Two-dimensional modelling of some CFC replacement compounds

The Cambridge 2-D Eulerian model has been used to study the potential atmospheric distributions and lifetimes of a number of CFC replacement compounds and their degradation products. The study has focused on HFC 134a and HCFCs 123, 141b and 142b and the major products formed by their atmospheric degradation. The loss of these compounds and their products by hydroxyl radical attack, photolysis and in-cloud hydrolysis have been investigated. The study has shown that HCFCs 141b and 142b have sufficiently long lifetimes to enter the stratosphere in significant quantities, where degradation leads to an increase in the total stratospheric chlorine concentration. The study has also highlighted areas where further experimental work would be valuable, in particular characterisation of the product channels for the degradation reactions and determination of the removal rates of the products in the aqueous phase.     

ISO Far-IR spectroscopy of IR-bright galaxies and ULIRGs

Based on far-infrared spectroscopy of a small sample of nearbyinfrared-bright and ultraluminous infrared galaxies (ULIRGs) with theISO Long Wavelength Spectrometer we find adramatic progression in ionic/atomic fine-structure emission line andmolecular/atomic absorption line characteristics in these galaxiesextending from strong [O III]52,88 m and [N III]57 m lineemission to detection of only faint [C II]158 m line emissionfrom gas in photodissociation regions in the ULIRGs. The molecularabsorption spectra show varying excitation as well, extending fromgalaxies in which the molecular population mainly occupies the groundstate to galaxies in which there is significant population in higherlevels. In the case of the prototypical ULIRG, the merger galaxy Arp220, the spectrum is dominated by absorption lines of OH, H₂O, CH,and [O I]. Low [O III]88 m line flux relative to the integratedfar-infrared flux correlates with low excitation and does not appear tobe due to far-infrared extinction or to density effects. A progressiontoward soft radiation fields or very dusty H II regions may explainthese effects.     

Late Quaternary climatic history of the Chilean Channels based on fossil pollen and beetle analyses,with an analysis of the modern vegetation and pollen rain

Fossil beetles and pollen were examined from an intermorainal bog at Puerto Edén, Isla Wellington, Chile (latitude 49°08'S, longitude 74°25'W). Wood from near the base of the section has an age of 12 960 ± 150 yr BP. Occurrence of flightless beetle species in the basal peat sample is evidence that some members of the biota survived the last glacial maximum in refugia. The assumption that the Chilean Channels were entirely ice-covered is incorrect. Plants and insects that invaded the deglaciated terrain were those of an Empetrum heathland in which patches of Nothofagus forest were restricted to sheltered locations. The climate supporting the heathland is inferred to have been windier and probably drier than that of the present day. From 13 000 yr BP to 9500 yr BP Nothofagus forest expanded, possibly in response to less windiness and more available moisture. Neither the fossil beetle nor pollen data support a return to significantly colder conditions between 11 000 and 10 000 yr BP at the time of the Younger Dryas Stade. From 9500 to 5500 yr BP the climate was as wet as that of the present day, based on an increased representation of the pollen of moorland plants and of aquatic beetle species. From 5500 to 3000 yr BP the climate was drier, as indicated by the expansion of Empetrum heath and the reduction in mesic habitats. From 3000 yr BP to the present-day mesic habitats dominated as the climate returned to a wetter mode. The alternatively wetter and drier episodes are attributed to latitudinal shifts in the position of storm tracks in the belt of Southern Westerlies.     

A linear and nonlinear study of Mira

Both linear and nonlinear calculations of the 331 day, long period variable star Mira have been undertaken to see what radial pulsation mode is naturally selected. Models are similar to those considered in the linear nonadiabatic stellar pulsation study of Ostlie and Cox (1986). Models are considered with masses near one solar mass, luminosities between 4000 and 5000 solar luminosities, and effective temperatures of approximately 3000 K. These models have fundamental mode periods that closely match the pulsation period of Mira. The equation of state for the stellar material is given by the Stellingwerf (1975ab) procedure, and the opacity is obtained from a fit by Cahn that matches the low temperature molecular absorption data for the Population I Ross-Aller 1 mixture calculated from the Los Alamos Astrophysical Opacity Library. For the linear study, the Cox, Brownlee, and Eilers (1966) approximation is used for the linear theory variation of the convection luminosity. For the nonlinear work, the method described by Ostlie (1990) and Cox (1990) is followed. Results showing internal details of the radial fundamental and first overtone modes behavior in linear theory are presented. Preliminary radial fundamental mode nonlinear calculations are discussed. The very tentative conclusion is that neither the fundamental or first overtone mode is excluded from being the actual observed one.     

