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.     

Dynamic stochastic estimation of physical variables

A fundamental problem facing the physical sciences today is analysis of natural variations and mapping of spatiotemporal processes. Detailed maps describing the space/time distribution of groundwater contaminants, atmospheric pollutant deposition processes, rainfall intensity variables, external intermittency functions, etc. are tools whose importance in practical applications cannot be overestimated. Such maps are valuable inputs for numerous applications including, for example, solute transport, storm modeling, turbulent-nonturbulent flow characterization, weather prediction, and human exposure to hazardous substances. The approach considered here uses the spatiotemporal random field theory to study natural space/time variations and derive dynamic stochastic estimates of physical variables. The random field model is constructed in a space/time continuum that explicitly involves both spatial and temporal aspects and provides a rigorous representation of spatiotemporal variabilities and uncertainties. This has considerable advantages as regards analytical investigations of natural processes. The model is used to study natural space/time variations of springwater calcium ion data from the Dyle River catchment area, Belgium. This dataset is characterized by a spatially nonhomogeneous and temporally nonstationary variability that is quantified by random field parameters, such as orders of space/time continuity and random field increments. A rich class of covariance models is determined from the properties of the random field increments. The analysis leads to maps of continuity orders and covariances reflecting space/time calcium ion correlations and trends. Calcium ion estimates and the associated statistical errors are calculated at unmeasured locations/instants over the Dyle region using a space/time kriging algorithm. In practice, the interpretation of the results of the dynamic stochastic analysis should take into consideration the scale effects.     

Porewater pressure increases in soil and rock from underground chemical and nuclear explosions

A review and analysis of chemical and nuclear explosive-induced porewater pressure increases and induced rise in groundwater table elevations (groundwater mounding) is presented. Our analysis indicates that residual pore pressure increases and groundwater mounding can be induced by underground chemical and nuclear explosions to scaled distances of 879 m/(kt)^1/3. This relationship is linear over seven orders of magnitude of explosive energy ranging from a 0.01 kg chemical explosion to a 100 kt nuclear explosion and is valid for a wide variety of saturated geological profiles. Underground chemical explosions, and probably underground nuclear explosions have the potential to induce liquefaction of water-saturated soils to scaled distances of about 260 m/(kt)^1/3.     

Upper Mississippi embayment shallow seismic velocities measured in situ

Vertical seismic compressional- and shear-wave (P-and S-wave) profiles were collected from three shallow boreholes in sediment of the upper Mississippi embayment. The site of the 60-m hole at Shelby Forest, Tennessee, is on bluffs forming the eastern edge of the Mississippi alluvial plain. The bluffs are composed of Pleistocene loess, Pliocene-Pleistocene alluvial clay and sand deposits, and Tertiary deltaic-marine sediment. The 36-m hole at Marked Tree, Arkansas, and the 27-m hole at Risco, Missouri, are in Holocene Mississippi river floodplain sand, silt, and gravel deposits. At each site, impulsive P- and S-waves were generated by man-made sources at the surface while a three-component geophone was locked downhole at 0.91-m intervals.

Consistent with their very similar geology, the two floodplain locations have nearly identical S-wave velocity (V_S) profiles. The lowest V_S values are about 130 m s⁻¹, and the highest values are about 300 m s⁻¹ at these sites. The shear-wave velocity profile at Shelby Forest is very similar within the Pleistocene loess (12 m thick); in deeper, older material, V_S exceeds 400 m s⁻¹.

At Marked Tree, and at Risco, the compressional-wave velocity (V_P) values above the water table are as low as about 230 m s⁻¹, and rise to about 1.9 km s⁻¹ below the water table. At Shelby Forest, V_P values in the unsaturated loess are as low as 302 m s⁻¹. V_P values below the water table are about 1.8 km s⁻¹. For the two floodplain sites, the V_P/V_S ratio increases rapidly across the water table depth. For the Shelby Forest site, the largest increase in the V_P/V_S ratio occurs at 20-m depth, the boundary between the Pliocene-Pleistocene clay and sand deposits and the Eocene shallow-marine clay and silt deposits.

