Environmental Isotopes as Indicators for Ground Water Recharge to Fractured Granite

To assess the contribution of accumulated winter precipitation and glacial meltwater to the recharge of deep ground water flow systems in fracture crystalline rocks, measurements of environmental isotope ratios, hydrochemical composition, and in situ parameters of ground water were performed in a deep tunnel. The measurements demonstrate the significance of these ground water recharge components for deep ground water flow systems in fractured granites of a high alpine catchment in the Central Alps, Switzerland. Hydrochemical and in situ parameters, as well as d18O in ground water samples collected in the tunnel, show only small temporal variations. The precipitation record of d18O shows seasonal variations of ~14‰ and a decrease of 0.23‰ ± 0.03‰ per 100 m elevation gain. d2H and d18O in precipitation are well correlated and plot close to the meteoric water line, as well as d2H and d18O in ground water samples, reflecting the meteoric origin of the latter. The depletion of 18O in ground water compared to 18O content in precipitation during the ground water recharge period indicates significant contributions from accumulated depleted winter precipitation to ground water recharge. The hydrochemical composition of the encountered ground water, Na-Ca-HCO3-SO4(-F), reflects an evolution of the ground water along the flowpath through the granite body. Observed tritium concentrations in ground water range from 2.6 to 16.6 TU, with the lowest values associated with a local negative temperature anomaly and anomalous depleted 18O in ground water. This demonstrates the effect of local ground water recharge from meltwater of submodern glacial ice. Such localized recharge from glaciated areas occurs along preferential flowpaths within the granite body that are mainly controlled by observed hydraulic active shear fractures and cataclastic faults.

Simplified theory of wideband spectra of liquid H2O and D2O (from 0 to 1000 cm(-1)) due to reorienting polar and vibrating H-bonded water molecules

A semi-phenomenological molecular model is presented, which is capable of describing with the use of analytical formulae, the wideband dielectric(1) and far-infrared spectra of ordinary and heavy water. In the model the vector of a dipole moment is presented as a sum of two components. The absolute value of the first one is constant; the second one changes harmonically with time. The key aspect of this work is consideration of FIR spectra due to the second component. In the context of the modified hybrid model presented in the work, reorientation of the dipoles in the rectangular potential well is considered, as a result of which the librational (near 700 cm (-1)) and translational (near 200 cm (-1)) absorption bands and the microwave Debye relaxation spectrum arise. It is shown that the time-dependent part of a dipole moment contributes most to the translational band, the relevant mechanism is taken to be stretching vibration of the H-bonded molecules. Previous linear-response molecular models were unsuccessful in describing this band (in heavy water) in terms of the complex dielectric permittivity. The spatial and time scales characteristic of water are estimated. (C) 2002 Elsevier Science B.V. All rights reserved.

Mutual Solubilities of Water and Hydrophobic Ionic Liquids

The ionic nature of ionic liquids (ILs) results in a unique combination of intrinsic properties that produces increasing interest in the research of these fluids as environmentally friendly "neoteric" solvents. One of the main research fields is their exploitation as solvents for liquid-liquid extractions, but although ILs cannot vaporize leading to air pollution, they present non-negligible miscibility with water that may be the cause of some environmental aquatic risks. It is thus important to know the mutual solubilities between ILs and water before their industrial applications. In this work, the mutual solubilities of hydrophobic yet hygroscopic imidazolium-, pyridinium-, pyrrolidinium-, and piperidinium-based ILs in combination with the anions bis(trifluoromethylsulfonyl)imide, hexafluorophosphate, and tricyanomethane with water were measured between 288.15 and 318.15 K. The effect of the ILs structural combinations, as well as the influence of several factors, namely cation side alkyl chain length, the number of cation substitutions, the cation family, and the anion identity in these mutual solubilities are analyzed and discussed. The hydrophobicity of the anions increases in the order [C(CN)3] <[PF6] <[Tf2N] while the hydrophobicity of the cations increases from [Cnmim] <[Cnmpy] [Cnmpyr] <[Cnmpip] and with the alkyl chain length increase. From experimental measurements of the temperature dependence of ionic liquid solubilities in water, the thermodynamic molar functions of solution, such as Gibbs energy, enthalpy, and entropy at infinite dilution were determined, showing that the solubility of these ILs in water is entropically driven and that the anion solvation at the IL-rich phase controls their solubilities in water. The COSMO-RS, a predictive method based on unimolecular quantum chemistry calculations, was also evaluated for the description of the water-IL binary systems studied, where it showed to be capable of providing an acceptable qualitative agreement with the experimental data.

A tentative determination of upwelling influence on the paleo-surficial marine water reservoir effect in southeastern Brazil.

