Water quality condition and trend in North Queensland waterways

The Queensland Environmental Protection Agency monitored water quality at 133 sites in North Queensland waterways between Cooktown and Bundaburg from 1992 to 2001. Condition of the waterways was rated by comparing recent data with the Queensland Water Quality Guidelines. Long-term trends were analysed using a censored regression technique that incorporates the effects of flow, temperature, seasonality and allows for long-term non-linear trends. Many sites were in good condition; those in poor condition were usually impacted by point source discharges; those in moderate condition were usually impacted by agricultural land use. There were no consistent long-term trends across the whole region. Recommendations for future programs include incorporating pressure indicators, ensuring high standards of quality assurance, including covariates such as rainfall in trend assessment and continuing programs over more than 10 years to allow detection of trends due to changes in land-use.     

The critical inclination problem: A simple treatment

A short analysis is presented in the hope of clarifying the situation.     

Distribution of Uranium in the crust of the northwestern canadian shield as shown by lake-sediment analysis

In 1972 a reconnaissance geochemical survey was carried out by the Geological Survey of Canada in the northwestern Canadian Shield. Samples of nearshore lake sediment were collected, by helicopter, from 36,000 sq. miles of the Bear and Slave Structural Provinces. Sample density was one per 10 miles. These samples have since been analyzed for 27 elements. This paper is concerned with the distribution of uranium in 1,241 samples from the western third of the survey area. This region mainly comprises the Bear Province, of Proterozoic age.The Bear Province, which is a metallogenic province for uranium, also appears to be a geochemical province for this element. Uranium is four times more abundant in lake sediments from this area (5.3 p.p.m. U) as compared to the eastern part of the Slave Province (1.3 p.p.m. U). The lake-sediment data are in agreement with analyses of composite rock samples from two parts of the survey area.Within the Bear Province the regional distribution of uranium is controlled mainly by the distribution of Proterozoic granitic rocks. Nearly all areas of 5 p.p.m. U or greater in lake sediments are underlain by Proterozoic granites, or are near to these rocks. Within the granite areas, uranium is distributed along two sets of regularly spaced linear trends. The highest contents in lake sediment, which include values up to 300 p.p.m. U, commonly occur near the intersections of the two trends. These trends correspond to a set of northeast and a set of northwest strike-slip faults and lineaments that were produced by east-west compression of the Bear Province during and after the Hudsonian Orogeny (1750 m.y.). Outside the western margin of the survey area, complex epigenetic mineralization is associated with northeasterly-trending faults. Uranium has been produced from veins of this type at Port Radium and at the Rayrock Mine. Since it is associated with faults, this type of mineralization tends to occur in topographic depressions, that often contain lakes and swamps. Lake-sediment analysis is believed to be an excellent means of detecting such mineralization, both within the survey area and possibly elsewhere in the Canadian Shield. The data obtained during 1972 provide a basis for more detailed prospecting in the region.     

ON THE THEORY OF HITCH-HIKING AS A SPATIAL STOCHASTIC PROCESS

Hitch-hiking has been ignored by traditional geography. In this article it is shown that ideas and techniques from the new geography yield substantial insights into its character as a spatial process.     

Bistability of the thermohaline circulation identified through comprehensive 2-parameter sweeps of an efficient climate model

The effect of changes in zonal and meridional atmospheric moisture transports on Atlantic overturning is investigated. Zonal transports are considered in terms of net moisture export from the Atlantic sector. Meridional transports are related to the vigour of the global hydrological cycle. The equilibrium thermohaline circulation (THC) simulated with an efficient climate model is strongly dependent on two key parameters that control these transports: an anomaly in the specified Atlantic–Pacific moisture flux (F_a) and atmospheric moisture diffusivity (K_q). In a large ensemble of spinup experiments, the values of F_a and K_q are varied by small increments across wide ranges, to identify sharp transitions of equilibrium THC strength in a 2-parameter space (between Conveyor On and Off states). Final states from this ensemble of simulations are then used as the initial states for further such ensembles. Large differences in THC strength between ensembles, for identical combinations of F_a and K_q, reveal the co-existence of two stable THC states (Conveyor On and Off)—i.e. a bistable regime. In further sensitivity experiments, the model is forced with small, temporary freshwater perturbations to the mid-latitude North Atlantic, to establish the minimum perturbation necessary for irreversible THC collapse in this bistable regime. A threshold is identified in terms of the forcing duration required. The model THC, in a Conveyor On state, irreversibly collapses to a Conveyor Off state under additional freshwater forcing of just 0.1 Sv applied for around 100 years. The irreversible collapse is primarily due to a positive feedback associated with suppressed convection and reduced surface heat loss in the sinking region. Increased atmosphere-to-ocean freshwater flux, under a collapsed Conveyor, plays a secondary role.     

