Some approaches for location of centroids of quartz grain outlines to increase homology between Fourier amplitude spectra

The ability to test for similarities and differences among families of shapes by closed-form Fourier expansion is greatly enhanced by the concept of homology. Underlying this concept is the assumption that each term of a Fourier series, when compared to the same term in another series, represents the same thing. A method that ensures homology is one which minimizes the centering error, as reflected in the first harmonic term of the Fourier expansion. The problem is to chose a set of edge points derived from a much larger, but variable, number of edge points such that a valid homologous Fourier series can be calculated. Methods are reviewed and criteria given to define a proper solution. An algorithm is presented which takes advantage of the fact that minimization of the error term can be accomplished by minimizing the distance between the origin of the polar coordinate system in the calculation of the Fourier series and the shape centroid. The use of this algorithm has produced higher quality solutions for quartz grain provenance studies.     

Characterization of permineralized kerogen from an Eocene fossil fern

The processes of organic maturation that occur during the permineralization of fossils and the detailed chemistry of the resulting products are incompletely understood. Primary among such processes is the geochemical alteration of biological matter to produce kerogen, such as that which comprises the cell walls of the fossils studied here: essentially unmetamorphosed, Eocene plant axes (specimens of the fossil fern Dennstaedtiopsis aerenchymata cellularly permineralized in cherts of the Clarno Formation of Oregon and the Allenby Formation of British Columbia). The composition and molecular structure of the kerogen that comprises the cell walls of such axes were analyzed using ultraviolet Raman spectroscopy (UV–Raman), solid state ¹³C nuclear magnetic resonance spectroscopy (¹³C NMR) and pyrolysis–gas chromatography–mass spectrometry (py–GC–MS).Cellularly well-preserved fern axes from both geologic units exhibit similar overall molecular structure, being composed primarily of networks of aromatic rings and polyene chains that, unlike more mature kerogens, lack large polycyclic aromatic hydrocarbon (PAH) constituents. The cell walls of the Allenby Formation specimens are, however, less altered than those of the Clarno chert, exhibiting more prevalent oxygen-containing and alkyl functional groups and comprising a greater fraction of rock mass.The study represents the first demonstration of the effectiveness (and limitations) of the combined use of UV–Raman, ¹³C NMR and py–GC–MS for the analysis of the kerogenous cell walls of chert-permineralized vascular plants.     

Scattering properties of planetary regolith analogs

The physics of scattering of electromagnetic waves by media in which the particles are in contact, such as planetary regoliths, has been thought to be relatively well understood when the particles are larger than the wavelength. However, this is not true when the particles are comparable with or smaller than the wavelength. We have measured the scattering parameters of planetary regolith analogs consisting of suites of well-sorted abrasives whose particles ranged from larger to smaller than the wavelength. We measured the variation of reflectance as the phase angle varied from 0.05° to 140°. The following parameters of the media were then deduced: the single scattering albedo, single scattering phase function, transport mean free path, and scattering, absorption, and extinction coefficients. A scattering model based on the equation of radiative transfer was empirically able to describe quantitatively the variation of intensity with angle for each sample. Thus, such models can be used to characterize scattering from regoliths even when the particles are smaller than the wavelength. The scattering parameters were remarkably insensitive to particle size. These results are contrary to theoretical predictions, but are consistent with earlier measurements of alumina abrasives that were restricted to small phase angles. They imply that a basic assumption made by virtually all regolith scattering models, that the regolith particles are the fundamental scattering units of the medium, is incorrect. Our understanding of scattering by regoliths appears to be incomplete, even when the particles are larger than the wavelength.     

Unique isoprene oxidation products demonstrate chlorine atom chemistry occurs in the Houston,Texas urban area

As part of the 2000 Texas Air Quality Study (TexAQS), we studied the isoprene oxidation process under ambient conditions to discern the presence of chlorine atom (Cl) chemistry in the Houston, Texas urban area. By measuring chloromethylbutenone (CMBO) and an isomer of chloromethylbutenal (CMBA), we clearly observed sixteen episodes of active Cl chemistry during the 24-day experiment. Estimated median Cl concentration during each of these episodes was between the detection limit of ~10² atoms cm⁻³ and 50 _{- 30} ^{+ 70} ×10⁴ 50_{ - 30}^{ + 70} \times {10^4} atoms cm⁻³. Cl concentration during all the episodes averaged 7.6 _{- 2.0} ^{+ 4.7} ×10⁴ 7.6_{ - 2.0}^{ + 4.7} \times {10^4} atoms cm⁻³ and thus amounted to less than 3% of the OH concentration during the same periods. During the episodes, the fraction of oxidation chemistry initiated by Cl ranged from 3–43% and was strongly dependent on the quantity and type of hydrocarbons present in the atmosphere. Because of its intermittent presence and low concentration, Cl is not a broadly influential oxidant in the Houston, Texas urban area.     

Ground water flow analysis of a mid-Atlantic outer coastal plain watershed, Virginia, U.S.A

Models for ground water flow (MODFLOW) and particle tracking (MODPATH) were used to determine ground water flow patterns, principal ground water discharge and recharge zones, and estimates of ground water travel times in an unconfined ground water system of an outer coastal plain watershed on the Delmarva Peninsula, Virginia. By coupling recharge and discharge zones within the watershed, flowpath analysis can provide a method to locate and implement specific management strategies within a watershed to reduce ground water nitrogen loading to surface water. A monitoring well network was installed in Eyreville Creek watershed, a first-order creek, to determine hydraulic conductivities and spatial and temporal variations in hydraulic heads for use in model calibration. Ground water flow patterns indicated the convergence of flow along the four surface water features of the watershed; primary discharge areas were in the nontidal portions of the watershed. Ground water recharge zones corresponded to the surface water features with minimal development of a regional ground water system. Predicted ground water velocities varied between < 0.01 to 0.24 m/day, with elevated values associated with discharge areas and areas of convergence along surface water features. Some ground water residence times exceeded 100 years, although average residence times ranged between 16 and 21 years; approximately 95% of the ground water resource would reflect land use activities within the last 50 years.     

The Development of Laser Ablation ICP-MS and Calibration Strategies: Examples from the Analysis of Trace Elements in Volcanic Glass Shards and Sulfide Minerals

This contribution presents a review of the recent developments in laser ablation inductively coupled plasma-mass spectrometry. We describe the important developments which have occurred in the laser systems used, leading to a spatial resolution of around 20 (im, and give an overview of the major instrument developments which have affected the geological applications of laser ablation ICP-MS. We describe the calibration of laser ablation for the analysis of trace elements in two different matrices: volcanic glass shards and sulfide minerals. We show how single glass shards can be analysed using the National Institute of Standards and Technology (NIST) glass certified reference materials for calibration and demonstrate the effect of using single spot analyses compared to rastering of the calibration sample. We show the importance of inter-shard variation and demonstrate that averaged single shard analyses produce data which compare well with bulk analyses. The calibration of the laser system for sulfide mineral analysis is discussed and two different strategies are proposed, one using spiked pressed powder pellets of sulfides and the other metal reference materials. We present conclusions and recommendations for the calibration of laser ablation ICP-MS instruments.