Groundwater recharge of carbonate aquifers of the Silesian-Cracow Triassic (southern Poland) under human impact

A Triassic carbonate unit has been intensively drained by zinc and lead ore mines and numerous borehole fields since the nineteenth century. Its groundwater recharge has increased due to: pumping of water from boreholes, mining activity, and urbanization. An approach to determine the amounts of the recharge at a variety of spatial scales is presented in the paper. Different methods were used to identify and quantify recharge components on a regional and local scale: mathematical modelling was performed for four aquifers included in an aquifer system, an analytical estimation based on the assumption that an average recharge is equal to the average discharge of the hydrogeological system—for six man-made drainage centres, and the method of water level fluctuation (WLF) was applied in one observation borehole. Results of modelling have been supplemented by observation of environmental tracers (δ¹⁸O, δ²H, ³H), noble gases temperatures, and ⁴He_exc in groundwater. The regional aquifer’s current recharge according to estimations performed by means of modelling varies from 39 to 101 mm/year on average. Depending on the aquifer site the average precipitation ranges from 779 to 864 mm/year. In the confined part of the aquifer average recharge ranges from 26 to 61 mm/year. Within outcrops average recharge varies from 96 to 370 mm/year. Current recharge estimated by the analytical method for man-made drainage centres varies from 158 up to 440 mm/year. High values are caused by different recharge sources like precipitation, induced leakage from shallow aquifers, and water losses from streams, water mains and sewer systems. Pumping of water, mining and municipal activities constitute additional factors accounting for the intensified recharge.     

Environmental risk evaluation of the use of mine spoils and treated sewage sludge in the ecological restoration of limestone quarries

The ecologic restoration criteria in areas degraded from extraction activities require making use of their mine spoils. These materials do not meet fertility conditions to guarantee restoration success and therefore, need the incorporation of organic amendments to obtain efficient substratum. Reducing the deficiencies in the organic material and restoration material nutrients with the contribution of treated sewage sludge is proposed in this work. This experiment was based on a controlled study using columns. The work was conducted with two mine spoils, both very rich in calcium carbonate. The first mineral, of poor quality, came from the formation of aggregates of crushed limestone (Z). The other residual material examined originated in limestone extraction, formed by the levels of interspersed non-limestone materials and the remains of stripped soils (D). Two treatments were undertaken (30,000 and 90,000 kg/ha of sewage sludge), in addition to a control treatment. The water contribution was carried out with a device that simulated either short-duration rain or a flooding irrigation system in order to cover the surface and then percolate through the soil. The collection of leached water took place 24 h after the applications. Different parameters of the leached water were determined, including pH, electrical conductivity, nitrate anions, ammonium, phosphates, sulphates and chlorides. The values obtained for each irrigation application are discussed, and the nitrate values obtained were very elevated.     

Liquid immiscibility in deep-seated magmas and the generation of carbonatite melts

This paper reviews the results of investigations of melt inclusions in minerals of carbonatites and spatially associated silicate rocks genetically related to various deep-seated undersaturated silicate magmas of alkaline ultrabasic, alkaline basic, lamproitic, and kimberlitic compositions. The analysis of this direct genetic information showed that all the deep magmas are inherently enriched in volatile components, the most abundant among which are carbon dioxide, alkalis, halides, sulfur, and phosphorus. The volatiles probably initially served as agents of mantle metasomatism and promoted melting in deep magma sources. The derived magmas became enriched in carbon dioxide, alkalis, and other volatile components owing to the crystallization and fractionation of early high-magnesium minerals and gradually acquired the characteristics of carbonated silicate liquids. When critical compositional parameters were reached, the accumulated volatiles catalyzed immiscibility, the magmas became heterogeneous, and two-phase carbonate-silicate liquid immiscibility occurred at temperatures of ≥1280–1250°C. The immiscibility was accompanied by the partitioning of elements: the major portion of fluid components partitioned together with Ca into the carbonate-salt fraction (parental carbonatite melt), and the silicate melt was correspondingly depleted in these components and became more silicic. After spatial separation, the silicate and carbonate-silicate melts evolved independently during slow cooling. Differentiation and fractionation were characteristic of silicate melts. The carbonatite melts became again heterogeneous within the temperature range from 1200 to 800–600°C and separated into immiscible carbonate-salt fractions of various compositions: alkali-sulfate, alkali-phosphate, alkali-fluoride, alkali-chloride, and Fe-Mg-Ca carbonate. In large scale systems, polyphase silicate-carbonate-salt liquid immiscibility is usually manifested during the slow cooling and prolonged evolution of deeply derived melts in the Earth’s crust. It may lead to the formation of various types of intrusive carbonatites: widespread calcite-dolomite and rare alkali-sulfate, alkali-phosphate, and alkali-halide rocks. The initial alkaline carbonatite melts can retain their compositions enriched in P, S, Cl, and F only at rapid eruption followed by instantaneous quenching.     

Crystallization of authigenic carbonates in mud volcanoes at Lake Baikal

This paper presents data on authigenic siderite first found in surface sediments from mud volcanoes in the Central (K-2) and Southern (Malen’kii) basins of Lake Baikal. Ca is the predominant cation, which substitutes Fe in the crystalline lattice of siderite. The enrichment of the carbonates in the ¹³C isotope (from +3.3 to +6.8‰ for the Malen’kii volcano and from +17.7 to +21.9‰ for K-2) results from the crystallization of the carbonates during methane generation via the bacterial destruction of organic matter (acetate). The overall depletion of the carbonates in ¹⁸O is mainly inherited from the isotopic composition of Baikal water.     

