New Data on Hydrogeochemical and Isotopic Composition of Natural Waters of the Baidar Valley (Crimean Peninsula)

—Results of study of natural waters of the Baidar valley (southwestern Crimean Peninsula) obtained during the 2018–2019 field works are presented. Major groundwater resources of the study area are confined to the Upper Jurassic aquifer complex, which serves as a recharge source for the aquifer systems of the Plain Crimean and the Azov–Kuban’ artesian basins and hydrogeologic folded region of the Crimean Mountains mega-anticlinorium. The regional waters are fresh and ultrafresh, predominantly of calcium bicarbonate composition, with TDS varying from 208 to 1269 mg/dm3. The study enabled their classification into eight geochemical groups: (1) waters of a regional fracture zone in carbonate-terrigenous rocks affected by continental salinization; (2) waters of a regional fracture zone affected by leaching of aluminosilicates and sulfide oxidation; (3) waters of a regional fracture zone dominated by sodium aluminosilicates in the fracture filling (long-term interaction in the water–rock system), affected by continental salinization; (4) regional fracture zones dominated by sodium aluminosilicates affected by anthropogenic continental salinization; (5) groundwaters in fracture–vein aquifers affected by leaching of aluminosilicates and sulfide oxidation; (6) fracture–vein aquifers affected by leaching of sodium aluminosilicates (long-term interaction in the water–rock system); (7) waters in fractured karst aquifers; and (8) surface waters subjected to continental salinization. Fracture karst waters, which were found to be most protected against human impact and continental salinization processes, are slightly alkaline (pH = 7.7), fresh (with average TDS = 444 mg/dm3), with low silicon concentrations (2.23 mg/dm3), and of calcium bicarbonate composition. Waters residing in regional fracture and fracture–vein zones are affected by continental salinization and anthropogenic load and are neutral to alkaline (pH = 7.1–8.6), predominantly fresh (TDS = 269–1269 mg/dm3), with average silicon concentrations of 4.61–4.70 mg/dm3, of calcium bicarbonate composition, with high concentrations of sulfate ion, magnesium, and sodium. The waters of the Chernaya River, Chernorechensk reservoir, and lakes, which are also affected by continental salinization, are slightly alkaline (pH = 8.3), brackish (TDS = 207–364 mg/dm3), with an average silicon concentration of 1.18 mg/dm3, of calcium bicarbonate composition, with high concentrations of chlorine ion, magnesium, and sodium. The calculated intensity of chemical-element migration in waters of the background composition follows the descending order: very strong, I17.7 > Br14.4; strong, Se2.83 > B2.22 > Sr1.46 > Sb1.12 > Be1.07 > Hg1.06; moderately strong, Zn0.74 > Mo0.50 > Li0.46 > Sc0.41 > Ag0.18 > As0.16 > Si0.123 > Ba0.122; weak, Cr0.10 > Cu0.096 > Bi0.080 > Sn0.068 > Tl0.067 > P0.062 > Ni0.043 > Ta0.040 > Ge0.034 > Cd0.028 > Fe0.026 > Rb0.024 > Co0.023 > Pb0.020 > W0.017 > V0.012; very weak (inert), Nb0.008 > Hf0.0033 > Mn0.0031 > La0.0029 > Cs0.0022 > Ti0.0018 > Ga0.0016 > Y0.0013 > Al0.0008 > Zr0.0008. All the studied waters are found to be of atmospheric origin and located along the global (GMWL) and local (LMWL) meteoric water lines. Their δ18O value varies from –9.9 to –3.3‰, and δD value, from –64.2 to –32.5‰. Sedimentary carbonate rocks, atmospheric carbon dioxide, organic compounds, and hydrolysis of aluminosilicate minerals serve as the source of δ13C bicarbonate ion in natural waters of the Baidar valley. Surface waters have a heavier carbon isotope composition (δ13C = –9.2 to –6.2‰), which is due to atmospheric CO2, plant growth, and associated microbial activity. Fracture karst waters are characterized by a lighter carbon isotope composition (δ13C = –12.8 to –11.0‰) because of their interaction with dispersed organic matter. Waters of the regional fracture and fracture–vein zones display the widest variation in δ13C (–15.5 to –6.9‰), which is associated with a mixed type of “isotope supply” to the waters. A complex hydrogeochemical field that has formed in the Baidar valley tends to be increasingly affected by the anthropogenic factor.

