Chemical Mechanism Development: Laboratory Studies and Model Applications

Within the German Tropospheric Research Programme (TFS) numerous kinetic and mechanistic studies on the tropospheric reaction/degradation of the following reactants were carried out: oxygenated VOC, aromatic VOC, biogenic VOC, short-lived intermediates, such as alkoxy and alkylperoxy radicals.At the conception of the projects these selected groups were classes of VOC or intermediates for which the atmospheric oxidation mechanisms were either poorly characterised or totally unknown. The motivation for these studies was the attainment of significant improvements in our understanding of the atmospheric chemical oxidation processes of these compounds, particularly with respect to their involvement in photooxidant formation in the troposphere. In the present paper the types of experimental investigations performed and the results obtained within the various projects are briefly summarised. The major achievements are highlighted and discussed in terms of their contribution to improving our understanding of the chemical processes controlling photosmog formation in the troposphere.     

Validation of the “Lokal-Modell” over heterogeneous land surfaces using aircraft-based measurements of the REEEFA experiment and comparison with micro-scale simulations

Summary An aircraft-based experimental investigation of the atmospheric boundary layer (ABL) structure and of the energy exchange processes over heterogeneous land surfaces is presented. The measurements are used for the validation of the mesoscale atmospheric model “Lokal-Modell” (LM) of the German Weather Service with 2.8 km resolution. In addition, high-resolution simulations using the non-hydrostatic model FOOT3DK with 250 m resolution are performed in order to resolve detailed surface heterogeneities. Two special observation periods in May 1999 show comparable convective boundary layer (CBL) conditions. For one case study vertical profiles and area averages of meteorological quantities and energy fluxes are investigated in detail. The measured net radiation is highly dependent on surface albedo, and the latent heat flux exhibits a strong temporal variability in the investigation area. A reduction of this variability is possible by aggregation of multiple flight patterns. To calculate surface fluxes from aircraft measurements at low altitude, turbulent energy fluxes were extrapolated to the ground by the budget method, which turned out to be well applicable for the sensible heat flux, but not for the latent flux. The development of the ABL is well captured by the LM simulation. The comparison of spatiotemporal averages shows an underestimation of the observed net radiation, which is mainly caused by thin low-level clouds in the LM compared to observed scattered CBL clouds. The sensible heat flux is reproduced very well, while the latent flux is highly overestimated especially above forests. The realistic representation of surface heterogeneities in the investigation area in the FOOT3DK simulations leads to improvements for the energy fluxes, but an overestimation of the latent heat flux still persists. A study of upscaling effects yields more structures than the LM fields when averaged to the same scale, which are partly caused by the non-linear effects of parameter aggregation on the LM scale.     

Geometry and chronology of growth and drowning of Middle Triassic carbonate platforms (Cernera and Bivera/Clapsavon) in the Southern Alps (northern Italy)

The depositional architecture and the geometric relationships between platform-slope deposits and basinal sediments along with paleontological evidence indicate the time interval of the younger Anisian Reitziites reitzi ammonoid zone to largely represent the main stage of platform aggradation at the Cernera and Bivera/Clapsavon carbonate platforms. Published and new U-Pb age data of zircons from volcaniclastic layers bracketing the stratigraphic interval of platform growth constrain the duration of platform evolution to a time span shorter than 1.8±0.7m.y., probably in the order of 0.5-1m.y., reflecting fast rates of vertical platform aggradation exceeding 500 m/m.y. In the range of growth potentials for shallow-water carbonate systems estimated in relation to the time span of observation, this high rate is in agreement with values for short intervals of 10⁵-10⁶yrs (e.g., Schlager 1999). After drowning, the platforms at Cernera and Bivera/Clapsavon were blanketed by thin pelagic carbonates. On the former platform flanks the draping sediments in places comprise red nodular pelagic limestones (Clapsavon Limestone) similar in facies to the Han Bulog Limestones occurring elsewhere in Middle Triassic successions of the Mediterranean Tethys. The drowning of vast areas of former carbonate platforms possibly triggered the onset of bottom-water circulation in adjacent basins as suggested by the abrupt transition from laminated to bioturbated pelagic nodular limestones in the Buchenstein Formation which occurred close to the time of initial platform submergence. During the Late Ladinian the topographic features of the drowned platforms were onlapped by rapidly deposited, predominantly clastic successions including coarse breccias and volcanic rocks sealing and preserving the peculiar stratigraphic setting.     