A modeling of the structure and favorable H-docking sites and defects for the high-pressure silica polymorph stishovite

Employing first-principles methods, the docking sites for H were determined and H, Al, and vacancy defects were modeled with an infinite periodic array of super unit cells each consisting of 27 contiguous symmetry nonequivalent unit cells of the crystal structure of stishovite. A geometry optimization of the super-cell structure reproduces the observed bulk structure within the experimental error when P1 translational symmetry was assumed and an array of infinite extent was generated. A mapping of the valence electrons for the structure displays mushroom-shaped isosurfaces on the O atom, one on each side of the plane of the OSi₃ triangle in the nonbonded region. An H atom, placed in a cell near the center of the super cell, was found to dock upon geometry optimization at a distance of 1.69 Å from the O atom with the OH vector oriented nearly perpendicular to the plane of the triangle such that the OH vector makes a angle of 91° with respect to [001]. However, an optimization of a super cell with an Al atom replacing Si and an H atom placed nearby in a centrally located cell resulted in an OH distance of 1.02 Å with the OH vector oriented perpendicular to [001] as observed in infrared studies. The geometry-optimized position of the H atom was found to be in close agreement with that (0.44, 0.12, 0.0) determined in an earlier study of the theoretical electron density distribution. The docking of the H atom at this site was found to be 330 kJ mol^–1 more stable than a docking of the atom just off the shared OO edge of the octahedra as determined for rutile. A geometry optimization of a super cell with a missing Si generated a vacant octahedra that is 20% larger than that of the SiO₆ octahedra. The valence electron density distribution displayed by the two-coordinate O atoms that coordinate the vacant octahedral site is very similar to those displayed by the bent SiOSi angles in coesite. The internal distortions induced by the defect were found to diminish rather rapidly with distance, with the structure annealing to that observed in the bulk crystal to within about three coordination spheres.     

Molecular modelling of rare earth element complexation in subduction zone fluids

Complexation of (trace) elements in fluids plays a critical role in determining element mobility in subduction zones, but to date, the atomic-scale processes controlling elemental solubilities are poorly understood. As a first step towards computer simulation of element complexation in subduction zone fluids, a thermodynamic cycle was developed to investigate the hydration environment and energetics of lanthanide complexes using density functional theory. The first solvation shell is explicitly defined and the remaining part of the aqueous fluid is modelled using a polarisable continuum model, which allows extrapolation to a broad pressure and temperature range.We illustrate our method by comparing solvation of lanthanide series elements in H₂O in the presence of fluoride or chloride for conditions relevant to subduction zones. The energetics of lanthanide- and lanthanide-fluoride/chloride hydration complexes were determined computationally. Calculated hydration free energies for trivalent lanthanides with explicit eight- and nine-fold coordinated first hydration shells show good agreement with literature data at room pressure and temperature. The hydration free energy is more negative for smaller complexes (heavy lanthanides) relative to larger complexes (light lanthanides), with the difference between La and Lu in water amounting to 361 kJ mol⁻¹. The hydration free energy of all lanthanide ions becomes less negative with increasing pressure (p) and temperature (T) up to 2.5 GPa and 1000 K (typical conditions in the upper part of subducting slabs). The free energy difference between light- and heavy-lanthanides remains essentially unchanged at elevated (p, T) conditions. There are minor geometrical differences in local hydration environment between light lanthanide-chloride (La-Nd) and heavy lanthanide-chloride (Pm-Lu) hydrated complexes, without a distinguishable energy difference. Complexation with fluoride is energetically more favourable than with chloride by 206 ± 4 kJ mol⁻¹ across the entire lanthanide series. The association of fluoride-water and chloride-water fragments with lanthanide-water complexes is energetically more favourable for aqueous lanthanide complexes surrounded by fewer first hydration shell water molecules.The methods developed in this study, in conjunction with simulation of the energetics of trace element incorporation into minerals, open the possibility to use molecular modelling to constrain elemental behaviour in subduction zones.     

