Using soil and Quaternary geological information to assess the intrinsic groundwater vulnerability of shallow aquifers: an example from Lithuania

Lithuania, in the Baltic region of northern Europe, is heavily dependent on groundwater resources for its public water supply, with a large proportion, especially in rural areas, derived from shallow Quaternary aquifers. A national groundwater-vulnerability methodology, based upon the UK approach, has been developed on behalf of the Lithuanian Ministry of Environmental Protection as a possible basis for the future protection of shallow groundwater resources for the rural inhabitants. Some modifications to the UK methodology were required to enable archive data to be used. The four aquifer classes depicted on the final groundwater vulnerability map are based upon the assessed relative permeabilities of the uppermost Quaternary deposits. The derivation of the classification of soil-leaching potential required a reassessment of Soviet-based soil wetness and particle-size classes and a calculation of subsoil-saturated hydraulic conductivity. A preliminary validation of the final maps against available shallow groundwater samples suggests that the methodology satisfactorily predicts the intrinsic groundwater vulnerability. The final methodology, based upon its low-cost approach using archive data, is relevant to the current needs of Lithuania and can be applied in other regions of similar geology and climate. Electronic Publication     

Ionic surfactants adsorption on heterogeneous surfacesAdsorption de tensioactifs ioniques sur les surfaces hétérogènes

The adsorption of surfactants from aqueous solution is a phenomenon of major importance in applications ranging from ore flotation and paint technology to enhanced oil recovery. As this paper will illustrate, the process is very complex and of high scientific interest; its results can be extended to the retention of organic compounds (humic and fulvic acids, pollutants...) on solids in the biosphere. For a good understanding of the mechanisms involved in surfactants adsorption at the hydrophilic solid–aqueous solution interface, thermodynamic models have to take into account: (i) the physical chemistry of the surfactant in aqueous solution for choosing the appropriate reference phase, (ii) the surface heterogeneity of the adsorbing solid, (iii) the intensity of normal adsorbate–adsorbent bonds responsible for adsorption, (iv) the intensity of lateral bonds that favour the formation of surface aggregates through cooperative process and finally, (v) suitable theoretical models to describe adsorption phenomena. Once this has been achieved, two systems can be discussed: systems characterised by strong normal adsorbate–adsorbent bonds, currently used in ore flotation, which lead, in the case of heterogeneous surfaces, to the formation of lamellar aggregates at monolayer concentration and bilayer formation for higher concentrations. Systems characterised by weak normal adsorbate–adsorbent bonds, currently used in enhanced oil recovery and hydrocarbon (bio)remediation, which correspond to: (i) formation of globular micelles at the solid surface near the CMC when the temperature is higher than the Krafft point, (ii) formation of bilayered lamellar aggregates in the opposite case, (iii) three-dimensional condensation on substrate (T<T_Krafft) if the ionic surfactant interacts with cations in the bulk. To cite this article: J.-M. Cases et al., C. R. Geoscience 334 (2002) 675–688.     

Surface heterogeneity of mineralsAnalyse de l'hétérogénéité superficielle des minéraux

The precise study of adsorption mechanisms at solid–liquid interfaces requires a good analysis of the surface heterogeneity of the studied solids. For that purpose, molecular probe technique is one of the most powerful, especially at solid–gas interfaces. Indeed, low-pressure gas adsorption coupled to modelling of derivative adsorption isotherms as a function of logarithm of pressure allows to study qualitatively and quantitatively the effect of surface heterogeneity on the energy distribution of adsorption centres. The present review points out the interests of that approach to determine the shape of particles, the presence of high-energy adsorption sites and the surface polarity. Results comparing adsorption at solid–gas and solid–liquid interfaces are also mentioned. To cite this article: F. Villiéras et al., C. R. Geoscience 334 (2002) 597–609.     

