Organic geochemistry and mineralogy suggest anthropogenic impact in speleothem chemistry from volcanic show caves of the Galapagos

20 páginas.- 8 figuras.- 1 tabla.- 94 referencias.- Supplemental information can be found online at https://doi.org/10.1016/j.isci.2022.104556
The network of lava tubes is one of the most unexploited natural wonders of the Galapagos Islands. Here, we provide the first morphological, mineralogical, and biogeochemical assessment of speleothems from volcanic caves of the Galapagos to understand their structure, composition, and origin, as well as to identify organic molecules preserved in speleothems. Mineralogical analyses revealed that moonmilk and coralloid speleothems from Bellavista and Royal Palm Caves were composed of calcite, opal-A, and minor amounts of clay minerals. Extracellular polymeric substances, fossilized bacteria, silica microspheres, and cell imprints on siliceous minerals evidenced microbe-mineral interactions and biologically-mediated silica precipitation. Alternating depositional layers between siliceous and carbonate minerals and the detection of biomarkers of surface vegetation and anthropogenic stressors indicated environmental and anthropogenic changes (agriculture, human waste, and cave visits) on these unique underground resources. Stable isotope analysis and Py-GC/MS were key to robustly identify biomarkers, allowing for implementation of future protection policies.
This research work received funding from the European Commission’s 7th Framework Programme under the Marie Curie Intra-European Fellowship PIEF-GA-2012-328689-DECAVE. The financial support from the Spanish Ministry of Science and Innovation (MCIN) under the research project TUBOLAN PID2019- 108672RJ-I00 funded by MCIN/AEI/10.13039/501100011033 is also acknowledged. In addition, this work received support from: i) the Portuguese Foundation for Science and Technology (FCT) under the MICROCENO project (PTDC/CTA-AMB/0608/2020), the EROFIRE project (PCIF-RPG-0079-2018) and the project UID/Multi/04449/2019 for HERCULES/UE. A.Z.M. was supported by the CEECIND/01147/2017 contract from FCT, and the Ramón y Cajal contract (RYC2019-026885-I) from the MCIN. M.L.C. and N.T.J.M. were supported by CEECIND/00349/2017 and 2021/00711/CEECIND contracts, respectively, funded by FCT. F.G. was financially supported by the ‘‘HIPATIA’’ research program of the University of Almería and a Ramón y Cajal Fellowship (RYC2020-029811-I) of MCIN.