Until recently, seismic velocity data for the embayment basin came from eartquake studies, crustal-scale seismic refraction and reflection profiles, sonic logs, and from analysis of dispersed earthquake surface waves. Since 1991, seismic data for shallow sediment obtained from reflection, refraction, crosshole and downhole techniques have been obtained for sites at the northern end of the embayment basin. The present borehole data, however, are measured from sites representative of large areas in the Mississippi embayment. Therefore, they fill a gap in information needed for modeling the response of the embayment to destructive seismic shaking.     

Lake Koronia, Greece: Shift from autotrophy to heterotrophy with cultural eutrophication and progressive water-level reduction

Lake Koronia, a Ramsar site, is shallow, polymictic, hypertrophic and until recently was aerially the fourth largest lake in Greece. Although exceeding 5 m in the past, lake depth has declined progressively from 3.8 m in 1980 to < 1 m in 1997, reducing surface area and water volume by 50% and 80%, respectively. Specific conductivityincreased from 1300 μS cm⁻¹ in 1977 to >6000 μS cm⁻¹ in 1991. Increased phosphate concentrations from the late 1970's (8–45 μg L⁻¹) to the late 1990's (100–1000 μg L⁻¹) document that the previously eutrophic system with a limited littoral zone switched to hypertrophy dominated by massive cyanobacteria blooms. Oxygen saturation of the water column increased progressively from about 80% in 1983 to full saturation about 1993, after which it decreased progressively to only 20% saturation in 1997. In spite of cyanobacteria dominance, community metabolism of the lake switched from progressively increasing autotrophy to rapidly advancing heterotrophy associated with progressive water-level reduction leading to fish extirpation in the lake.     

Torngat ultramafic lamprophyres and their relation to the North Atlantic Alkaline Province

Geological mapping and diamond exploration in northern Quebec and Labrador has revealed an undeformed ultramafic dyke swarm in the northern Torngat Mountains. The dyke rocks are dominated by an olivine-phlogopite mineralogy and contain varying amounts of primary carbonate. Their mineralogy, mineral compositional trends and the presence of typomorphic minerals (e.g. kimzeyitic garnet), indicate that these dykes comprise an ultramafic lamprophyre suite grading into carbonatite. Recognized rock varieties are aillikite, mela-aillikite and subordinate carbonatite. Carbonatite and aillikite have in common high carbonate content and a lack of clinopyroxene. In contrast, mela-aillikites are richer in mafic silicate minerals, in particular clinopyroxene and amphibole, and contain only small amounts of primary carbonate. The modal mineralogy and textures of the dyke varieties are gradational, indicating that they represent end-members in a compositional continuum.

The Torngat ultramafic lamprophyres are characterized by high but variable MgO (10–25 wt.%), CaO (5–20 wt.%), TiO₂ (3–10 wt.%) and K₂O (1–4 wt.%), but low SiO₂ (22–37 wt.%) and Al₂O₃ (2–6 wt.%). Higher SiO₂, Al₂O₃, Na₂O and lower CO₂ content distinguish the mela-aillikites from the aillikites. Whereas the bulk rock major and trace element concentrations of the aillikites and mela-aillikites overlap, there is no fractional crystallization relation between them. The major and trace element characteristics imply related parental magmas, with minor olivine and Cr-spinel fractionation accounting for intra-group variation.

The Torngat ultramafic lamprophyres have a Neoproterozoic age and are spatially and compositionally closely related with the Neoproterozoic ultramafic lamprophyres from central West Greenland. Ultramafic potassic-to-carbonatitic magmatism occurred in both eastern Laurentia and western Baltica during the Late Neoproterozoic. It can be inferred from the emplacement ages of the alkaline complexes and timing of Late Proterozoic processes in the North Atlantic region that this volatile-rich, deep-seated igneous activity was a distal effect of the breakup of Rodinia. This occurred during and/or after the rift-to-drift transition that led to the opening of the Iapetus Ocean.