Previous work has suggested that seasonal and inter-annual upwelling of deep, cold, radiocarbon depleted waters from the South Atlantic has caused variations in the reservoir effect (R) through time along the southern coast of Brazil. This work aims to examine the possible upwelling influence on the paleo-reservoir age of Brazilian surficial coastal waters based on paired terrestrial/marine samples obtained from archaeological remains. On the Brazilian coast there are hundreds of shell-middens built up by an ancient culture that lived between 6500 to 1500 years ago, but there are few located on open coast with a known upwelling influence. Three archaeological sites located in a large headland in Arraial do Cabo and Ilha de Cabo Frio, southeastern coast of Brazil with open ocean conditions and a well-known strong and large upwelling of the Malvinas/Falkland current were chosen for this study. The 14C age differences between carbonized seed and marine samples varied from 281 ± 44 to 1083 ± 51 14C yr. There are also significant age differences between carbonized seed samples (977 14C yr) and marine samples (200 and 228 14C yr) from the same archaeological layer that cannot be explained by a reservoir effect or an old-wood effect for charcoal. Therefore the present data from the southeastern Brazilian coast are inconclusive for identifying an upwelling effect on R. To do so it would be necessary to more precisely define the present-pre-bomb R in upwelling regions and to analyze paired marine/terrestrial samples that are contemporaneous beyond doubt.

Expressed sequence tag-derived microsatellites for the cool-water marine copepod Calanus finmarchicus

The copepod Calanus finmarchicus is the major contributor to zooplankton biomass in the North Atlantic and Norwegian Sea, but recent studies have shown a 70% decrease in abundance as well as a northward shift in the species' range. Insights into dispersal capabilities gained from population genetic studies will be crucial in predicting the response of C. finmarchicus communities to climate change and, consequently, we have developed a set of expressed sequence tag-derived microsatellite markers to allow fine-scale elucidation of population structuring and dispersal. Ten polymorphic markers displayed between two and 19 alleles, with levels of expected heterozygosity ranging from 0.044 to 0.924.

Identifying an O-2 supply pathway in CO oxidation on Au/TiO2(110): A density functional theory study on the intrinsic role of water

Au catalysis has been one of the hottest topics in chemistry in the last 10 years or so. How O-2 is supplied and what role water plays in CO oxidation are the two challenging issues in the field at the moment. In this study, using density functional theory we show that these two issues are in fact related to each other. The following observations are revealed: (i) water that can dissociate readily into OH groups can facilitate O-2 adsorption on TiO2; (ii) the effect of OH group on the O-2 adsorption is surprisingly long-ranged; and (iii) O-2 can also diffuse along the channel of Ti (5c) atoms on TiO2(1 10), and this may well be the rate-limiting step for the CO oxidation. We provide direct evidence that O-2 is supplied by O-2 adsorption on TiO2 in the presence of OH and can diffuse to the interface of Au/TiO2 to participate in CO oxidation. Furthermore, the physical origin of the water effects on Au catalysis has been identified by electronic structure analyses: There is a charge transfer from TiO2 in the presence of OH to O-2, and the O-2 adsorption energy depends linearly on the 02 charge. These results are of importance to understand water effects in general in heterogeneous catalysis.

A density functional theory study of hydroxyl and the intermediate in the water formation reaction on Pt

Density functional theory has been used to study the adsorption of hydroxyl at low and high coverages and also to investigate the nature of the intermediate in the H2O formation reaction on Pt(111). At low coverages [1/9 of a monolayer (ML) to 1/3 ML] OH binds preferentially at bridge and top sites with a chemisorption energy of similar to2.25 eV. At high coverages (1/2 ML to 1 ML) H bonding between adjacent hydroxyls causes: (i) an enhancement in OH chemisorption energy by about 15%; (ii) a strong preference for OH adsorption at top sites; and (iii) the formation of OH networks. The activation energy for the diffusion of isolated OH groups along close packed rows of Pt atoms is 0.1 eV. This low barrier coupled with H bonding between neighboring OH groups indicates that hydroxyls are susceptible to island formation at low coverages. Pure OH as well as coadsorbed OH and H can be ruled out as the observed low temperature intermediate in the water formation reaction. Instead we suggest that the intermediate consists of a mixed OH+H2O overlayer with a macroscopic surface coverage of 3/4 ML in a 2:1 ratio of OH and H2O. (C) 2001 American Institute of Physics.

