30 resultados para Water rock interactions

em QUB Research Portal - Research Directory and Institutional Repository for Queen's University Belfast


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A large hydrochemical data-set for the East Yorkshire Chalk has been assessed. Controls on the distribution of water qualities within this aquifer reflect: water-rock interactions (affecting especially the carbonate system and associated geochemistry); effects of land-use change (especially where the aquifer is unconfined); saline intrusion and aquifer refreshening (including ion exchange effects); and aquifer overexploitation (in the semi-confined and confined zones of the aquifer). Both Sr and I prove useful indicators of groundwater ages, with I/Cl ratios characterising two sources of saline waters. The hydrochemical evidence clearly reveals the importance of both recent management decisions and palaeohydrogeology in determining the evolution and distribution of groundwater salinity within the artesian and confined zones of the aquifer. Waters currently encountered in the aquifer are identified as complex (and potentially dynamic) mixtures between modern recharge waters, modern seawater, and old seawaters which entered the aquifer many millennia ago.

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Ubiquitous noxious hydrophobic substances, such as hydrocarbons, pesticides and diverse industrial chemicals, stress biological systems and thereby affect their ability to mediate biosphere functions like element and energy cycling vital to biosphere health. Such chemically diverse compounds may have distinct toxic activities for cellular systems; they may also share a common mechanism of stress induction mediated by their hydrophobicity. We hypothesized that the stressful effects of, and cellular adaptations to, hydrophobic stressors operate at the level of water : macromolecule interactions. Here, we present evidence that: (i) hydrocarbons reduce structural interactions within and between cellular macromolecules, (ii) organic compatible solutes-metabolites that protect against osmotic and chaotrope-induced stresses-ameliorate this effect, (iii) toxic hydrophobic substances induce a potent form of water stress in macromolecular and cellular systems, and (iv) the stress mechanism of, and cellular responses to, hydrophobic substances are remarkably similar to those associated with chaotrope-induced water stress. These findings suggest that it may be possible to devise new interventions for microbial processes in both natural environments and industrial reactors to expand microbial tolerance of hydrophobic substances, and hence the biotic windows for such processes.

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A semi-phenomenological model describing wideband dielectric and far-infrared spectra of liquid water was proposed recently by the same authors [J. Mol. Struct. 606 (2002) 9], where a small dipole-moment component changing harmonically with time determines a weak absorption band (termed here the R-band) centred at the wavenumber v similar to 200 cm(-1). In the present work, a rough molecular theory of the R-band based on the concept of elastic interactions is given. Stretching and bending of hydrogen bonds cause restricted rotation (RR) of a polar water molecule in terms of a dimer comprising the H- bonded molecules. Analytical expression for the RR frequency nu(str) is derived as a function of the RR amplitude, geometrical parameters and force constants. The density g(nu(str)) of frequency distribution is shown to be centred in the R-band. The spectrum of the dipolar auto-correlation function calculated for this structural-dynamical model is found. A composite model comprising two intermolecular potentials is proposed, which yields for water a good description of the experimental wideband (from 0 to 1000 cm(- 1)) spectra of complex permittivity and of absorption coefficient. The presented interpretation of these spectra is based on a concept that water presents a two-component solution, with components differing by the types of molecular rotation. (C) 2003 Elsevier B.V. All rights reserved.

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The structural interactions of biological macromolecules, their biochemical activities and, ultimately, the metabolic function of cellular systems are dependent upon weak inter- and intra-molecular forces such as hydrogen bonds, Van der Waals forces, and the hydrophobic effect. Water molecules, and those of hydrophobic substances such as hydrocarbons, can take part in and/or modify these interactions and thereby determine the operational and structural stability of the microbial cell and its macromolecular systems. We explain how the cytosol, plasma membrane and the extracellular solution form a material and energetic continuum; and discuss the behavior of hydrophobic substances of extracellular origin as they migrate into the plasma membrane and into the cell's interior. The adverse effects of substances with a log P octanol-water =2, that partition into the hydrophobic domains of biological macromolecules, are discussed in relation to microbial cell function; and we speculate whether the cellular stress that they induce is symmetrical or asymmetrical in nature. In the context of the microbial environment, we take a situational-functional approach to consider how hydrophobic stressors interact with the microbial cell, and what types of evasion tactics microbes can employ to minimize their inhibitory activities. Finally, we discuss the ecological implications of hydrocarbon-induced cellular stress for microbial systems.

