Steady-state kinetics and equilibrium between ground water and granitic rock

A hypothesis is presented that the dissolution of albite includes the exchange of sodium for hydrogen ion in a surface layer of the mineral and the structural collapse of the residual anionic lattice of the layer. The ion exchange is described by the first law of diffusion (D_25°C = 3 × 10^?22 and 1.5 × 10^?20 cm²sec^?1 at P_CO2 = 0 and 26.2 atm, respectively). The surface residual layer reaches a steady-state thickness ranging from n × 10^?8 to n × 10^?5 cm according to the temperature and P_CO2. The increase in aqueous sodium with time in a continuous ground-water system is described by a simple exponential equation. The equation is used to estimate the percolation time of ground water from the data on the chemical composition of a water sample. The probable times range from 14 to 3840 days for various ground-water systems and are compared to the times of percolation calculated from the geothermal and hydraulic data. Both estimates are found to be in general agreement. The concentrations of Al and Si in cold water from granitic rocks are shown to be controlled by the chemical equilibrium with respect to an aged aluminosilicate. The aluminosilicate precipitates from ground water as an amorphous isoelectric solid. Its chemical composition is represented by a simplified stoichiometric formula [Al(OH)₃](_1?x)[SiO₂]_x and varies linearly with pH of the solution. The atoms of Al, O and H tend to occupy a fixed position in the solid given by the gibbsite structure upon aging in the field. The solubility product of the solid is estimated from the published data on experimental and field research into the dissolution of feldspars: logK = (1 ? x) × log [Al³⁺] + xlog [H₄SiO₄] ? (3 ? 3x) log [H⁺] = 8.56 ? 11.26x, where x is the molar fraction of silica in the aluminosilicate.     

Lead Removal from Aqueous Solution by Natural and Pretreated Zeolites

Hazardous metal cations enter water through the natural geochemical route or from the industrial wastes. Their separation and removal can be achieved by adsorptive accumulation of the cations on a suitable adsorbent. In the present work, toxic Pb(II) ions are removed from water by accumulating it on the surface of natural zeolite in three different forms; one untreated and two treated samples, one sample treated with 2 M HCI solution and other is treated with 3 M NaOH solution. Natural zeolite is mainly composed of clinoptilolite, and mordenite, with amount of non-zeolite phase (smectite and illite) and C and CT opal. The adsorption experiments are carried out using a batch process in environments of different pH, initial Pb(II) concentration, interaction time and amount of zeolites. Treated zeolite samples show high exchange capacity for Pb(II) compared to untreated sample, however, acid-treated sample shows an exceedingly good exchange capacity. Equilibrium data fitted well with the Langmuir isotherm model with maximum adsorption capacity of 115, 126, and 132 mg g⁻¹ of untreated natural zeolites, alkali-treated zeolites and acid-treated zeolites respectively. The rates of adsorption were found to confirm to pseudo-first order kinetic with good correlation and the overall rate of lead ions uptake.     

Sedimentary geochemical record of recent environmental changes around Lake Middle Marviken,Sweden

Geochemical properties of sediments deposited in Lake Middle Marviken over the last 185 years record the impacts of a succession of environmental changes that have occurred in the watershed. Clear-cutting of forests for wood and charcoal and extensive water harnessing to support the local iron mills from 1897 to 1957 is recorded by low C/N ratios, high black carbon, and low TOC and N_total accumulation rates. Larger δ¹³C and δ¹⁵N values in sediments deposited during this period imply higher productivity. Fluctuations in N_total and P_total accumulation rates show that the lake chemistry has varied between P or N-depleted systems that affected the δ¹⁵N values. Organic matter in the sediments is predominantly immature terrestrial material. Furthermore, hydrocarbon CPI, TAR, and P_aq values conform with the observed geochemical trends, variations in organic matter sources, and changes in the watershed. Accumulation rates of Cd, Pb, Zn, and S remained mostly unchanged throughout the period of mining, but an increase from 1957 to 1980 is most likely associated with air-borne industrial and fossil fuel emissions from regional urbanization. In situ microbial processes, such as iron and manganese reduction, also appear to be important in carbon cycling and in affecting the sediment and water chemistry of this lake.     

Lithostratigraphy and U-Pb zircon dating in the overturned limb of the Siviez-Mischabel nappe: a new key for Middle Penninic nappe geometry.

Detailed field work and zircon analysis have improved the knowledge of the lithostratigraphy at the base of the Siviez-Mischabel nappe in the Mattertal (St-Niklaus-Törbel area). They confirm the existence of an overturned limb and clarify the structure of the St-Niklaus syncline. The following formations can be observed:

• Polymetamorphic gneisses; composed of paragneisses, amphibolites and micaschists (Bielen Unit, pre-Ordovician).
• Fine-grained, greyish quartzite and graywacke with kerogen-rich horizons (Törbel Formation, presumed Carboniferous).
• Green or white micaschists characterized by brown carbonate spots associated with white conglomeratic quartzites (Moosalp Formation, Early Permian).
• Massive, green or white, fine grained, microconglomeratic or conglomeratic quartzites with characteristic pink quartz pebbles (Bruneggjoch Formation, Late Permian-Early Triassic).

This coherent overturned sequence can be observed from the St-Niklaus area to the Moosalp pass to the north. Detailed mapping revealed that the St-Niklaus syncline is symmetrical and connects the overturned limb of the Siviez-Mischabel nappe to the normal series of the Upper Stalden zone. U-Pb zircon geochronology on magmatic and detrital zircons allowed constraining ages of these formations. Detrital zircons display ages ranging from 2900 ± 50 to 520 ± 4 Ma in the Törbel Formation, and from 514 ± 6 to 292 ± 9 Ma in the Moosalp Formation. In addition, the Permian Randa orthogneiss is intrusive into the polymetamorphic gneisses and into the Permo-Carboniferous metasediments of the overturned limb of the Siviez-Mischabel nappe. This revision clarified also the lithostratigraphy of the nearby and subjacent Lower Stalden zone composed of an overturned limb with Permo-Carboniferous formations. This has critical implications for the tectonic setting of the nappes in the region, speaking for few recumbent folds with well preserved normal and overturned limbs instead of a succession of imbricate thrust sheets in a normal stratigraphic position.     

