhanced erosion may have been due to intermittent humid phases, during mainly an arid interval, coupled with the absence of a dense protective land plant cover following the mass extinction during the latest Permian. The apex of the ⁸⁷Sr/⁸⁶Sr curve at the Olenekian/Anisian boundary coincides with cessation of the large-scale clastic sedimentation and also marks the final recovery of land vegetation, as indicated by the renewed onset of coal formation in the Middle Triassic. The rising ⁸⁷Sr/⁸⁶Sr values from the Middle Carnian to the Late Norian coincide with the uplift and erosion of the Cimmeride-Indosinian orogens marking the closure of the Palaeotethys. The subsequent Rhaetian decline that continues into Jurassic (Pliensbachian/Toarcian boundary), on the other hand, coincides with the opening of the Vardar Ocean and its eastern continuation in the Izmir-Ankara Ophiolitic Belt.Samples from the Upper Muschelkalk are more radiogenic than the global trend. This may reflect separation of the basin from the open ocean. Due to strong meteoric influx from a large land mass in the north, the Germanic Basin became increasing brackish up section in the north and east, but because of the high evaporation rates, the salt content was not much reduced in the southern and central basin where a rich, but increasingly endemic, marine fauna survived.     

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     

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.