Mechanistic studies on the degradation of gasoline oxygenates by advanced oxidation technologies and the reaction of 4-methyl-1,2,4-triazoline-3,5-dione with tetracyclopropylethylene

Gasoline oxygenates (MTBE, methyl tert-butyl ether; DIPE, di-isopropyl ether; ETBE, ethyl tert-butyl ether; TAME, tert-amyl ether) are added to gasoline to boost octane and enhance combustion. The combination of large scale use, high water solubility and only minor biodegradability has now resulted in a significant gasoline oxygenate contamination occurring in surface, ground, and drinking water systems. Combination of hydroxyl radical formation and the pyrolytic environment generated by ultrasonic irradiation (665 kHz) leads to the rapid degradation of MTBE and other gasoline oxygenates in aqueous media. ^ The presence of oxygen promotes the degradation processes by rapid reaction with carbon centered radicals indicating radical processes involving O 2 are significant pathways. A number of the oxidation products were identified. The formation of products (alcohols, ketones, aldehydes, esters, peroxides, etc) could be rationalized by mechanisms which involve hydrogen abstraction by OH radical and/or pyrolysis to form carboncentered radicals which react with oxygen and follow standard oxidation chain processes. ^ The reactions of N-substituted R-triazolinediones (RTAD; R = CH 3 or phenyl) have attracted considerable interest because they exhibit a number of unusual mechanistic characteristics that are analogous to the reactions of singlet oxygen (1O2) and offer an easy way to provide C-N bond(s) formation. The reactions of triazolinedione with olefins have been widely studied and aziridinium imides are generally accepted to be the reactive intermediates. ^ We observed the rapid formation of an unusual intermediate upon mixing tetracyclopropylethylene with 4-methyl-1,2,4-triazoline-3,5-dione in CDCl 3. Detailed characterization by NMR (proton, 13C, 2-D NMRs) indicates the intermediate is 5,5,6,6-tetracyclopropyl-3-methyl-5,6-dihydro-oxazolo[3,2- b][1,2,4]-triazolium-2-olate. Such products are extremely rare and have not been studied. Upon warming the intermediate is converted to 2 + 2 diazetidine (major) and ene product (minor). ^ To further explore the kinetics and dynamics of the reaction activation energies were obtained using Arrhenius plots. Activation energies for the formation of the intermediate from reactants, and 2+2 adduct from the intermediate were determined as 7.48 kcal moll and 19.8 kcal mol−1 with their pre-exponential values of 2.24 × 105 dm 3 mol−1 sec−1 and 2.75 × 108 sec−1, respectively, meaning net slow reactions because of low pre-exponential values caused by steric hindrance. ^

Marl Prairie/Slough Gradients; Patterns and Trends in Shark Slough and Adjacent Marl Prairies (CERP monitoring activity 3.1.3.5), First Annual Report (2005)

The work on CERP monitoring item 3.1.3.5 (Marl prairie/slough gradients) is being conducted by Florida International University (Dr Michael Ross, Project Leader), with Everglades National Park (Dr. Craig Smith) providing administrative support and technical consultation. As of January 2006 the funds transferred by ACOE to ENP, and subsequently to FIU, have been entirely expended or encumbered in salaries or wages. The project work for 2005 started rather late in the fiscal year, but ultimately accomplished the Year 1 goals of securing a permit to conduct the research in Everglades National Park, finalizing a detailed scope of work, and sampling marsh sites which are most easily accessed during the wet season. 46 plots were sampled in detail, and a preliminary vegetation classification distinguished three groups among these sites (Sawgrass marsh, sawgrass and other, and slough) which may be arranged roughly along a hydrologic gradient from least to most persistently inundated . We also made coarser observations of vegetation type at 5-m intervals along 2 transects totaling ~ 5 km. When these data were compared with similar observations made in 1998-99, it appeared that vegetation in the western portion of Northeast Shark Slough (immediately east of the L-67 extension) had shifted toward a more hydric type during the last 6 years, while vegetation further east was unchanged in this respect. Because this classification and trend analysis is based on a small fraction of the data set that will be available after the first cycle of sampling (3 years from now), the results should not be interpreted too expansively. However, they do demonstrate the potential for gaining a more comprehensive view of marsh vegetation structure and dynamics in the Everglades, and will provide a sound basis for adaptive management.