General characteristics of the geochemical evolution of silicic melts during the development of massive sulfide magmatic ore systems: Evidence from the investigation of melt inclusions

The investigation of melt inclusions in the minerals of volcanic rocks from the massive sulfide deposits of Siberia and the Urals revealed some specific features in the development of their magmatic ore systems. It was shown that the petrochemical and rare earth element compositions of melt inclusions reflect the geodynamic conditions of their formation: island arc conditions for the massive sulfide deposits of Rudny Altai, eastern Tuva, and the Salair Range and a back arc basin environment for the Yaman-Kasy deposit. The silicic melts of inclusions from the volcanic rocks of massive sulfide deposits show some specific features with respect to the contents of volatile components. In all of the ore deposits studied, fluorine content was always low (0.03–0.08 wt %), whereas chlorine content (0.13–0.28 wt %) was higher than the average value for silicic melts (0.17 wt %). There is a strong differentiation of water content in melt inclusions, both between deposits and between various volcanics from a single deposit. Ore-bearing melts show the highest water contents of 3.34–4.07 wt %. High Cu contents in the silicic melts of the Yubileinoe and Kyzyl-Tashtyg deposits (up to 7118 and 3228 ppm, respectively) may indicate the affinity of some ore components to particular silicic magmas. This is supported by the elevated contents of Cu in the porphyry Cu deposits of Romania (Valea Morii), Mongolia (Bayan Ula), and Bolivia. On the other hand, the silicic melts of inclusions from the molybdenum-uranium deposit of the Strel’tsovka ore field show high contents of another group of ore components (U and F).     

Experimental study of fluorine and chlorine contents in mica (biotite) and their partitioning between mica,phonolite melt,and fluid

This paper reports the results of a study of the composition of mica (biotite) crystallizing in the system of phonolite melt-Cl- and F-bearing aqueous fluid at T ～ 850°C, P = 200 MPa, and \(f_{O_2 } \) = Ni-NiO, as well as data on F and Cl partitioning between coexisting phases. It was established that Cl content in mica is significantly lower than in phonolite melt and, especially, in fluid. Fluorine shows a different behavior in this system: its content in mica is always higher than in phonolite melt but lower than in fluid. The mica-melt partition coefficients of Cl and F also behave differently. The Cl partition coefficient gradually increases from 0.17 to 0.33 with increasing Cl content in the system, whereas the partition coefficient of F sharply decreases from 3.0 to 1.0 with increasing total F content. The apparent partition coefficients of F between biotite and groundmass (melt) in various magmatic rocks are usually significantly higher than the experimental values. It was supposed that the higher ^Bt/glassD_F values in natural samples could be related to the influence of later oxidation reactions, reequilibration of biotite at continuously decreasing \(f_{H_2 O} \)/f _HF ratio, and an increase in this coefficients with decreasing total F content in the system.     

Inclusions of silicate and sulfate melts in chrome diposide from the Inagli deposit,Yakutia, Russia

Melt inclusions were studied in chrome diopside from the Inagli deposit of gemstones in the Inagli massif of alkaline ultrabasic rocks of potassic affinity in the northwestern Aldan shield, Yakutia, Russia. The chrome diopside is highly transparent and has an intense green color. Its Cr₂O₃ content varies from 0.13 to 0.75 wt %. Primary and primary-secondary polyphase inclusions in chrome diopside are dominated by crystal phases (80–90 vol %) and contain aqueous solution and a gas phase. Using electron microprobe analysis and Raman spectroscopy, the following crystalline phases were identified. Silicate minerals are represented by potassium feldspar, pectolite [NaCa₂Si₃O₈(OH)], and phlogopite. The most abundant minerals in the majority of inclusions are sulfates: glaserite (aphthitalite) [K₃Na(SO₄)₂], glauberite [Na₂Ca(SO₄)₂], aluminum sulfate, anhydrite (CaSO₄), gypsum (CaSO₄ × 2H₂O), barite (BaSO₄), bloedite [Na₂Mg(SO₄)₂ × 4H₂O], thenardite (NaSO₄), polyhalite [K₂Ca₂Mg(SO₄)₄ × 2H₂O], arcanite (K₂SO₄), and celestite (SrSO₄). In addition, apatite was detected in some inclusions. Chlorides are probably present among small crystalline phases, because some analyses of aggregates of silicate and sulfate minerals showed up to 0.19–10.3 wt % Cl. Hydrogen was identified in the gas phase of polyphase inclusions by Raman spectroscopy. The composition of melt from which the chrome diopside crystallized was calculated on the basis of the investigation of silicate melt inclusions. This melt contains 53.5 wt % SiO₂, considerable amounts of CaO (16.3 wt %), K₂O (7.9 wt %), Na₂O (3.5 wt %), and SO₃ (1.4 wt %) and moderate amounts of Al₂O₃ (7.5 wt %), MgO (5.8 wt %), FeO (1.1 wt %), and H₂O (0.75 wt %). The content of Cr₂O₃ in the melt was 0.13 wt %. Many inclusions were homogenized at 770–850°C, when all of the crystals and the gas phase were dissolved. The material of inclusions heated up to the homogenization temperature became heterogeneous even during very fast quenching (two seconds) producing numerous small crystals. This fact implies that most of the inclusions contained a salt (rather than silicate) melt of sulfate-dominated composition. Such inclusions were formed from salt globules (with a density of about 2.5 g/cm³) occurring as an emulsion in the denser (2.6 g/cm³) silicate melt from which the chrome diopside crystallized.