Abstract
The aim of the study was to develop the hydrogeochemical profiling of caves based on the elemental composition of water and silty soil samples and a multivariate statistical analysis. Major and trace elements, including rare earths, were determined in the water and soil samples. The general characteristics of water, anions content, inorganic and organic carbon fractions and nitrogen species (NO3− and NH4+) were also considered. The ANOVA—principal component analysis (PCA) and two-way joining analysis were applied on samples collected from Cloșani Cave, Romania. The ANOVA-PCA revealed that the hydrogeochemical characteristics of Ca2+-HCO3− water facies were described by five factors, the strongest being associated with water-carbonate rock interactions and the occurrence of Ca, Mg and HCO3− (43.4%). Although organic carbon fractions have a lower influence (20.1%) than inorganic ones on water characteristics, they are involved in the chemical processes of nitrogen and of the elements involved in redox processes (Fe, Mn, Cr and Sn). The seasonal variability of water characteristics, especially during the spring, was observed. The variability of silty soil samples was described by four principal components, the strongest influence being attributed to rare earth elements (52.2%). The ANOVA-PCA provided deeper information compared to Gibbs and Piper diagrams and the correlation analysis.
Highlights
Caves are nonrenewable geological formations that include mineral deposits; paleontological remains; distinctive microbiology and archaeological, historical and cultural material remains
It was demonstrated that the inductively coupled plasma multielemental spectrometric techniques combined with a multivariate statistical analysis provided an advanced modeling of the water and solid samples in caves compared to the classical geochemical diagrams
The ANOVA-principal component analysis (PCA) revealed that the hydrogeochemical characteristics of the Ca2+ -HCO3 −
Summary
Caves are nonrenewable geological formations that include mineral deposits; paleontological remains; distinctive microbiology and archaeological, historical and cultural material remains. The formation of the speleothem is influenced by the concentration of the acids in the water, temperature and humidity of the cave; ground climate; annual rainfall and the density of the plant cover [1]. As major components in the karst system, pH and redox conditions, influence the trace element chemistry and the equilibrium between their mobile and nonmobile species [2]. Cave deposits, detrital materials and sediments are natural sources of metals occurrences in water [3,4]. Elevated concentrations of Ca, Mg, Sr and K in a cave can be explained by mineral weathering of the local bedrock and soil atop the cave under the influence of water and their transfer to the cave through dripping [5]
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