Stable sulfur and oxygen isotope ratios of the Świętokrzyski National Park spring waters generated by natural and anthropogenic factors (south-central Poland)

This paper presents the results of an isotopic study of spring waters in Świętokrzyski (Holy Cross Mountain) National Park (ŚNP), south-central Poland. The δ34SV-CDT and δ18OV-SMOW of soluble sulfates (n = 40) varied from 0.5‰ to 18.1‰ and from 3.5‰ to 12.2‰, respectively. The average δ34S values are closely similar to those of rainwater, soils and rocks (comprising scattered pyrite). This suggests that soluble sulfates in the springs originated from mixing of recent and historic deposition, sulfates derived from pyrite oxidation, and CS-mineralization in soils and debris. An additional anthropogenic sulfur input (inorganic fertilizer) occurs in the water of spring S-61 located in the Świętokrzyski National Park buffer zone. The δ18OV-SMOW of spring waters (n = 4) were in the range of −10.6‰ to −10.2‰ indicating that they are derived from vadose groundwater in ŚNP. This was the first isotope study of spring waters in the national parks of Poland. It enabled the determination of sulfur pathways and discrimination between natural and anthropogenic sources of this element in a relatively pristine area.

► We examined the spring waters from Świętokrzyski National Park in Poland. ► We determined the stable S and O isotope ratios. ► The δ34S pattern is similar to that of rainwater, soils and geologic makeup. ► The δ18O–H2O is indicative of present vadose origin of spring waters. ► Sulfur reduction and oxidation of S species are dominant fractionation processes.