A tight binding model for water

We demonstrate for the first time a tight binding model for water incorporating polarizable oxygen atoms. A novel aspect is that we adopt a ``ground up'' approach in that properties of the monomer and dimer only are fitted. Subsequently we make predictions of the structure and properties of hexamer clusters, ice-XI and liquid water. A particular feature, missing in current tight binding and semiempirical hamiltonians, is that we reproduce the almost two-fold increase in molecular dipole moment as clusters are built up towards the limit of bulk liquid. We concentrate on properties of liquid water, particularly dielectric constant and self diffusion coefficient, which are very well rendered in comparison with experiment. Finally we comment on the question of the contrasting densities of water and ice which is central to an understanding of the subtleties of the hydrogen bond.

A Description of the Stationary Wave Pattern of a Marine Craft in Shallow and Intermediate Water Depths

A stationary phase model is used to study supercritical waves generated by high speed ferries. Some general relationships in terms of wave angle, propagation direction, dispersion relationship and depth wavelength relationship are explored and discussed. In particular, it is shown that the wave pattern generated by high speed craft at supercritical speeds depends mainly on the relationship of water depth and ship speed and that the wave patterns are similar in terms of location of crests and troughs for a given depth Froude number. In addition it is found that the far field wave pattern can be described adequately using a single moving point source. The theoretical model compares well with towing tank measurements and full scale data over a range of parameters and hull shapes. The paper also demonstrates that the far field wave pattern at supercritical speeds should be non-dimensionalised by water depth and not hull length unlike it is usually done for subcritical speeds.

The photo-oxidation of water by sodium persulfate, and other electron acceptors, sensitised by TiO2

A number of different electron acceptors are tested for efficacy in the oxidation of water to oxygen, photocatalysed by titanium dioxide. The highly UV-absorbing metal ion electron acceptors, Ce4+ and Fe3+, appear ineffective at high concentration (10(-2) M), due to UV-screening, but more effective at lower concentrations (10(-3) M). The metal-depositing electron acceptor, Ag+, is initially effective, but loses activity upon prolonged irradiation due to metal deposition which promotes electron-hole recombination as well as UV-screening the titania particles. Most striking of the electron acceptors tested is persulfate, particularly in alkaline solution (0.1 M NaOH). The kinetics of the photo-oxidation of water by persulfate, photocatalysed by titania are studied as a function of pH, [S2O82-] and incident light intensity (I). The initial rate of water oxidation increases with pH, is directly proportional to the concentration of persulfate present and depends upon I-0.6. The TiO2/alkaline persulfate photosystem is robust and shows very little evidence of photochemical wear upon repeated irradiation. The results of this work are discussed with regard to previous work in this area and current mechanistic thinking. The formal quantum efficiency of the TiO2/alkaline persulfate photosystem was estimated as ca. 2%. (C) 2004 Elsevier B.V. All rights reserved.

Low flow water quality in rivers; septic tank systems and high-resolution phosphorus signals

Rural point sources of phosphorus (P), including septic tank systems, provide a small part of the overall phosphorus budget to surface waters in agricultural catchments but can have a disproportionate impact on the low flow P concentration of receiving rivers. This has particular importance as the discharges are approximately constant into receiving waters and these have restricted dilution capacity during ecologically sensitive summer periods. In this study, a number of identified high impact septic systems were replaced with modern sequential batch reactors in three rural catchments during a monitoring period of 4 years. Sub-hourly P monitoring was conducted using bankside-analysers. Results show that strategic replacement of defective septic tank systems with modern systems and polishing filters decreased the low flow P concentration of one catchment stream by 0.032 mg TP L- 1 (0.018 mg TRP L- 1) over the 4 years. However two of the catchment mitigation efforts were offset by continued new-builds that increased the density of septic systems from 3.4 km- 2 to 4.6 km- 2 and 13.8 km- 2 to 17.2 km- 2 and subsequently increased low flow P concentrations. Future considerations for septic system mitigation should include catchment carrying capacity as well as technology changes.

Investigating Hydraulically Active Fractures in A Shallow Meta-Sedimentary Bedrock Aquifer Using Single Well Tracer Testing, Mount Stewart, Northern Ireland