The role of land surface dynamics in glacial inception: a study with the UVic Earth System Model

The first results of the UVic Earth System Model coupled to a land surface scheme and a dynamic global vegetation model are presented in this study. In the first part the present day climate simulation is discussed and compared to observations. We then compare a simulation of an ice age inception (forced with 116 ka BP orbital parameters and an atmospheric CO₂ concentration of 240 ppm) with a preindustrial run (present day orbital parameters, atmospheric [CO₂] = 280 ppm). Emphasis is placed on the vegetations response to the combined changes in solar radiation and atmospheric CO₂ level. A southward shift of the northern treeline as well as a global decrease in vegetation carbon is observed in the ice age inception run. In tropical regions, up to 88% of broadleaf trees are replaced by shrubs and C₄ grasses. These changes in vegetation cover have a remarkable effect on the global climate: land related feedbacks double the atmospheric cooling during the ice age inception as well as the reduction of the meridional overturning in the North Atlantic. The introduction of vegetation related feedbacks also increases the surface area with perennial snow significantly.     

Comparison of heat and bromide as ground water tracers near streams

Heat and bromide were compared as tracers for examining stream/ground water exchanges along the middle reaches of the Santa Clara River, California, during a 10-hour surface water sodium bromide injection test. Three cross sections that comprise six shallow (<1 m) piezometers were installed at the upper, middle, and lower sections of a 17 km long study reach, to monitor temperatures and bromide concentrations in the shallow ground water beneath the stream. A heat and ground water transport simulation model and a closely related solute and ground water transport simulation model were matched up for comparison of simulated and observed temperatures and bromide concentrations in the streambed. Vertical, one-dimensional simulations of sediment temperature were fitted to observed temperature results, to yield apparent streambed hydraulic conductivities in each cross section. The temperature-based hydraulic conductivities were assigned to a solute and ground water transport model to predict sediment bromide concentrations, during the sodium bromide injection test. Vertical, one-dimensional simulations of bromide concentrations in the sediments yielded a good match to the observed bromide concentrations, without adjustment of any model parameters except solute dispersivities. This indicates that, for the spatial and temporal scales examined on the Santa Clara River, the use of heat and bromide as tracers provide comparable information with respect to apparent hydraulic conductivities and fluxes for sediments near streams. In other settings, caution should be used due to differences in the nature of conservative (bromide) versus nonconservative (heat) tracers, particularly when preferential flowpaths are present.     

Environmental history of an urban lake: a palaeolimnological study of Lake Jyväsjärvi, Finland

Sedimentary diatom frustules and chironomid remains, in addition to the chemical stratigraphy of 32 elements and organic pollutants such as resin acids, PCB, DDT and its metabolites, were studied from core samples taken from Lake Jyväsjärvi in Central Finland (64° 14 N, 25° 47 E). The sediment profile covered over 200 years, with the oldest samples representing a period of very low human interference. The town of Jyväskylä was established on the lake shore in 1837, and the lake received untreated municipal wastewater from the town up until, 1977. A paper mill started operations in 1872 and began discharging effluent into Lake Jyväsjärvi. In recent years this effluent loading has been reduced. Based on the biological and chemical properties of the sediment strata, five developmental phases were distinguished and named as follows: (1) a pre-industrial phase (approximately up until the 1860s); (2) a phase of early changes in the lake ecosystem (from the 1870s to ca. 1940s); (3) a phase of increasing eutrophication (from ca. 1950 to ca. 1965); (4) a phase of severe pollution (from ca. 1966 to the early-1990s); and (5) a phase of recovery, which proceeded more quickly during the late-1990s following long-term hypolimnetic aeration. It was estimated that the ecological status of the lake changed from good to moderate during the second phase. Due to the poor chemical status of the lake (including increased concentrations of harmful substances) and the pronounced changes in diatom and chironomid communities, the ecological status from 1950 to the early-1990s was classified as bad. The present ecological status, after a slow recovery of about 20 years, can be classified as moderate/poor. Chemical analysis of the sediment revealed that some elements (C, N, P, S, Ba, Cd, Cu, Fe, Pb, Ni and Zn) followed the known history of municipal waste water discharge into the lake, but Hg, Cr and persistent organic pollutants had different stratigraphies, and therefore mainly originated from other sources. Pronounced changes in profundal benthic communities (chironomids) started about 80 years later than those in diatoms, but later changes in chironomid assemblages were greater than those in diatoms.     