Decameter storm radiation,I

A log-periodic array, 3 km long in the E-W direction is in operation at the Clark Lake Radio Observatory. The solar brightness distribution is swept once per second in the 65-20 MHz frequency range. The analysis of the interferometer records allows the determination of one dimensional solar burst positions, to an accuracy of 0.1 R at 60 MHz and 0.3 R at 30 MHz, approximately.Six long duration noise storms have been observed over an eight month period, extending from January to September, 1971. The storms are described and their relation to chromospheric active regions and flares is discussed. Decametric storms are found to be related to complexes of interacting active regions. The interaction is studied in terms of the number of simultaneous flares observed to occur in the various active regions. On the average, twice as many simultaneous flares are observed than would be expected if flares occurred at random. An analysis of coronal magnetic field maps computed from longitudinal photospheric fields shows magnetic arcades and some divergent field lines at the site of storm regions. Decimeter and meter wavelength sources are found to be associated with all decameter storms. At decimeter wavelengths double or multiple sources are often seen above individual active regions forming part of the chromospheric complex.     

The tidal and wind induced hydrodynamics of the composite system Adriatic Sea/Lagoon of Venice

A shallow water hydrostatic 2D hydrodynamic numerical model, based on the boundary conforming coordinate system, was used to simulate aspects of both general and small scale oceanic features occurring in the composite system constituted by the Adriatic Sea and the Lagoon of Venice (Italy), under the influence of tide and realistic atmospheric forcing. Due to a specific technique for the treatment of movable lateral boundaries, the model is able to simulate efficiently dry up and flooding processes within the lagoon. Firstly, a model calibration was performed by comparing the results of the model, forced using tides and ECMWF atmospheric pressure and wind fields, with observations collected for a set of 33 mareographic stations uniformly distributed in the Adriatic Sea and in the Lagoon of Venice. A second numerical experiment was then carried out by considering only the tidal forcing. Through a comparison between the results obtained in the two experiments it was possible to assess the reliability of the estimated parameter through the composite forcing. Model results were then verified by comparing simulated amplitude and phase of each tidal constituent as well as tidal velocities simulated at the inlets of the lagoon and in the Northern Adriatic Sea with the corresponding observed values. The model accurately reproduces the observed harmonics: mean amplitude differences rarely exceed 1 cm, while phase errors are commonly confined below 15°. Semidiurnal and diurnal currents were correctly reproduced in the northern basin and a good agreement was obtained with measurements carried out at the lagoon inlets. On this basis, the outcomes of the hydrodynamic model were analyzed in order to investigate: (i) small-scale coastal circulation features observed at the interface between the adjoining basins, which consist often of vortical dipoles connected with the tidal flow of Adriatic water entering and leaving the Lagoon of Venice and with along-shore current fields connected with specific wind patterns; (ii) residual oscillations, which are often connected to meteorological forcing over the basin. In particular, it emerges that small-scale vortical features generated near the lagoon inlet can be efficiently transported toward the open sea, thus contributing to the water exchange between the two marine regions, and a realistic representation of observed residual oscillations in the area would require a very detailed knowledge of atmospheric as well as remote oceanic forcing.     

Estimation of baseflow residence times in watersheds from the runoff hydrograph recession: method and application in the Neversink watershed,Catskill Mountains,New York

A method for estimation of mean baseflow residence time in watersheds from hydrograph runoff recession characteristics was developed. Runoff recession characteristics were computed for the period 1993–96 in the 2 km² Winnisook watershed, Catskill Mountains, southeastern New York, and were used to derive mean values of subsurface hydraulic conductivity and the storage coefficient. These values were then used to estimate the mean baseflow residence time from an expression of the soil contact time, based on watershed soil and topographic characteristics. For comparison, mean baseflow residence times were calculated for the same period of time through the traditional convolution integral approach, which relates rainfall δ¹⁸O to δ¹⁸O values in streamflow. Our computed mean baseflow residence time was 9 months by both methods. These results indicate that baseflow residence time can be calculated accurately using recession analysis, and the method is less expensive than using environmental and/or artificial tracers. Published in 2002 by John Wiley & Sons, Ltd.     

Impact of horizontal eddy diffusivity on Lagrangian statistics for coastal pollution from a major marine fairway

Lagrangian trajectory methods are often applied as deterministic transport models, where transport is due strictly to advection without taking into account stochastic elements of particle dispersion, which raises questions about validity of the model results. The present work investigates the impact of horizontal eddy diffusivity for a case study of coastal pollution in the Gulf of Finland, where the pollutants are assumed to originate from a major fairway and are transported to the coast by surface currents. Lagrangian trajectories are calculated using the TRACMASS model from velocity fields calculated by the Rossby Centre circulation model for 1982 to 2001. Three cases are investigated: (1) trajectory calculation without eddy diffusivity, (2) stochastic modelling of eddy diffusivity with a constant diffusion coefficient and (3) stochastic modelling of eddy diffusivity with a time- and space-variable diffusion coefficient. It is found that the eddy diffusivity effect increases the spreading rate of initially closely packed trajectories and the number of trajectories that eventually reach the coast. The pattern of most frequently hit coastal sections, the probability of hit to each such section and the time the pollution spends offshore are virtually invariant with respect to inclusion of eddy diffusivity.