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.     

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.     

Temporal variability in summertime bottom hypoxia in shallow areas of Mobile Bay,Alabama

This paper addresses temporal variability in bottom hypoxia in broad shallow areas of Mobile Bay, Alabama. Time-series data collected in the summer of 2004 from one station (mean depth of 4 m) exhibit bottom dissolved oxygen (DO) variations associated with various time scales of hours to days. Despite a large velocity shear, stratification was strong enough to suppress vertical mixing most of the time. Bottom DO was closely related to the vertical salinity gradient (ΔS). Hypoxia seldom occurred when ΔS (over 2.5 m) was <2 psu and occurred almost all the time when ΔS was >8 psu in the absence of extreme events like hurricanes. Oxygen balance between vertical mixing and total oxygen demand was considered for bottom water from which oxygen demand and diffusive oxygen flux were estimated. The estimated decay rates at 20°C ranging between 0.175–0.322 d⁻¹ and the corresponding oxygen consumption as large as 7.4 g O₂ m⁻² d⁻¹ fall at the upper limit of previously reported ranges. The diffusive oxygen flux and the corresponding vertical diffusivity estimated for well mixed conditions range between 8.6–9.5 g O₂ m⁻² d⁻¹ and 2.6–2.9 m² d⁻¹, respectively. Mobile Bay hypoxia is likely to be associated with a large oxygen demand, supported by both water column and sediment oxygen demands, so that oxygen supply from surface water during destratification events would be quickly exhausted to return to hypoxic conditions within a few hours to days after destratification events are terminated.     

Orion: A 1–5 Micron Focal Plane for the 21st Century

The Orion program is a project to develop a 2K × 2K infrared focal plane using InSb p-on-n diodes for detectors. It is the natural follow-up to the successful Aladdin 1K × 1K program started in the early 90's. The work is being done at the Raytheon Infrared Operations Division (RIO, previously known as the Santa Barbara Research Center) by many of the same people who created the Aladdin focal plane. The design is very similar to the successful Aladdin design with the addition of reference pixels, whole array readout (no quadrants), two-adjacent-side buttability, and a packaging design that includes going directly to the ultimate focal plane size of 4K × 4K. So far we have successfully made a limited number of hybrid modules with InSb detectors. In this paper we will describe the design features and test data taken from some of these devices. This revised version was published online in July 2006 with corrections to the Cover Date.     

Conceptual models for carbonate aquifers. 1969

The very diverse types of ground‐water behavior in carbonate terrains can be classified by relating the flow type to a particular hydrogeologic environment each exhibiting a characteristic cave morphology. The ground water may move by diffuse flow, by retarded flow, or by free flow. Diffuse flow occurs in less soluble rocks such as extremely shaley limestones or crystalline dolomites. Integrated conduits are rare. Caves tend to be small, irregular, and often little more than solutionally widened joints. Retarded flows occur in artesian environments and in situations where unfavorable stratigraphy forces ground water to be confined to relatively thin beds. Network cave patterns are characteristic since hydrodynamic forces are damped by the external controls. Solution occurs along many available joints. Free flowing aquifers are those in which solution has developed a subsurface drainage system logically regarded as an underground extension of surface streams. These streams may have fully developed surface tributaries as well as recharge from sinkholes and general infiltration. Characteristic cave patterns are those of integrated conduit systems which are often truncated into linear, angulate, and branchwork caves. Free Flow aquifers may be further subdivided into Open aquifers lying beneath karst plains and Capped aquifers in which significant parts of the drainage net lie beneath an insoluble cap rock. Other geologic factors such as structure, detailed lithology, relief, and locations of major streams, control the details of cave morphology and orientation of the drainage network.