Estimates of the second dissociation constant of H2S from the surface sulfidation of crystalline sulfur

The adsorption of hydrogen sulfide (Γ_H2S) and protons (Γ_H⁺) on the surface of crystalline sulfur was investigated experimentally in H₂S-bearing solutions at temperatures of 25, 50, and 70°C, NaCl concentrations of 0.1 and 0.5 mol/dm⁻³ and log C_H⁺ values in the range −2.3 to −5. At all temperatures, the dominant process on the surface of the sulfur was deprotonation, and the average values of Γ_H2S were very close to the highest values determined for Γ_H⁺. This finding, combined with the lack of detectable proton adsorption in H₂S-free solutions, suggests that proton adsorption/desorption on the surface of sulfur occurs through formation of ≡ S − H₂S complexes in the presence of H₂S.We propose that this complexation represents sulfidation of the sulfur surface, a process analogous to hydroxylation of oxide surfaces, and that the sulfidation can be described by the reaction: ≡ S + H₂S = ≡SSH₂⁰ β° The deprotonation of the ≡ SH° complex occurs via the reaction: ≡ SSH₂⁰ = ≡SSH⁻ + H⁺ β⁻ Values of 2.9, 2.8, and 2.9 (± 0.23) were obtained for −log β⁻ at 25, 50, and 70°C, respectively. These data were employed to estimate the second dissociation constant for hydrogen sulfide in aqueous solutions using the extrapolation method proposed by Schoonen and Barnes (1988) and yielded corresponding values for the constant of 17.4 ± 0.3, 15.7, and 14.5, respectively. The value for 25°C is in very good agreement with the experimentally determined values of Giggenbach (1971) at 17 ± 0.1; Meyer et al. (1983) at 17 ± 1; Licht and Manassen (1987) at 17.6 ± 0.3; and Licht et al. (1990) at 17.1 ± 0.3.     

Chemical weathering of a marine terrace chronosequence, Santa Cruz, California I: Interpreting rates and controls based on soil concentration-depth profiles

The spatial and temporal changes in element and mineral concentrations in regolith profiles in a chronosequence developed on marine terraces along coastal California are interpreted in terms of chemical weathering rates and processes. In regoliths up to 15 m deep and 226 kyrs old, quartz-normalized mass transfer coefficients indicate non-stoichiometric preferential release of Sr > Ca > Na from plagioclase along with lesser amounts of K, Rb and Ba derived from K-feldspar. Smectite weathering results in the loss of Mg and concurrent incorporation of Al and Fe into secondary kaolinite and Fe-oxides in shallow argillic horizons. Elemental losses from weathering of the Santa Cruz terraces fall within the range of those for other marine terraces along the Pacific Coast of North America.Residual amounts of plagioclase and K-feldspar decrease with terrace depth and increasing age. The gradient of the weathering profile b_s is defined by the ratio of the weathering rate, R to the velocity at which the profile penetrates into the protolith. A spreadsheet calculator further refines profile geometries, demonstrating that the non-linear regions at low residual feldspar concentrations at shallow depth are dominated by exponential changes in mineral surface-to-volume ratios and at high residual feldspar concentrations, at greater depth, by the approach to thermodynamic saturation. These parameters are of secondary importance to the fluid flux q_h, which in thermodynamically saturated pore water, controls the weathering velocity and mineral losses from the profiles. Long-term fluid fluxes required to reproduce the feldspar weathering profiles are in agreement with contemporary values based on solute Cl balances (q_h = 0.025-0.17 m yr⁻¹).During saturation-controlled and solute-limited weathering, the greater loss of plagioclase relative to K-feldspar is dependent on the large difference in their respective solubilities instead of the small difference between their respective reaction kinetics. The steady-state weathering rate under such conditions is defined as

     

Risk and uncertainty analysis of gas pipeline failure and gas combustion consequence