Optimized and robust experimental design: a non-linear application to EM sounding

Pragmatic experimental design requires objective consideration of several classes of information including the survey goals, the range of expected Earth responses, acquisition costs, instrumental capabilities, experimental conditions and logistics. In this study we consider the ramifications of maximizing model parameter resolution through non-linear experimental design. Global optimization theory is employed to examine and rank different EM sounding survey designs in terms of model resolution as defined by linearized inverse theory. By studying both theoretically optimal and heuristic experimental survey configurations for various quantities of data, it is shown that design optimization is critical for minimizing model variance estimates, and is particularly important when the inverse problem becomes nearly underdetermined. We introduce the concept of robustness so that survey designs are relatively immune to the presence of potential bias errors in important data. Bias may arise during practical measurement, or from designing a survey using an appropriate model.     

The detection of binary companions to subdwarf B stars

Intermediate dispersion spectroscopy of a sample of 40 hot subdwarf B stars between 5500 and 9000Å has been obtained. The sample includes a large fraction of targets which have been studied photometrically. Seven targets show strong lines arising from the infrared Ca  ii triplet, the unequivocal signature of a cool companion. The positive Ca  ii identifications include known photometric binaries and new targets; all are associated with a photometric red excess. Assuming a canonical value for the subdwarf luminosity, all of the detected companions are overluminous compared with the main sequence. The detection procedure indicates an improved and more secure method for the measurement of the binary frequency of hot subdwarfs.     

The impact of drilling fluid and well cuttings on polychaete feeding guilds from the US northeastern continental shelf

The effect of recent drilling operations (fluid and well cuttings) on polychaete feeding guilds from the continental shelf off Atlantic City, New Jersey, was examined. Although there were some adverse effects on macrobenthos from 2160 metric tons of cuttings and mud solids discharged into the marine environment, the composition of polychaete feeding guilds remained essentially unchanged. This key trophic relationship between polychaetes and the changing environment due to the drilling operation was apparently uninterrupted. This relationship remains to be examined in other natural and perturbed habitats.     

Channel constituents in beryl

The electronic absorption spectra of Fe²⁺ in non-chromium beryls are examined. Fe²⁺ in the Al-rich six-coordinate site produces absorption bands at about 820 nm and 970 nm polarizedE‖c. Fe²⁺ in the channel produces bands at 820 nm (⊥c) and 2100 nm (‖c). Some blue beryls which are more intensely colored than most aquamarines, have an absorption band at ～700 nm (‖c) which is suggested to arise from an Fe²⁺/Fe³⁺ intervalence interaction. Fe²⁺ in both the six-coordinate site and the channel is identified in the Mössbauer spectra. The Mössbauer spectra of deep blue beryls are unusual and have not been satisfactorily explained. Color changes which accompany heating and irradiation are strongly influenced by the channel iron.     

A simple pore water hydrogen diffusion syringe sampler

Molecular hydrogen (H(2)) is an important intermediate product and electron donor in microbial metabolism. Concentrations of dissolved H(2) are often diagnostic of the predominant terminal electron-accepting processes in ground water systems or aquatic sediments. H(2) concentrations are routinely measured in ground water monitoring wells but are rarely measured in saturated aquatic sediments due to a lack of simple and practical sampling methods. This report describes the design and development (including laboratory and field testing) of a simple, syringe-based H(2) sampler in (1) saturated, riparian sediments, (2) surface water bed sediments, and (3) packed intervals of a fractured bedrock borehole that are inaccessible by standard pumped methods.