Equilibrium H/H fractionations in organic molecules: I. Experimental calibration of ab initio calculations

Carbon-bound hydrogen in sedimentary organic matter can undergo exchange over geologic timescales, altering its isotopic composition. Studies investigating the natural abundance distribution of ¹H and ²H in such molecules must account for this exchange, which in turn requires quantitative knowledge regarding the endpoint of exchange, i.e., the equilibrium isotopic fractionation factor (α_eq). To date, relevant data have been lacking for molecules larger than methane. Here we describe an experimental method to measure α_eq for C-bound H positions adjacent to carbonyl group (H_α) in ketones. H at these positions equilibrates on a timescale of days as a result of keto-enol tautomerism, allowing equilibrium ²H/¹H distributions to be indirectly measured. Molecular vibrations for the same ketone molecules are then computed using Density Functional Theory at the B3LYP/6-311G** level and used to calculate α_eq values for H_α. Comparison of experimental and computational results for six different straight and branched ketones yields a temperature-dependent linear calibration curve with slope = 1.081−0.00376T and intercept = 8.404−0.387T, where T is temperature in degrees Celsius. Since the dominant systematic error in the calculation (omission of anharmonicity) is of the same size for ketones and C-bound H in most other linear compounds, we propose that this calibration can be applied to analogous calculations for a wide variety of organic molecules with linear carbon skeletons for temperatures below 100 °C. In a companion paper (Wang et al., 2009) we use this new calibration dataset to calculate the temperature-dependent equilibrium isotopic fractionation factors for a range of linear hydrocarbons, alcohols, ethers, ketones, esters and acids.     

Global-scale near infrared variability on Mars: Analysis of 2003 Mars opposition observations from HST/NICMOS

We have used HST/NICMOS to observe approximately 57% of the martian surface in 7 narrow band filters (0.97, 1.08, 1.13, 1.66, 1.90, 2.12, and 2.15 μm) during the 2003 opposition (Ls∼250°) and at a resolution of ∼12 km/pixel. Principal components analysis (PCA) of the dataset has identified regional variability on scales of hundreds of kilometers associated with differences in the near-infrared spectrum of Mars. Visualization of the data in principal component space has allowed us to identify spectral endmembers associated with the south polar cap, the classic bright terrains, northern Syrtis Major, southern Syrtis Major, Tyrrhena Terra, and Acidalia Planitia. The two Syrtis Major endmembers and the Tyrrhena Terra endmember differ in their absolute reflectivities but have the same spectral shape at wavelengths longer than 1.6 μm. The Acidalia endmember is distinct from the other dark terrain endmembers because it exhibits a strong negative near-IR spectral slope. Comparisons with spectral library measurements cannot provide unique constraints on the surface mineralogy for these sparsely-sampled spectral data. However, the observed spectral variations between Tyrrhena Terra and Syrtis Major are consistent with variations in iron- and sulfur-bearing minerals, and the relatively strong negative spectral slope in the spectrum of Acidalia is consistent with the presence of hydrated alteration products. Additional comparison with previous NICMOS observations taken in 1997 at Ls∼150° indicate that the average near-IR spectral slope of the Acidalia region is more negative during the late northern fall than during the mid northern summer. This may indicate seasonal variations in the presence of either adsorbed water or re-hydrated minerals in the regolith of Acidalia.     

Climate, weather, and north polar observations from the Mars Reconnaissance Orbiter Mars Color Imager

The Mars Reconnaissance Orbiter observes Mars from a nearly circular, polar orbit. From this vantage point, the Mars Color Imager extends the ∼5 Mars years record of Mars Global Surveyor global, visible-wavelength multi-color observations of meteorological events and adds measurements at three additional visible and two ultraviolet wavelengths. Observations of the global distribution of ozone (which anti-correlates with water vapor) and water ice and dust clouds allow tracking of atmospheric circulation. Regional and local observations emphasize smaller scale atmospheric dynamics, especially those related to dust lifting and subsequent motion. Polar observations detail variations related to the polar heat budget, including changes in polar frosts and ices, and storms generated at high thermal contrast boundaries.     

Spatial and Temporal Patterns Associated with Permitted Tree Removal in Austin,Texas, 2002–2011

A wide-ranging set of physical, urban, demographic, socioeconomic, and policy characteristics determines the spatial distribution of urban forests. Information on the characteristics surrounding tree removals on both public and private properties has received less attention in the literature. The purpose of this research was to analyze the spatiotemporal trends and geographic patterns of tree removals in Austin, Texas, between 2002 and 2011 in an effort to understand how site-specific characteristics influence urban tree removal and affect the overall distribution of Austin's urban forest. We examined permitted tree removals using a geographic information system (GIS) as well as spatial and statistical analyses. Specifically, we evaluated the degree to which variables related to various physical, urban, and socioeconomic conditions predicted tree removals. The results indicate that permitted tree removals and their associated characteristics in Austin have varied over the ten-year study period. Permitted tree removals increased over the study period and took place in the urban core and along the urban periphery. Permitted tree removals were more likely to be undertaken by college graduates and owner-occupants and to occur in more densely populated areas, closer to major streets, and on properties with older structures. The results of this research provide urban forest professionals with information on the location and intensity of permitted tree removals and the significant characteristics driving urban tree loss.     