Taking into account a general concept of risk parameters and knowing that natural gas provides very significant portion of energy, firstly, it is important to insure that the infrastructure remains as robust and reliable as possible. For this purpose, authors present available statistical information and probabilistic analysis related to failures of natural gas pipelines. Presented historical failure data is used to model age-dependent reliability of pipelines in terms of Bayesian methods, which have advantages of being capable to manage scarcity and rareness of data and of being easily interpretable for engineers. The performed probabilistic analysis enables to investigate uncertainty and failure rates of pipelines when age-dependence is significant and when it is not relevant. The results of age-dependent modeling and analysis of gas pipeline reliability and uncertainty are applied to estimate frequency of combustions due to natural gas release when pipeline failure occurs. Estimated age-dependent combustion frequency is compared and proposed to be used instead of conservative and age-independent estimate. The rupture of a high-pressure natural gas pipeline can lead to consequences that can pose a significant threat to people and property in the close vicinity to the pipeline fault location. The dominant hazard is combustion and thermal radiation from a sustained fire. The second purpose of the paper is to present the combustion consequence assessment and application of probabilistic uncertainty analysis for modeling of gas pipeline combustion effects. The related work includes performance of the following tasks: to study gas pipeline combustion model, to identify uncertainty of model inputs noting their variation range, and to apply uncertainty and sensitivity analysis for results of this model. The performed uncertainty analysis is the part of safety assessment that focuses on the combustion consequence analysis. Important components of such uncertainty analysis are qualitative and quantitative analysis that identifies the most uncertain parameters of combustion model, assessment of uncertainty, analysis of the impact of uncertain parameters on the modeling results, and communication of the results’ uncertainty. As outcome of uncertainty analysis the tolerance limits and distribution function of thermal radiation intensity are given. The measures of uncertainty and sensitivity analysis were estimated and outcomes presented applying software system for uncertainty and sensitivity analysis. Conclusions on the importance of the parameters and sensitivity of the results are obtained using a linear approximation of the model under analysis. The outcome of sensitivity analysis confirms that distance from the fire center has the greatest influence on the heat flux caused by gas pipeline combustion.     

Assessing impacts of invasive phytoplankton: The Baltic Sea case

There is an increasing understanding and requirement to take into account the effects of invasive alien species (IAS) in environmental quality assessments. While IAS are listed amongst the most important factors threatening marine biodiversity, information on their impacts remains unquantified, especially for phytoplankton species. This study attempts to assess the impacts of invasive alien phytoplankton in the Baltic Sea during 1980-2008. A bioinvasion impact assessment method (BPL - biopollution level index) was applied to phytoplankton monitoring data collected from eleven sub-regions of the Baltic Sea. BPL takes into account abundance and distribution range of an alien species and the magnitude of the impact on native communities, habitats and ecosystem functioning. Of the 12 alien/cryptogenic phytoplankton species recorded in the Baltic Sea only one (the dinoflagellate Prorocentrum minimum) was categorized as an IAS, causing a recognizable environmental effect.     

Qualitative behaviour of the trajectories of test bodies in five-dimensional spherically-symmetric gravitational field

Qualitative behaviour of the trajectories of test bodies is investigated in the five-dimensional gravitation theory for the spherically-symmetric solution. The Binnet formula is obtained for the trajectory. The region of the existence of circular trajectories as well as the regions of their stability are specially investigated using the method of numerical calculations. The values of the free parameters in the five-dimensional gravitation theory are estimated for the solar system.     

Chemical Weathering of Pleistocene Glacial Outwash Sediments: A Comparison of Contemporary and Long-term Rates for Soils and Groundwaters

Pore water solutes increase to depths of up to six meters in unsaturated 10 kyr-old glacial outwash sediments in the Trout Lake Basin of northern Wisconsin, USA. After correction for evapotranspiration, these increases reflect weathering gradients produced from plagioclase, calc-magnesium pyroxenes, and amphiboles. In spite of relatively abundant K-feldspar, solute K and Rb reflect negative gradients produced by nutrient plant uptake and cycling. Weathering rates are calculated from solute gradients (b _solute), hydraulic fluxes (q _h ), volumetric BET surface areas (S _v ), and mineral-specific stoichiometric coefficients (β) such that $ R_{\text{solute}} = \frac{{q_{h} }}{{b_{\text{solute}} \beta {\kern 1pt} {\kern 1pt} S_{v} }} $ Average plagioclase weathering rates (R _plag = 1.6–3.1 × 10^?15 mol m^?2 s^?1) bracket rates calculated for other Quaternary glaciated landscapes. Deeper soil pore waters are as chemically concentrated as underlying groundwaters which, based on hydrologic analyses, have traveled distances up to several kilometers over transient times of hundreds of years. Pore water recharge essentially sets solute compositions close to thermodynamic saturation, thus limiting additional weathering potential along these ground water flow paths. Solid-state elemental and mineral gradients, unlike solute gradients, are essentially invariant with soil depth, reflecting low weathering intensities produced over the relatively short geologic time since sediment deposition. A spreadsheet calculator reproduces modest mass loses from such profiles and indicates that present-day weathering is kinetically and not saturation/transport controlled.