Knowledge of groundwater flow/mass transport, in poorly productive aquifers which underlie over 65% of the island of Ireland, is necessary for effective management of catchment water quality and aquatic ecology. This research focuses on a fractured low-grade Ordovician/Silurian greywacke sequence which underlies approximately 25% of the northern half of Ireland. Knowledge of the unit’s hydrogeological properties remain largely restricted to localised single well open hole “transmissivity” values. Current hydrogeological conceptual models of the Greywacke view the bulk of groundwater flowing through fractures in an otherwise impermeable bedrock mass.
Core analysis permits fracture characterisation, although not all identified fractures may be involved in groundwater flow. Traditional in-situ hydraulic characterisation relies on cumbersome techniques such as packer testing or geophysical borehole logging (e.g. flowmeters). Queen’s University Belfast is currently carrying out hydraulic characterization of 16 boreholes at its Greywacke Hydrogeological Research Site at Mount Stewart, Northern Ireland.
Development of dye dilution methods, using a recently-developed downhole fluorometer, provided a portable, user-friendly, and inexpensive means of detecting hydraulically active intervals in open boreholes. Measurements in a 55m deep hole, three days following fluorescent dye injection, demonstrated the ability of the technique to detect two discrete hydraulically active intervals corresponding to zones identified by caliper and heat-pulse flowmeter logs. High resolution acoustic televiewer logs revealed the zones to correspond to two steeply dipping fractured intervals. Results suggest the rock can have effective porosities of the order of 0.1%.
Study findings demonstrate dye dilution’s utility in characterizing groundwater flow in fractured aquifers. Tests on remaining holes will be completed at different times following injection to identify less permeable fractures and develop an improved understanding of the structural controls on groundwater flow in the uppermost metres of competent bedrock.

Cooking rice in a high water to rice ratio reduces inorganic arsenic content

Total arsenic and arsenic speciation was performed on different rice types (basmati, long-grain, polished ([white] and wholegrain [brown]) that had undergone various forms of cooking. The effect of rinse washing, low volume (2.5 : 1 water : rice) and high volume (6 : 1 water : rice) cooking, as well as steaming, were investigated. Rinse washing was effective at removing circa. 10% of the total and inorganic arsenic from basmati rice, but was less effective for other rice types. While steaming reduced total and inorganic arsenic rice content, it did not do so consistently across all rice types investigated. Low volume water cooking did not remove arsenic. High volume water : rice cooking did effectively remove both total and inorganic arsenic for the long-grain and basmati rice (parboiled was not investigated in high volume cooking water experiment), by 35% and 45% for total and inorganic arsenic content, respectively, compared to uncooked (raw) rice. To reduce arsenic content of cooked rice, specifically the inorganic component, rinse washing and high volume of cooking water are effective.

Mutual Solubilities of Ammonium-Based Ionic Liquids with Water and with Water/Methanol Mixture

Over the last two decades, ionic liquids have gained importance as alternative solvents to conventional VOCs in the field of homogeneous catalysis. This success is not only due to their ability to dissolve a large amount of metal catalysts, but it is also due to their potential to enhance yields of enantiopure products. The art of preparation of a specific enantiomer is a highly desired one and searched for in pharmaceutical industry. This work presents a study on solubility in water and in water/methanol mixture of a set of ILs composed of the bis (trifluoromethylsulfonyl) imide anion and of the N-alkyl-triethyl-ammonium cation (abbrev. [NR,222][NTf2]) with the alkyl chain R ranging from 6 to 12 carbons. Mutual solubilities between ILs and water, as well as between ILs and methanol/water mixture were investigated in detail. These solubilities were measured using two well-known and accurate experimental techniques based on a volumetric and a cloud-point methods. Both methods enabled us to measure the Tx diagrams reflecting the mutual solubilities between water (or water/methanol) and selected ILs in the temperature range from 293.15 to 338.15 K. The data were fitted by using the modified Flory-Huggins equation proposed by de Sousa and Rebelo and compared also with the prediction carried out by the Cosmo-RS methodology

Temperature and water potential relations of tropical Trametes and other wood-decay fungi from the indigenous forests of Zimbabwe

Three isolates each, of nine different Trametes and five other wood inhabiting basidiomycetes, were collected from the indigenous forests of Zimbabwe, and the impact of temperature (20-60 degrees C), osmotic and matric potential (-0.5 to - 8.0 MPa), and their interactions on in vitro growth compared. Generally, there was no significant difference between growth of isolates of the same species in relation to temperature. Temperature relationships of the species studied correlated well with their geographic distributions. Species occurring in hot, dry regions tolerated a wide temperature range, with some showing unusually high thermotolerance (55 degrees, T. socotrana, T. cingulata and T. cervina). There were significant intra-strain differences for individual species in relation to solute potential on glycerol-modified media. Generally, growth of ail species was better on glycerol- and KCl-modified osmotic media than on a metrically-modified medium (PEG 8000) at 25, 30 and 37 degrees. The limits for growth on the osmotic media were significantly wider than matric medium, being - 4.5 to - 5.0 and - 2.5 to - 4.5 MPa, respectively. An Irpex sp. grew at lower water potentials than all other species, with good growth at - 7.0 MPa. This study suggests that the capacity of these fungi for effective growth over a range of temperatures, osmotic and matric potentials contributes to their rapid wood decay capacities in tropical climates.