The chemistry of several calcium sulphate systems was successfully modelled in multi-component acid-containing sulphate solutions using the mixed solvent electrolyte (MSE) model for calculating the mean activity coefficients of the electrolyte species. The modelling involved the fitting of binary mean activity, heat capacity and solubility data, as well as ternary solubility data. The developed model was shown to accurately predict the solubility of calcium sulphate from 25 to 95 °C in simulated zinc sulphate processing solutions containing MgSO4, MnSO4, Fe2(SO4)3, Na2SO4, (NH4)2SO4 and H2SO4. The addition of H2SO4 results in a significant increase in the calcium sulphate solubility compared to that in water. By increasing the acid concentration, gypsum, which is a metastable phase above 40 °C, dehydrates to anhydrite, and the conversion results in a decrease in the solubility of calcium sulphate. In ZnSO4–H2SO4 solutions, it was found that increasing MgSO4, Na2SO4, Fe2(SO4)3 and (NH4)2SO4 concentrations do not have a pronounced effect on the solubility of calcium sulphate. From a practical perspective, the model is valuable tool for assessing calcium sulphate solubilities over abroad temperature range and for dilute to concentrated multi-component solutions.

Geochemical transformations in the system «water - rock» constitute the genetic basis of karst morphogesis. The article demonstrates that corrosion and chemical sedimentation are largely responsible for the morphological look of êàðñòîâûõcavities. The basic method used is thermodynamic calculations of geochemical equilibria, which determine an aggressiveness of natural solutions.

The change of isobar-isothermal potential (free energy of Gibbs) was used as a measure of chemical affinity of matters, i.e. their capabilities to enter into a reaction between them with formation of other matters.

Variety of hydrochemical situations taking place in carbonate êàðñòå, summarized in five typical conditions, which include considerable part of possible karst morphogenetic settings, while others can be obtained by combination of the examined ones. Every situation is described by hydrochemical calculations.

The second part of the paper is dedicated to practical application of the described methodology, i.e. to the calculations of thermodynamic equilibria observed in the underground streams of the Krasnaya (Red) Cave in Crimea. Close connection of morphological look of the cave with geochemical transformations is shown, which control corrosion and chemical accumulation along the whole length of the karst system.

This paper describes the breeding and roosting caves used by the White-rumped Swiftlet (Aerodramus spodiopygius) on Upolu and Savai’i, Samoa. Because these sites tend to be permanent and often difficult to locate, their locations and other information to help find them are provided as a guide for future workers. This study lasted four years and followed close after two devastating cyclones (Val & Ofa) so the data can form the basis for further study once the populations have fully recovered and equilibria for the populations is reached.

The hydrogeological approach to defining hypogene speleogenesis (HS) relates it to ascending groundwater flow (AF). HS develops where AF causes local disequilibria conditions favoring dissolution and supports them during sufficiently long time in course of the geodynamic and hydrogeological evolution. The disequilibrium conditions at depth are invoked by changing physical-chemical parameters along an AF paths, or/and by the interaction between circulation systems of different scales and hydrody-namic regimes. The association of HS with AF suggests a possibility to discern regulari-ties of development and distribution of HS from the perspectives of the regional hy-drogeological analysis. In mature artesian basins of the cratonic type, settings favorable for AF and HS, are as follows: 1) marginal areas of discharge of the groundwaters of the 2nd hydrogeological story (H-story), 2) zones of topography-controlled upward cir-culation within the internal basin area (at the 1st and, in places, at the 2nd H-stories; 3) crests of anticlinal folds or uplifted tectonic blocs within the internal basin area where the upper regional aquitard is thinned or partially breached; 4) linear-local zones of deep-rooted cross-formational faults conducting AF from internal deep sources across the upper H-stories. Hydrodynamics in the 3rd and 4th stories is dominated by ascending circulation strongly controlled by cross-formational tectonic structures. Specific circula-tion pattern develops in large Cenozoic carbonate platforms (the Florida-type), side-open to the ocean, where AF across stratified sequences in the coastal parts, driven by both topography-induced head gradients and density gradients, involves mixing with the seawater. The latter can be drawn into a platform at deep levels and rise in the plat-form interior (the Kohout’s scheme). In folded regions, AF and HS are tightly con-trolled by faults, especially those at junctions between large tectonic structures. In young intramontaine basins with dominating geostatic regime, HS is favored at margin-al discharge areas where circulation systems of different origins and regimes may inter-act, such as meteoric waters flows from adjacent uplifted massifs, basinal fluids expelled from the basin’s interiors, and endogenous fluids rising along deep-rooted faults. Spe-cific and very favorable settings for HS are found in regions of young volcanism with carbonate formations in a sedimentary cover

This manuscript offers preliminary geochemical evidence that investigates the potential for hypogene speleogenesis in the Cumberland Plateau of southeastern Kentucky, U.S.A. The region was traditionally considered a classic example of epigenic karst, but new insights have uncovered tantalizing observations that suggest alternatives to simple carbonic acid speleogenesis. Such first-order observations have included natural petroleum seeps at the surface and in caves, occasional cave morphologies consistent with action of hypogene fluids, and prolific gypsum within cave passages. To this point, geochemical data from caves and springs verify carbonic acid as the primary dissolutional agent; however, these same analyses cannot rule out sulfuric acid as a secondary source of dissolution. In this paper, Principal Component Analysis of ionic data reveals two components that coordinate with parameters associated with “karst water” and shallow brine. In contrast, molar ratios of Ca+ and Mg+ as compared to HCO3 - and SO4 2- closely follow the reaction pathway stipulated by the carbonate equilibria reactions. Despite these data, the role, if any, of hypogene speleogenesis in the karst of the Cumberland Plateau remains inconclusive. It is very likely that carbonic acid dominates speleogenesis; however, contributions from sulfuric acid may influence our understanding of “inception” and carbon flux within these aquifers.