Electronic environments in carrollite, CuCo2S4, determined by soft X-ray photoelectron and absorption spectroscopy

Fracture surfaces of a natural carrollite specimen have been characterised by synchrotron and conventional X-ray photoelectron spectroscopy and near-edge X-ray absorption spectroscopy. For the synchrotron X-ray measurements, the mineral surfaces were prepared under clean ultra high vacuum and were unoxidised. The characterisation was undertaken primarily to establish unequivocally the oxidation state of the Cu in the mineral, but also to obtain information on the electronic environments of the Co and S, and on the surface species. Experimental and simulated Cu L_2,3-edge absorption spectra confirmed an oxidation state of Cu^I, while Co 2p photoelectron and Co L_2,3 absorption spectra were largely consistent with the Co^III established previously by nuclear magnetic resonance spectroscopy. S 2p photoelectron spectra provided no evidence for S to be present in the bulk in more than one state, and were consistent with an oxidation state slightly less negative than S^-II. Therefore it was concluded that carrollite can be best represented by Cu^ICo^III₂(S₄)^-VII. The Cu^I oxidation state is in agreement with that expected for Cu tetrahedrally coordinated by S, but is in disagreement with the Cu^II deduced previously from some magnetic, magnetic resonance and Cu L-edge X-ray absorption spectroscopic measurements. A significant concentration of S species with core electron binding energies both lower and higher than the bulk value were formed at fracture surfaces, and these entities were assigned to monomeric and oligomeric surface S species. The density of Cu d states calculated for carrollite differed from that previously reported but was consistent with the observed Cu L₃ X-ray absorption spectrum. The initial oxidation of carrollite in air under ambient conditions was confirmed to be congruent, unlike the incongruent reaction undergone by a number of non-thiospinel sulfide minerals.     

Ouachita, Appalachian, and Ancestral Rockies deformations recorded in mesoscale structures on the foreland Ozark plateaus

Mesoscale structures in Paleozoic rocks of the Ozark plateaus reveal four Pennsylvanian deformation episodes in midcontinent North America. The two earliest episodes can be assigned to progressive northwestward docking of the Ouachita terrane with North America. Early extensional structures (Event 1) indicate a northwest/southeast maximum horizontal stress (Hmax) during Early Pennsylvanian Ouachita terrane advance. Event 2 extensional and strike-slip structures indicate Hmax across the Ozark plateaus that varies systematically from north-northwest/south-southeast in the south to northeast/southwest in the north. This suggests development of a slip-line deformation field in response to minor northeastward lateral escape of lithospheric blocks away from the northwestward-moving Ouachita terrane's leading edge, which acted as an indenter in western Arkansas, southeastern Oklahoma, and Texas. Younger contractional and strike-slip structures of Event 3 indicate northeast/southwest Hmax across the entire Ozark plateaus, and deformation orientation and intensity are not readily assigned to Ouachita foreland deformation and may be related to Middle Pennsylvanian Ancestral Rockies contractional deformation. Finally, Event 4 contractional structures indicate northwest/southeast Hmax consistent with southern Appalachian late stage convergence.Deformation episodes are localized along basement fault zones, particularly at major bends, suggesting minor restraining-bend uplifts along strike-slip faults. Geometries of conjugate normal fault and hybrid shear joint arrays indicate localized areas of high differential stress consistent with basement block uplift at these bends. High-angle faults reactivated in a reverse sense and bedding-parallel veins suggest tensile minimum stresses and pore fluid pressures exceeding lithostatic stress, consistent with brine pulses driven into the midcontinent during Late Paleozoic orogeny (as proposed by other authors).