Water Quality and Hydrogeochemical Characteristics of Some Karst Water Sources in Apuseni Mountains, Romania

Human activities and natural factors determine the hydrogeochemical characteristics of karst groundwaters and their use as drinking water. This study assesses the hydrogeochemical characteristics of 14 karst water sources in the Apuseni Mountains (NW Romania) and their potential use as drinking water sources. As shown by the Durov and by the Piper diagrams, the chemical composition of the waters is typical of karst waters as it is dominated by HCO3− and Ca2+, having a circumneutral to alkaline pH and total dissolved solids ranging between 131 and 1092 mg L−1. The relation between the major ions revealed that dissolution is the main process contributing to the water chemistry. Limestone and dolostone are the main Ca and Mg sources, while halite is the main Na and Cl source. The Gibbs diagram confirmed the rock dominance of the water chemistry. The groundwater quality index (GWQI) showed that the waters are of excellent quality, except for two waters that displayed medium and good quality status. The quality of the studied karst waters is influenced by the geological characteristics, mainly by the water–rock interaction and, to a more limited extent, by anthropogenic activities. The investigated karst waters could be exploited as drinking water resources in the study area. The results of the present study highlight the importance of karst waters in the context of good-quality water shortage but also the vulnerability of this resource to anthropogenic influences.

Land cover and land use change in karst region Devetashko plateau

The Corine Land Cover (CLC) is a digital data about land cover which is distributed into 44 classes whereas for the territory of Bulgaria the CLC classes are 36. The minimal mapping unit is 25 hectares (for 2D objects and 100 m for linear objects). Data sets for the years 1990, 2000, 2006, 2012, and 2018 are available, as well as for the changes which have occurred between each couple of years (1990–2000, 2000–2006, 2006–2012, and 2012–2018). The great data sets provide to track over a nearly 30-year period of land cover changes in model karst regions which are strongly vulnerable to anthropogenic and natural influences. This paper considers the changes in the land cover types on the Devetashko plateau – a typical karst plateau in North Bulgaria. Land cover and land use changes affect directly the processes of modern karst-genesis, the soil-vegetation cover, the quantity and quality of underground karst waters.

Antimicrobial resistant Escherichia coli from karst waters, surfaces and bat guano in Slovenian caves

Escherichia coli, one of the primary intestinal commensal bacteria in humans and endothermic animals, is commonly considered an indicator of faecal pollution. E. coli strains were isolated from karst rivers under different hydrological conditions, from footpaths in tourist caves and from bat guano. Isolates were tested for phenotypic resistance to ampicillin, chloramphenicol, ciprofloxacin, nalidixic acid, tetracycline and trimethoprim. The highest percentage of antimicrobial resistant E. coli was found in karst waters, followed by those from surface swabs and from bat guano. Several isolates from rivers and swabs exhibited multidrug-resistant phenotype. Environmental conditions impact the populations of E. coli; a positive correlation between dissolved oxygen and E. coli counts, and a negative correlation between conductivity and E. coli concentrations have been observed for karst rivers. Malenščica (Slovenia), a drinking water resource with an extensive catchment area, contained a relative high percentage of antimicrobial-resistant E. coli strains. None of the isolates from bat guano was resistant to ampicillin, chloramphenicol, and tetracycline. Future monitoring of bats should consider a regular follow-up of indicative microbial disease indicators in fresh guano. Regular cleansing of tourist footpaths in caves and disinfection barriers at the cave entrances reduce the concentration and transmission of E. coli significantly. A future, more detailed, study on characterization of additional E. coli isolates is needed to reveal their pathogeneicity, mechanisms of antibiotic resistance, mobile genetic elements, and gene transfer frequencies to other members of the karst microbiome.

