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.     

Atmospheric deposition of Be and Be in New Zealand rain (1996-98)

Beryllium isotope concentrations were determined in monthly rainfall collections at three sites across New Zealand (36 to 45° S), from October 1996 to November 1998. At the northern sites of Leigh (near Auckland) and Gracefield (near Wellington), ⁷Be and ¹⁰Be concentrations are relatively constant at 1.2 to 1.4 × 10⁷ atoms kg⁻¹ rain and 2.1 to 2.6 × 10⁷ atoms kg⁻¹ rain, respectively. These concentrations correspond to annual flux rates of ∼15 and ∼27 × 10⁹ atoms m⁻² y⁻¹, respectively. At the southern site of Dunedin, concentrations are similar to those at the northern sites, but flux rates are significantly lower at ∼ 9 and ∼19 × 10⁹ atoms m⁻² y⁻¹, respectively, because of lower average rainfall east of the Southern Alps mountain range. These results are broadly similar to those reported by Brown et al. (1989) and Knies et al. (1994) for rain from midlatitude sites in the USA sampled from 1986 to 1994. Mean ⁷Be/¹⁰Be ratios for New Zealand (0.47 to 0.61) are, however, significantly lower than for the USA (0.69 to 0.78), due in part to the addition of ¹⁰Be from re-suspended dust. Subtraction of the dust component increases the New Zealand ⁷Be/¹⁰Be ratios to 0.70 (Leigh), 0.65 (Gracefield) and 0.50 (Dunedin). The adjusted results provide evidence for transfer of older stratospheric air to the troposphere in late-spring-summer, an effect which is strongest in the north. The overall reduction of ⁷Be/¹⁰Be from north to south implies an increase in residence time from ∼ 80 to ∼100 d for Be isotopes in the atmosphere above New Zealand.     

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.     

Recent Rapid Regional Climate Warming on the Antarctic Peninsula

The Intergovernmental Panel on Climate Change (IPCC) confirmed that mean global warming was 0.6 ± 0.2 °C during the 20th century and cited anthropogenic increases in greenhouse gases as the likely cause of temperature rise in the last 50 years. But this mean value conceals the substantial complexity of observed climate change, which is seasonally- and diurnally-biased, decadally-variable and geographically patchy. In particular, over the last 50 years three high-latitude areas have undergone recent rapid regional (RRR) warming, which was substantially more rapid than the global mean. However, each RRR warming occupies a different climatic regime and may have an entirely different underlying cause. We discuss the significance of RRR warming in one area, the Antarctic Peninsula. Here warming was much more rapid than in the rest of Antarctica where it was not significantly different to the global mean. We highlight climate proxies that appear to show that RRR warming on the Antarctic Peninsula is unprecedented over the last two millennia, and so unlikely to be a natural mode of variability. So while the station records do not indicate a ubiquitous polar amplification of global warming, the RRR warming on the Antarctic Peninsula might be a regional amplification of such warming. This, however, remains unproven since we cannot yet be sure what mechanism leads to such an amplification. We discuss several possible candidate mechanisms: changing oceanographic or changing atmospheric circulation, or a regional air-sea-ice feedback amplifying greenhouse warming. We can show that atmospheric warming and reduction in sea-ice duration coincide in a small area on the west of the Antarctic Peninsula, but here we cannot yet distinguish cause and effect. Thus for the present we cannot determine which process is the probable cause of RRR warming on the Antarctic Peninsula and until the mechanism initiating and sustaining the RRR warming is understood, and is convincingly reproduced in climate models, we lack a sound basis for predicting climate change in this region over the coming century.     

UV Laser Ablation ICP-MS: Some Applications in the Earth Sciences

This study reports a series of applications of UV laser ablation ICP-MS in the geological sciences. The advantages and disadvantages of the PQ "S" option and the use of nitrogen in the carrier gas are discussed. A general problem common to all ablation techniques is the calibration technique and experiments involving synthetic calibration samples are covered. Zircon geochemistry and geochronology by LA-ICP-MS are discussed and data are presented for REE, Hf and U for a standard zircon (91500) as well as a series of zircons from Zimbabwe. The potential of using Ce and Eu anomalies in petrologic studies is illustrated by zircons from a fractionated gabbroic-granite in the Urals. The potential of the LA-ICP-MS method to utilise standard X-ray fluorescence glass discs is demonstrated as a useful semi-quantitative tool in determining REE patterns. LA-ICP-MS is a powerful tool in the analysis of the platinum group elements (and Re) and some examples are given in the successful application of the technique to partitioning in iron meteorites.     

The glacilacustrine sedimentary environment of Bowser Lake in the northern Coast Mountains of British Columbia, Canada

Bowser Lake, a fiord lake in the northern Coast Mountains of British Columbia, contains a thick Holocene fill consisting mainly of silt and clay varves. These sediments were carried into the lake by proglacial Bowser River which drains a high-energy, heavily glacierized basin. Sedimentation in the lake is controlled by seasonal snow and ice melt, by autumn rainstorms, and by rare, but very large jökulhlaups from glacier-dammed lakes in the upper Bowser River basin which complicate environmental inferences from the sedimentary record. Sediment is dispersed through the deep western part of the lake by energetic turbidity currents. The turbidity currents apparently do not overtop a sill that separates the western basin from much shallower areas to the east. Large amounts of silt and clay are deposited from suspension in the eastern part of the lake, but sediment accumulation rates there are much lower than to the west. Several strong acoustic reflectors punctuate the varved fill in the western basin; these may be thick or relatively coarse beds deposited during jökulhlaups or exceptionally large storms. The contemporary sediment yield to Bowser Lake, estimated from sediments in the lake, is about 360 t km^-2a^-1. This is a relatively high value, but it is less than yields insome other, similar montane basins with extensive snow and ice cover.The most likely explanation for the difference is that large amounts of sediment have been, and continue to be, stored on the Bowser delta andin small proglacial lakes.