Trace metals in acid sediments and waters, Pimpama catchment, southeast Queensland, Australia

The Pimpama River floodplain has developed over the last several thousand years as a result of sea-level fluctuations that shaped the lower catchment and enabled the formation of sedimentary pyrite. The subsequent production of sulfuric acid due to the oxidation of this pyrite enhances the breakdown of metal-bearing sediments and can lead to leaching of major and trace metals into the waters of the region. The seasonal pattern of rainfall and current land-use activities are important aspects that intensify the natural production of acid and influence the release and distribution of metals. To identify the source and migration of metals in the Pimpama catchment and to understand the impact of pyrite oxidation on the distribution of metals in sediments and waters, several components of the drainage system were analyzed: bedrock, sediments from river bed and bank, and water. The elements analyzed in this study (V, Cr, Co, Ni, Cu, Zn and Pb) are all present in the bedrock material which explains their occurrence in the unconsolidated sediments of the floodplain. These metals concentrate in the upper section of the sedimentary sequence and their presence is related to clay minerals such as smectite, organic matter and iron phases. However, Zn, Mo and Co occur in higher amounts than the local background and within standard shale. This comparison suggests that the diagenetic processes alone cannot explain the higher concentrations and it is concluded that these metals also have an anthropogenic source. The formation of sulfuric acid creates conditions for higher mobility of some metals, such as Cr, Co, Ni, Cu, Zn, but does not affect less mobile ones such as Mo and Pb. Over the longterm, the production of acid influences the breakdown of mineral phases and enhances the process of weathering. Over the short term, every rain event leaches acid from sediments and mobilizes metals resulting in a substantial reduction in the quality of river water. Received: 2 October 1998 · Accepted: 16 February 1999     

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.     

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.     

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.     

Simulation of monsoon depressions using MM5: sensitivity to cumulus parameterization schemes

Summary The sensitivity of the simulation of the monsoon depressions to the cumulus parameterization schemes used in a numerical model is studied using the Pennsylvania State University – National Center for Atmospheric Research (PSU-NCAR) model MM5 version 3.6.2. Three different cases of monsoon depressions were studied with a two way interacting domains of 45 km and 15 km resolutions. Two different cumulus parameterization schemes namely Grell (GR) and Kain-Fritsch (KF) were used for the sensitivity study. The model was integrated for 48 hours with the initial and boundary conditions of European Center for Medium Range Weather Forecasting Reanalysis (ERA-40) data. The results show that both the schemes are able to simulate the large scale features of the monsoon depressions realistically. However, both the schemes failed to simulate the exact location of the depression after 24- and 48-hour simulation. The rainfall simulations of both the schemes were very different. The model with the GR scheme tends to over predict the rainfall. The KF scheme could simulate the distribution of the rainfall comparable to the observations. The KF scheme could simulate the maximum observed rainfall but due to locational errors of the simulated depression, the location of the maximum rainfall was not exact. It is also seen that the resolution of the model has a positive impact on the rainfall simulation. The GR and KF schemes were able to realistically simulate the apparent heat sources, but the apparent moisture profile simulated with KF scheme was more comparable to the verifying analysis. The root mean square errors of mean sea-level pressure, temperature, zonal wind and meridional wind were smaller for KF simulation compared to the GR simulation. Permanent affiliation: Center for Development of Advanced Computing, Pune University Campus, Ganeshkhind, Pune-411 007, India.     

Effects of atmospheric dynamics and ocean resolution on bi-stability of the thermohaline circulation examined using the Grid ENabled Integrated Earth system modelling (GENIE) framework

We have used the Grid ENabled Integrated Earth system modelling (GENIE) framework to undertake a systematic search for bi-stability of the ocean thermohaline circulation (THC) for different surface grids and resolutions of 3-D ocean (GOLDSTEIN) under a 3-D dynamical atmosphere model (IGCM). A total of 407,000 years were simulated over a three month period using Grid computing. We find bi-stability of the THC despite significant, quasi-periodic variability in its strength driven by variability in the dynamical atmosphere. The position and width of the hysteresis loop depends on the choice of surface grid (longitude-latitude or equal area), but is less sensitive to changes in ocean resolution. For the same ocean resolution, the region of bi-stability is broader with the IGCM than with a simple energy-moisture balance atmosphere model (EMBM). Feedbacks involving both ocean and atmospheric dynamics are found to promote THC bi-stability. THC switch-off leads to increased import of freshwater at the southern boundary of the Atlantic associated with meridional overturning circulation. This is counteracted by decreased freshwater import associated with gyre and diffusive transports. However, these are localised such that the density gradient between North and South is reduced tending to maintain the THC off state. THC switch-off can also generate net atmospheric freshwater input to the Atlantic that tends to maintain the off state. The ocean feedbacks are present in all resolutions, across most of the bi-stable region, whereas the atmosphere feedback is strongest in the longitude–latitude grid and around the transition where the THC off state is disappearing. Here the net oceanic freshwater import due to the overturning mode weakens, promoting THC switch-on, but the atmosphere counteracts this by increasing net freshwater input. This increases the extent of THC bi-stability in this version of the model. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.