Integrating Stalagmite, Vertebrate, and Pollen Sequences to Investigate Holocene Vegetation and Climate Change in the Southern Midwestern United States

Speleothem carbon and oxygen isotopic records from Onondaga Cave, south-central Missouri, and Beckham Creek Cave, north-central Arkansas, are compared with the Cupola Pond and Oldfield Swamp pollen series from southeastern Missouri and the Rodgers Shelter and Modoc Shelter vertebrate biostratigraphic sequences from central Missouri and southwestern Illinois. Similar, and roughly contemporaneous, shifts between deciduous forest and steppe indicators throughout the Holocene are revealed in each database. These independent proxies record steppe conditions between approximately 9000 and 1500 cal yr B.P. A shift toward lighter speleothem carbon may reflect a change from warm and dry to cool and dry conditions between 4500 and 3000 yr B.P. The sensitive response of speleothem δ¹³C to changes in vegetation emphasizes their importance as paleoclimate records in an area containing few other millenial-scale climate proxies.     

Recent shifts in coastline change and shoreline stabilization linked to storm climate change

Since cuspate coastlines are especially sensitive to changes in wave climate, they serve as potential indicators of initial responses to changing wave conditions. Previous work demonstrates that Cape Hatteras and Cape Lookout, North Carolina, which are largely unaffected by shoreline stabilization efforts, have become increasingly asymmetric over the past 30 years, consistent with model predictions for coastline response to increases in Atlantic Ocean summer wave heights and resulting changes in the distribution of wave‐approach angles. Historic and recent shoreline change observations for Cape Fear, North Carolina, and model simulations of coastline response to an increasingly asymmetric wave climate in the presence of beach nourishment, produce comparable differences in shoreline change rates in response to changes in wave climate. Results suggest that the effect of beach nourishment is to compensate for – and therefore to mask – natural responses to wave climate change that might otherwise be discernible in patterns of shoreline change alone. Therefore, this case study suggests that the effects of wave climate change on human‐modified coastlines may be detectable in the spatial and temporal patterns of shoreline stabilization activities. Similar analyses of cuspate features in areas where the change in wave climate is less pronounced (i.e. Fishing Point, Maryland/Virginia) and where local geology appears to exert control on coastline shape (i.e. Cape Canaveral, Florida), suggest that changes in shoreline configuration that may be arising from shifting wave climate are currently limited to sandy wave‐dominated coastlines where the change in wave climate has been most pronounced. However, if hurricane‐generated wave heights continue to increase, large‐scale shifts in patterns of erosion and accretion will likely extend beyond sensitive cuspate features as the larger‐scale coastline shape comes into equilibrium with changing wave conditions. Copyright © 2014 John Wiley & Sons, Ltd.     

Computerized detection of seamounts from Seasat type geodetic data

Abstract

Geoid heights and vertical deflections derived from satellite radar altimetry contain characteristic signals that may be reproduced and explained by simple models for seamount gravitation acting on the sea surface. Computer algorithms capable of automatic operation and able to detect, approximately locate, and estimate parameters constraining the shape of actual sea‐mounts were written and tested. The computer program which utilized a digital high‐pass filter combined with a roughness sensor was effective in separating the seamount produced geoid undulation/vertical deflection pattern from the remaining data track features, simultaneously detecting and locating along the track such signals. Tests of the algorithm on several SEASAT passes over known bathymetry produced mixed results. Meaningful shape constraints were obtained by matching the geoid anomaly calculated from the seamount model to the actual mean sea level pattern for some seamounts. Results for other seamounts were poor and possible reasons for the failure are discussed. It is concluded that a computerized seamount detection program for radar altimetry data is feasible, but it will have to be more complex than the present one for fully successful operation.     

Book review

Geotechnical Aspects of Coastal and Offshore Structures. Edited by Yudhair and A. S. Balasubramaniam. Proceedings of the Symposium on Geotechnical Aspects of Coastal and Offshore Structures, Bangkok, December 14–18,1981. Rotterdam: A. A. Balkema, 1983. 280 pp. $40.00.

The Seaside Naturalist: A Guide to Nature Study at the Seashore. Written and illustrated by D. A. Coulombe. Englewood Cliffs, N.J.: Prentice‐Hall, Inc., 1984. 246 pp. $12.95.

Ichnology, Trace Fossils in Sedimentology and Stratigraphy. By A. A. Ekdale, R. G. Bromley, and S. G. Pemberton. Society of Economic Paleontologists and Mineralogists, Short Course No. 15. Tulsa, Okla.: S.E.P.M., 1984. 317 pp. S.E.P.M. members, $16.00; non‐members, $20.00.     

PEDOGENESIS IN LATE PREHISTORIC INDIAN MOUNDS,UPPER MISSISSIPPI VALLEY

Inceptisols are developed on silt loam, loam, and sandy loam Indian mounds at the Keller Mound Group and Bluff Top Mound in northeastern Iowa. The mounds date to the Allamakee Phase of the Late Woodland Period (ca. 1650–1250 B.P.) and are built with fill obtained from the A, E, and upper B horizons of pre-existing soils (Alfisols). Differences in the morphologic and chemical characteristics of soils on different mounds are attributed to textural differences of the mounds' fill. Coarse-textured mound fill is pedogenically altered at a faster rate than fine-textured fill, but total carbon percentage of the A horizon attains a steady state faster in fine-textured mound fill. Total phosphorus content is used to determine from which horizons of pre-existing soils the specific layers of mound fill originated. Rates and pathways of pedogenesis in mound fill may not provide good analogues for the early stages of soil development in materials that have not undergone previous weathering and subsequent modification by humans. Nevertheless, mound soils are useful benchmarks for some pedologic studies since they provide time lines for evaluating minimum rates for development of argillic and albic horizons, as well as attainment of the Alfisol order.