Natural Gradient Tracer Test to Evaluate Natural Attenuation of MTBE Under Anaerobic Conditions

A natural gradient tracer test using perdeuterated MTBE was conducted in an anaerobic aquifer to determine the relative importance of dispersion and degradation in reducing MTBE concentrations in ground water. Preliminary ground water chemistry and hydraulic conductivity data were used to place the tracer within an existing dissolved MTBE plume at Port Hueneme, California. Following one year of transport, the tracer plume was characterized in detail.
Longitudinal dispersion was identified as the dominant mechanism for lowering the perdeuterated MTBE concentrations. The method of moments was used to determine the longitudinal and lateral dispersion coefficients (0.85 m²/day and 0.08 m²/day, respectively). A mass-balance analysis, carried out after one year of transport, accounted for 110% of the injected mass and indicated that no significant mass loss occurred. The plume structure created by zones of higher and lower hydraulic conductivity at the site was complex, consisting of several localized areas of high tracer concentration in a lower concentration plume. This is important because the aquifer has generally been characterized as exhibiting fairly minor heterogeneity. In addition, the tracer plume followed a curved flowpath that deviated from the more macroscopic direction of ground water flow inferred from local ground water elevation measurements and the behavior of the existing plume. Understanding the mass balance, plume structure, curvature of the tracer plume, and consequently natural attenuation behavior required the detailed sampling approach employed in this study. These data imply that a detailed understanding of site hydrogeology and an extensive sampling network may be critical for the correct interpretation of monitored natural attenuation of MTBE.     

Neoarchaean magmatism and metamorphism of the western granulites in the central domain of the Mozambique belt, Tanzania: U–Pb shrimp geochronology and PT estimates

U–Pb sensitive high resolution ion microprobe (SHRIMP) dating of zircons from charnockitic and garnet–biotite gneisses from the central portion of the Mozambique belt, central Tanzania indicate that the protolith granitoids were emplaced in a late Archaean, ca. 2.7 Ga, magmatic event. These ages are similar to other U–Pb and Pb–Pb ages obtained for other gneisses in this part of the belt. Zircon xenocrysts dated between 2.8 and 3.0 Ga indicate the presence of an older basement. Major and trace element geochemistry of these high-grade gneisses suggests that the granitoid protoliths may have formed in an active continental margin environment. Metamorphic zircon rims and multifaceted metamorphic zircons are dated at ca. 2.6 Ga indicating that these rocks were metamorphosed some 50–100 my after their emplacement. Pressure and temperature estimates on the charnockitic and garnet–biotite gneisses were obscured by post-peak metamorphic compositional homogenisation; however, these estimates combined with mineral textures suggest that these rocks underwent isobaric cooling to 800–850 °C at 12–14 kbar. It is considered likely that the granulite facies mineral assemblage developed during the ca. 2.6 Ga event, but it must be considered that it might instead represent a pervasive Neoproterozoic, Pan African, granulite facies overprint, similar to the ubiquitous eastern granulites further to the east.     

The postglacial history of three Picea species in New England, USA

Given the difficulty of separating the three Picea species—P. glauca, P. mariana, and P. rubens (white, black, and red spruce)—in the pollen record, little is known about their unique histories in eastern North America following deglaciation. Here we report the first use of a classification tree analysis (CART) to distinguish pollen grains of these species. It was successfully applied to fossil pollen from eight sites in Maine and one in Massachusetts. We focused on the late glacial/early Holocene (14,000 to 8000 cal yr B.P.) and the late Holocene (1400 cal yr B.P. to present)—the two key periods since deglaciation when Picea has been abundant in the region. The result shows a shift from a Picea forest of P. glauca and P. mariana in the late glacial to a forest of P. rubens and P. mariana in the late Holocene. The small number of P. rubens grains identified from the late glacial/early Holocene samples (<5%) suggests that that species was either absent or rare at most of the sites. The occurrence and distribution of the three species do not reveal any geographic or temporal trend during late glacial time, but the data suggest that they were distributed in local patches on the landscape. The results of this study indicate that the recent population expansion of Picea (1000 to 500 cal yr B.P.) was likely the first time since deglaciation that P. rubens was abundant in the region.     

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.