Pilot SERS Monitoring Study of Two Natural Hypersaline Lake Waters from a Balneary Resort during Winter-Months Period

Abstract

Water samples from two naturally hypersaline lakes, renowned for their balneotherapeutic properties, were investigated through a pilot SERS monitoring program. Nanotechnology-based techniques were employed to periodically measure the ultra-sensitive SERS molecular characteristics of the raw water-bearing microbial community and the inorganic content. Employing the Pearson correlation coefficient revealed a robust linear relationship between electrical conductivity and pH and Raman and SERS spectral data of water samples, highlighting the interplay complexity of Raman/SERS signals and physicochemical parameters within each lake. The SERS data obtained from raw waters with AgNPs exhibited a dominant, reproducible SERS feature resembling adsorbed β-carotene at submicromole concentration, which could be related to the cyanobacteria-AgNPs interface and supported by TEM analyses. Notably, spurious SERS sampling cases showed molecular traces attributed to additional metabolites, suggesting multiplexed SERS signatures. The conducted PCA demonstrated observable differences in the β-carotene SERS band intensities between the two lakes, signifying potential variations in picoplankton abundance and composition or environmental influences. Moreover, the study examined variations in the SERS intensity ratio I245/I1512, related to the balance between inorganic (Cl−-induced AgNPs aggregation) and organic (cyanobacteria population) balance, in correlation with the electrical conductivity. These findings signify the potential of SERS data for monitoring variations in microorganism concentration, clearly dependent on ion concentration and nutrient dynamics in raw, hypersaline water bodies.