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.     

Oxygen isotope salt effects at high pressure and high temperature and the calibration of oxygen isotope geothermometers

The influence of NaCl, CaCl₂, and dissolved minerals on the oxygen isotope fractionation in mineral-water systems at high pressure and high temperature was studied experimentally. The salt effects of NaCl (up to 37 molal) and 5-molal CaCl₂ on the oxygen isotope fractionation between quartz and water and between calcite and water were measured at 5 and 15 kbar at temperatures from 300 to 750°C. CaCl₂ has a larger influence than NaCl on the isotopic fractionation between quartz and water. Although NaCl systematically changes the isotopic fractionation between quartz and water, it has no influence on the isotopic fractionation between calcite and water. This difference in the apparent oxygen isotope salt effects of NaCl must relate to the use of different minerals as reference phases. The term oxygen isotope salt effect is expanded here to encompass the effects of dissolved minerals on the fractionations between minerals and aqueous fluids. The oxygen isotope salt effects of dissolved quartz, calcite, and phlogopite at 15 kbar and 750°C were measured in the three-phase systems quartz-calcite-water and phlogopite-calcite-water. Under these conditions, the oxygen isotope salt effects of the three dissolved minerals range from ∼0.7 to 2.1‰. In both three-phase hydrothermal systems, the equilibrium fractionation factors between the pairs of minerals are the same as those obtained by anhydrous direct exchange between each pair of minerals, proving that the use of carbonate as exchange medium provides correct isotopic fractionations for a mineral pair.When the oxygen isotope salt effects of two minerals are different, the use of water as an indirect exchange medium will give erroneous fractionations between the two minerals. The isotope salt effect of a dissolved mineral is also the main reason for the observation that the experimentally calibrated oxygen isotope fractionations between a mineral and water are systematically 1.5 to 2‰ more positive than the results of theoretical calculations. Dissolved minerals greatly affect the isotopic fractionation in mineral-water systems at high pressure and high temperature. If the presence of a solute changes the solubility of a mineral, the real oxygen isotope salt effect of the solute at high pressure and high temperature cannot be correctly derived by using the mineral as reference phase.     

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.     

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.