Geostatistics and Bayesian updating for transmissivity estimation in a multiaquifer system in Manitoba,Canada

In ground water flow and transport modeling, the heterogeneous nature of porous media has a considerable effect on the resulting flow and solute transport. Some method of generating the heterogeneous field from a limited dataset of uncertain measurements is required. Bayesian updating is one method that interpolates from an uncertain dataset using the statistics of the underlying probability distribution function. In this paper, Bayesian updating was used to determine the heterogeneous natural log transmissivity field for a carbonate and a sandstone aquifer in southern Manitoba. It was determined that the transmissivity in m²/sec followed a natural log normal distribution for both aquifers with a mean of -7.2 and - 8.0 for the carbonate and sandstone aquifers, respectively. The variograms were calculated using an estimator developed by Li and Lake (1994). Fractal nature was not evident in the variogram from either aquifer. The Bayesian updating heterogeneous field provided good results even in cases where little data was available. A large transmissivity zone in the sandstone aquifer was created by the Bayesian procedure, which is not a reflection of any deterministic consideration, but is a natural outcome of updating a prior probability distribution function with observations. The statistical model returns a result that is very reasonable; that is homogeneous in regions where little or no information is available to alter an initial state. No long range correlation trends or fractal behavior of the log-transmissivity field was observed in either aquifer over a distance of about 300 km.     

A mapping of the electron localization function for the silica polymorphs: evidence for domains of electron pairs and sites of potential electrophilic attack

The electron localization function, η, evaluated for first-principles geometry optimized model structures generated for quartz and coesite, reveals that the oxide anions are coordinated by two hemispherically shaped η-isosurfaces located along each of the SiO bond vectors comprising the SiOSi angles. With one exception, they are also coordinated by larger banana-shaped isosurfaces oriented perpendicular to the plane centered in the vicinity of the apex of each angle. The hemispherical isosurfaces, ascribed to domains of localized bond-pair electrons, are centered ～0.70 Å along the bond vectors from the oxide anions and the banana-shaped isosurfaces, ascribed to domains of localized nonbonding lone-pair electrons, are centered ～0.60 Å from the apex of the angle. The oxide anion comprising the straight SiOSi angle in coesite is the one exception in that the banana-shaped isosurface is missing; however, it is coordinated by two hemispherically shaped isosurfaces that lie along the bond vectors. In the case of a first-principles model structure generated for stishovite, the oxide anion is coordinated by five hemispherically shaped η-isosurfaces, one located along each of the three SiO bond vectors (ascribed to domains of bonding-electron pairs) that are linked to the anion with the remaining two (ascribed to domains of nonbonding-electron pairs) located on opposite sides of the plane defined by three vectors, each isosurface at a distance of ～0.5 Å from the anion. The distribution of the five isosurfaces is in a one-to-one correspondence with the distribution of the maxima displayed by experimental Δρ and theoretical ??²ρ maps. Isosurface η maps calculated for quartz and the (HO) ₃ SiOSi(OH) ₃ molecule also exhibit maxima that correspond with the (3,?3) maxima displayed by distributions of ??²ρ. Deformation maps observed for the SiOSi bridges for the silica polymorphs and a number of silicates are similar to that calculated for the molecule but, for the majority, the maxima ascribed to lone-pair features are absent. The domains of localized nonbonding-electron pair coordinating the oxide anions of quartz and coesite provide a basis for explaining the flexibility and the wide range of the SiOSi angles exhibited by the silica polymorphs with four-coordinate Si. They also provide a basis for explaining why the SiO bond length in coesite decreases with increasing angle. As found in studies of the interactions of solute molecules with a solvent, a mapping of η-isosurfaces for geometry-optimized silicates is expected to become a powerful tool for deducing potential sites of electrophilic attack and reactivity for Earth materials. The positions of the features ascribed to the lone pairs in coesite correspond with the positions of the H atoms recently reported for an H-doped coesite crystal.