Development of face recognition: Infancy to early childhood

Perception and recognition of faces are fundamental cognitive abilities that form a basis for our social interactions. Research has investigated face perception using a variety of methodologies across the lifespan. Habituation, novelty preference, and visual paired comparison paradigms are typically used to investigate face perception in young infants. Storybook recognition tasks and eyewitness lineup paradigms are generally used to investigate face perception in young children. These methodologies have introduced systematic differences including the use of linguistic information for children but not infants, greater memory load for children than infants, and longer exposure times to faces for infants than for older children, making comparisons across age difficult. Thus, research investigating infant and child perception of faces using common methods, measures, and stimuli is needed to better understand how face perception develops. According to predictions of the Intersensory Redundancy Hypothesis (IRH; Bahrick & Lickliter, 2000, 2002), in early development, perception of faces is enhanced in unimodal visual (i.e., silent dynamic face) rather than bimodal audiovisual (i.e., dynamic face with synchronous speech) stimulation. The current study investigated the development of face recognition across children of three ages: 5 – 6 months, 18 – 24 months, and 3.5 – 4 years, using the novelty preference paradigm and the same stimuli for all age groups. It also assessed the role of modality (unimodal visual versus bimodal audiovisual) and memory load (low versus high) on face recognition. It was hypothesized that face recognition would improve across age and would be enhanced in unimodal visual stimulation with a low memory load. Results demonstrated a developmental trend (F(2, 90) = 5.00, p = 0.009) with older children showing significantly better recognition of faces than younger children. In contrast to predictions, no differences were found as a function of modality of presentation (bimodal audiovisual versus unimodal visual) or memory load (low versus high). This study was the first to demonstrate a developmental improvement in face recognition from infancy through childhood using common methods, measures and stimuli consistent across age.

Diversity Patterns of Amphibians in Lowland Amazonian Forests in Southeastern Peru

Biological diversity is threatened worldwide and it is a priority to generate more information that can be used both for understanding ecological processes and determining conservation strategies. For my dissertation, I focused on amphibian diversity patterns in lowland rainforests of southwestern Amazonia to evaluate the importance of habitat heterogeneity in the region. My main purpose was to test the hypothesis that amphibian communities in different forest types differ in species richness, composition, and abundance. I used standardized visual encounter surveys to quantify the species composition and abundance of amphibians at four sites, each containing four forest types (floodplain, terra firme, bamboo, and palm swamp). I used leaf-litter plots to evaluate the effect of soil and leaf-litter characteristics on species richness and abundance of leaf-litter frogs. I intensively sampled at one site and then sampled three other sites (distance among sites varied 3.5-105 km) to evaluate whether the patterns observed at one site were similar elsewhere. I also updated the information on threatened and potentially threatened amphibians in Peru and my study region. I found that no species appears to have experienced population declines in southeastern Peru, suggesting that the region still contains the original species pool. My results support the hypothesis that amphibian communities differ across forest types and that patterns observed at the local scale (one site) are similar at the regional scale (four sites). My data also indicate that there is no correlation between species composition and geographic distance among sites. Instead, an important proportion of the gamma diversity is represented by habitat-related beta diversity. My leaf-litter plot data showed that part of the variation in the leaf-litter community structure is explained by soil and litter characteristics. I found that soil total phosphorus and, to a lesser extent, humidity, leaf-litter mass, and pH is linked to species presence/absence and abundance. My study provides the first standardized, quantitative comparison of amphibian community structure across four major forest types in southwestern Amazonia and highlights the fact that forest types are complementary and necessary for maintaining high species richness in the region.