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Accurate conceptual models of groundwater systems are essential for correct interpretation of monitoring data in catchment studies. In surface-water dominated hard rock regions, modern ground and surface water monitoring programmes often have very high resolution chemical, meteorological and hydrological observations but lack an equivalent emphasis on the subsurface environment, the properties of which exert a strong control on flow pathways and interactions with surface waters. The reasons for this disparity are the complexity of the system and the difficulty in accurately characterising the subsurface, except locally at outcrops or in boreholes. This is particularly the case in maritime north-western Europe, where a legacy of glacial activity, combined with large areas underlain by heterogeneous igneous and metamorphic bedrock, make the structure and weathering of bedrock difficult to map or model. Traditional approaches which seek to extrapolate information from borehole to field-scale are of limited application in these environments due to the high degree of spatial heterogeneity. Here we apply an integrative and multi-scale approach, optimising and combining standard geophysical techniques to generate a three-dimensional geological conceptual model of the subsurface in a catchment in NE Ireland. Available airborne LiDAR, electromagnetic and magnetic data sets were analysed for the region. At field-scale surface geophysical methods, including electrical resistivity tomography, seismic refraction, ground penetrating radar and magnetic surveys, were used and combined with field mapping of outcrops and borehole testing. The study demonstrates how combined interpretation of multiple methods at a range of scales produces robust three-dimensional conceptual models and a stronger basis for interpreting groundwater and surface water monitoring data.

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The high level of escapes from Atlantic salmon farms, up to two million fishes per year in the North Atlantic, has raised concern about the potential impact on wild populations. We report on a twogeneration experiment examining the estimated lifetime successes, relative to wild natives, of farm, F1 and F2 hybrids and BC1 backcrosses to wild and farm salmon. Offspring of farm and hybrids (i.e. all F1 , F2 and BC1 groups) showed reduced survival compared with wild salmon but grew faster as juveniles and displaced wild parr, which as a group were significantly smaller. Where suitable habitat for these emigrant parr is absent, this competition would result in reduced wild smolt production. In the experimental conditions, where emigrants survived downstream, the relative estimated lifetime success ranged from 2% (farm) to 89% (BC1 wild) of that of wild salmon, indicating additive genetic variation for survival . Wild salmon primarily returned to fresh water after one sea winter (1SW) but farm and hybrids produced proportionately more 2SW salmon. However, lower overall survival means that this would result in reduced recruitment despite increased 2SW fecundity. We thus demonstrate that interaction of farm with wild salmon results in lowered fitness, with repeated escapes causing cumulative fitness depression and potentially an extinction vortex in vulnerable populations.

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A simple molecular analytical theory of dielectric relaxation in strongly polar fluids is considered in terms of a semi- phenomenological approach. Theoretical spectra epsilon(v), a(v) of complex permittivity and absorption coefficient are fully determined by a form of intermolecular potential well, in which a dipole reorients. In a recent publication by VI. Gaiduk, O.F. Nielsen, and T.S. Perova [J. Molliq 95 (1002) 1-25] the wideband spectra of liquid H2O and D2O were described in terms of a composite model comprising the rectangular and the cosine squared potential wells. Much better results are achieved in this work, where the rectangular well is replaced by a well with a rounded bottom termed the hat-curved well. The spectrum of the auto-correlation function (ACF) is calculated for such a potential. The proposed theory of a composite model, comprising hat-curved and parabolic wells, is applied for liquid water. This model is capable for describing the Debye relaxation region, the second relaxation region in the submillimeter wavelength range, and the far infra-red (FIR) e(v), a(v) spectra, where an intense librational band and an additional weak band are placed, respectively, near 700 cm(-1) and 200 cm(-1). The latter band reflects the features of so-called specific (viz. directly related to H-bonds) interactions and the former band reflects the features of unspecific interactions. The physical mechanisms connected with these types of interactions are discussed in terms of two relevant types of water structure (types of molecular rotation). The proposed theory is also applied to a non-associated liquid in terms of one hat-curved potential well. (C) 2004 Elsevier B.V. All rights reserved.

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Concentrations and isotopic compositions of NO-3 from the Oldman River (OMR) and some of its tributaries (Alberta, Canada) have been determined on a monthly basis since December 2000 to assess temporal and spatial variations of riverine NO-3 sources within the OMR basin. For the OMR sites, NO-3 -N concentrations reached up to 0.34 mg L-1, d15N-NO-3 values varied between –0.3 and +13.8‰, and d18O-NO-3 values ranged from –10.0 to +5.7‰. For the tributary sites, NO-3 -N concentrations were as high as 8.81 mg L-1, d15N-NO-3 values varied between –2.5 and +23.4‰, and d18O-NO-3 values ranged from –15.2 to +3.4‰. Tributaries in the western, relatively pristine forested part of the watershed add predominantly NO-3 to the OMR with d15N-NO-3 indicative of soil nitrification. In contrast, tributaries in the eastern agriculturally-urban-industrially-used part of the basin contribute NO-3 with d15N-NO-3 values of about +16‰ indicative of manure and/or sewage derived NO-3. This difference in d15N-NO-3 values of tributaries was found to be independent of the season, but rather indicates a spatial change in the NO-3 source, which correlates with land use changes within the OMR basin. As a consequence of tributary influx, d15N-NO-3 values in the Oldman River increased from +6‰ in the downstream direction (W to E), although [NO-3 -N] increased only moderately (generally