Invisible dye tracing – an efficient technique for study of groundwater channels

We studied excitation spectra of uranine fluorescence in eluates from charcoal traps saturated in cave waters and in reference uranine solutions and found that the most appropriate excitation wavelength is 295±5 nm, because it excites fluorescence of uranine many times stronger than fluorescence of natural fluorescent compounds in groundwater. This allows us to lower the detection limit of uranine fluorescence with one order of magnitude, even below the level of natural fluorescence of karst waters at integral UV excitation.

Isotopic-geochemical features of thermal water of the Kyndyg deposit (Republic of Abkhazia)

Subject. The aim of the work is to study the mechanism and sources of water formation, as well as the peculiarities of carbonate mineralization in the aquifer of the Kyndyg thermal water deposit. Materials and methods. The samples of water (8) and deposited carbonates (15), collected at different seasons at three sites, characterized by different temperatures and distances from the source, were investigated. pH, Eh, and electrical conductivity were determined by an electrochemical method. For the determination of HCO3 – , Cl– , SO4 2–, titrimetric, mercurymetric and turbidimetric methods were used. Trace element composition was determined by ICP-MS (NexION 300S); strontium isotopic composition – by MC-ICP-MS (Neptune Plus) using the bracketing technique after Sr chromatographic separation. Results. The chloride-calcium hydrochemical type prevails in the studied waters. A number of trace elements in water exceeds the clarke concentrations for groundwater in the supergene zone of mountain landscapes. 87Sr/86Sr isotope ratios (0.7065–0.7072) in thermal waters suggest that their composition is determined rather by the isotopic characteristics of the rocks through which water drains than by the influence of sea water. Among the newly formed carbonates, aragonite prevails. In contrast to thermal water, the concentrations of most metals in carbonates are below the clarke values; only Sr and Se are increased, which content is significantly increased in water as well. Deposited carbonates are characterized by 87Sr/86Sr values (0.7028–0.7074), which are lower than in the source thermal waters. Conclusions. On the basis of hydrogeological, hydrochemical and geochemical data, it can be assumed that the waters of this aquifer complex are formed mainly due to fresh fractured karst waters of lower Cretaceous limestones with submerged monocline dipping into the zone of slow circulation and mixing with sedimentogenic sodium chloride waters. The geochemical data and the presence of scandium anomaly suggest that the underlying Jurassic volcanogenic rocks also participate in water exchange.

The Problems of Preserving the Paleolithic Image of a Camel in the Kapova Cave

The article presents an analysis of the causes for the unsatisfactory conservation state of the Upper Paleolithic wall image of a two-humped camel in the Kapova cave (South Ural, Republic of Bashkortostan). The work in revealing the monument's original colorful painting without a preliminary scientific examination of the layered calcite crusts, the absence among the organizers and participants of restoration specialists, archaeologists and karstologists with extensive work experience in the Kapova Cave - an archaeological monument of national significance, led to the corrosion of these unique images' colorful layers. The karstological and archaeological studies of the "Horses and Signs" panel in the Chaos Hall were undertaken in 2009 by the article's authors and are still ongoing. The discovery of the two-humped camel image and its significance for studying the culture of the Upper Paleolithic has pushed to the background the significant issue of preserving this image. The article presents the first review of the causes for the unsuccessful exposure of the monument's drawing. The modern state of the Chaos Hall in the Kapova Cave provides unfavorable conditions for the preservation of these drawings, exposed from beneath calcite crusts, which have acted as a natural preservative. The main factor of destruction is tied to the abundant focal infiltration of karst waters, which have variable physical and chemical parameters due to the high permeability of the rock mass. At the same time, there are no tested methods of protecting paint layers of exposed images in caves, which puts the Kapova Cave drawings at risk of rapid degradation. At the present stage of cave exploration, new clearing of drawings is unacceptable and may lead to their destruction.