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.     

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.     

The Darwin Rise demise: the western Pacific guyot heights trace the trans-Pacific Mendocino fracture zone

The Darwin Rise has been proposed so many times and in so many forms and places that the time has come to make a more comprehensive examination of the region. Lying on the NW Pacific Plate between the Geisha Guyots, the Mid-Pacific Mountains, the equator, and the trenches, the region is roughly bounded by magnetic anomaly M20 (147 Ma). It was subjected to a massive outpouring of lava about 105 to 120 Ma, which created the guyots and seamounts in that region. Guyots are excellent tools for studying events of long ago because they eroded in the same lowstand in the Cretaceous and guyot relief, therefore, is a surrogate for paleo-sealevel. The relief is derived by subtracting the break depth of the summit plateau of a guyot from the regional depth. Guyot relief would necessarily be less in the center than to the periphery if the feature formed on a pre-existing rise, as has been postulated. The existence of a paleo-Darwin Rise would give concentric contours for the region in question. Of the sixty guyots used in this study, thirty-seven of these guyots were surveyed using SASS multibeam in the Marcus-Wake seamount group. Twenty-three guyots were surveyed using random track single-beam sonar surveys. An entirely different scenario is shown. Data revealed a major fracture passing through the area coevally or after the guyots formed. Because the depths to the summit are not the same now, vertical tectonics occurred after subaerial erosion. This means the fracture formed during and after the erosion (roughly 105 Ma) and influenced the normal sequence of events in guyot formation. Depending on how one deciphers trends through the Hess Rise morass, SASS bathymetry shows a continuation of the Surveyor/Mendocino fracture zone swarm inside the M20 region to the NE of these data. The fracture swarm continues to the western Pacific trench system. Based on this information, if the Darwin Rise ever existed, it had to have done so elsewhere.     

Remote sensing techniques for landslide studies and hazard zonation in Europe

An inventory is presented of researches concerning the use of remote sensing for landslide studies and hazard zonation as mainly carried out in the countries belonging to the European Community. An overview is given of the applicability of remote sensing in the following phases of landslide studies:

1. (1) Detection and classification of landslides. Special emphasis is given to the types of imagery required at different scales of analysis.

2. (2) Monitoring the activity of existing landslides using G.P.S., photogrammetrical techniques and radar interferometry.

3. (3) Analysis and prediction in space and time of slope failures. The different factors required in a landslide hazard study are evaluated, and the optimum remote sensing imagery for obtaining each of these factors is indicated.

Examples are given of research work carried out in these three phases from EC countries. Finally an evaluation is given of the aspects of uncertainty associated with the use of remote sensing data, and conclusions are given as to the incorporation of remote sensing techniques within the overall framework of techniques.     

Contrasting stable isotope behavior between calcite and dolomite marbles,Lone Mountain,Nevada

 Late Proterozoic to Cambrian carbonate rocks from Lone Mountain, west central Nevada, record multiple post-depositional events including: (1) diagenesis, (2) Mesozoic regional metamorphism, (3) Late Cretaceous contact metamorphism, related to the emplacement of the Lone Mountain granitic pluton and (4) Tertiary hydrothermal alteration associated with extension, uplift and intrusion of silicic porphyry and lamprophyre dikes. Essentially pure calcite and dolomite marbles have stable isotopic compositions that can be divided into two groups, one with positive δ¹³C values from+3.1 to +1.4 ‰ (PDB) and high δ¹⁸O values from +21.5 to +15.8 ‰ (SMOW), and the other with negative δ¹³C values from –3.3 to –3.6‰ and low δ¹⁸O values from +16.9 to +11.1‰. Marbles also contain minor amounts of quartz, muscovite and phlogopite. Brown and blue luminescent, clear, smooth textured quartz grains from orange luminescent calcite marbles have high δ¹⁸O values from +23.9 to +18.1‰, while brown luminescent, opaque, rough textured quartz grains from red luminescent dolomite marbles typically have low δ¹⁸O values from +2.0 to +9.3‰. The δ¹⁸O values of muscovite and phlogopite from marbles are typical of micas in metamorphic rocks, with values between +10.4 and +14.4‰, whereas mica δD values are very depleted, varying from −102 to −156‰. No significant lowering of the δ¹⁸O values of Lone Mountain carbonates is inferred to have occurred during metamorphism as a result of devolatilization reactions because of the essentially pure nature of the marbles. Bright luminescence along the edges of fractures, quartz cements and quartz overgrowths in dolomite marbles, low δD values of micas, negative δ¹³C values and low δ¹⁸O values of calcite and dolomite, and depleted δ¹⁸O values of quartz from dolomite marbles all indicate that meteoric fluids interacted with Lone Mountain marbles during the Tertiary. Partial oxygen isotopic exchange between calcite and low ¹⁸O meteoric fluids lowered the δ¹⁸O values of calcite, resulting in uniform quartz-calcite fractionations that define an apparent pseudoisotherm. These quartz-calcite fractionations significantly underestimate both the temperature of metamorphism and the temperature of post-metamorphic alteration. Partial oxygen isotopic exchange between quartz and meteoric fluids also resulted in ¹⁸O depletion of quartz from dolomite marbles. This partial exchange was facilitated by an increase in the surface area of the quartz as a result of its dissolution by meteoric fluids. The negative δ¹³C values in carbonates result from the oxidation of organic material by meteoric fluids following metamorphism. Stable isotopic data from Lone Mountain marbles are consistent with the extensive circulation of meteoric hydrothermal fluids throughout western Nevada in Tertiary time. Received: 1 February 1994/Accepted: 12 September 1995