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Surface water and deep and shallow groundwater samples were taken from selected parts of the Grand-Duchy of Luxembourg to determine the isotopic composition of nitrate and sulfate, in order to identify sources and/or processes affecting these solutes. Deep groundwater had sulfate concentrations between 20 and 40 mg/L, d34Ssulfate values between -3.0 and -20.0‰, and d18Osulfate values between +1.5 and +5.0‰; nitrate was characterized by concentrations varying between

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Experimental measurements of density at different temperatures ranging from 293.15 to 313.15 K, the speed of sound and osmotic coefficients at 298.15 K for aqueous solution of 1-ethyl-3-methylimidazolium bromide ([Emim][Br]), and osmotic coefficients at 298.15 K for aqueous solutions of 1-butyl-3-methylimidazolium chloride ([Bmim][Cl]) in the dilute concentration region are taken. The data are used to obtain compressibilities, expansivity, apparent and limiting molar properties, internal pressure, activity, and activity coefficients for [Emim][Br] in aqueous solutions. Experimental activity coefficient data are compared with that obtained from Debye-Hückel and Pitzer models. The activity data are further used to obtain the hydration number and the osmotic second virial coefficients of ionic liquids. Partial molar entropies of [Bmim][Cl] are also obtained using the free-energy and enthalpy data. The distance of the closest approach of ions is estimated using the activity data for ILs in aqueous solutions and is compared with that of X-ray data analysis in the solid phase. The measured data show that the concentration dependence for aqueous solutions of [Emim][Br] can be accounted for in terms of the hydrophobic hydration of ions and that this IL exhibits Coulombic interactions as well as hydrophobic hydration for both the cations and anions. The small hydration numbers for the studied ILs indicate that the low charge density of cations and their hydrophobic nature is responsible for the formation of the water-structure-enforced ion pairs.

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Applications such as soil, rock and oil-well grouting all require enormous amounts of cement and are good examples of areas where a high volume of fly ash could partially replace cement to produce low-cost, environmentally safe and durable concrete. There is an increasing need to identify the rheological properties of cement grout using a simple test to determine the fluidity, and other properties of underwater grouts such as washout resistance and compressive strength. This paper presents statistical models developed using a fractorial design which was carried out to model the influence of key parameters on properties affecting the performance of underwater grout. Such responses of fluidity included mini-slump and flow time measured by Marsh cone, washout resistance, unit weight and compressive strength. The models are valid for mixes with 0.40 to 0.60 water-to-cementitious materials ratio, 0.02 to 0.08% of anti-washout admixture, by mass of binder, and 0.6 to 1.8% of superplasticizer, by mass of cementitious materials. The grout was made with 50% of pulverized-fuel ash replacement, by mass ofcementitious materials. Also presented are the derived models that enable the identification of underlying primary factors and their interactions that influence the modelled responses of underwater cement grout. Such parameters can be useful to reduce the test protocol needed for proportioning of underwater cement grout. This paper highlighted the influence of W/CM and dosage of antiwashout admixture and superplasticizer on fluidity, washout resistance and compressive strength and attempted also to demonstrate the usefulness of the models to improve understanding of trade-offs between parameters.

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In attempting to understand the distributions of both introduced species and the native species on which they impact, there is a growing trend to integrate studies of behaviour with more traditional life history/ecological approaches. The question of what mechanisms drive the displacement of the freshwater amphipod Gammarus duebeni by the often introduced G pulex is presented as a case study Patterns of displacement are well documented throughout Europe, but the speed and direction of displacement between these species can be varied. From early studies proposing interspecific competition as causal in these patterns, I review research progress to date. I show there has been no evidence for interspecific competition operating, other than the field patterns themselves, a somewhat tautological argument. Rather, the increased recognition of behavioural attributes with respect to the cannibalistic and predatory nature of these species gave rise to a series of studies unravelling the processes driving field patterns. Both species engage in 'intraguild predation' (IGP), with moulting females particularly vulnerable to predation by congeneric males. G pulex is more able both to engage in and avoid this interaction with G duebeni. However, several factors mediate the strength and asymmetry of this IGP, some biotic (e.g. parasitism) and others abiotic (e.g. water chemistry). Further, a number of alternative hypotheses that may account for the displacement (hybridization; parasite transmission) have been tested and rejected. While interspecific competition has been modelled mathematically and found to be a weak interaction relative to IGP, mechanisms of competition between these Gammarus species remain largely untested empirically. Since IGP may be finely balanced in some circumstances, I conclude that the challenge to detect interspecific competition remains and we require assessment of its role, if any, in the interaction between these species. Appreciation of behavioural attributes and their mediation should allow us to more fully understand, and perhaps predict, species introductions and resultant distributions.