Rare Earth Elements Variations in a Hyperacid Crater Lake and Their Relations With Changes in Phreatic Activity, Physico-Chemical Parameters, and Chemical Composition: The Case of Poás Volcano (Costa Rica)

Decades of geochemical monitoring at active crater lakes worldwide have confirmed that variations in major elements and physico-chemical parameters are useful to detect changes in volcanic activity. However, it is still arduous to identify precursors of single phreatic eruptions. During the unrest phase of 2009–2016, at least 679 phreatic eruptions occurred at the hyperacid and hypersaline crater lake Laguna Caliente of Poás volcano (Costa Rica). In this study, we investigate the temporal variations of Rare Earth Elements (REE) dissolved in Laguna Caliente in order to 1) scrutinize if they can be used as a new geochemical tool to monitor changes of phreatic activity at hyperacid crater lakes and 2) identify the geochemical processes responsible for the variations of REE concentrations in the lake. The total concentration of REE varies from 950 to 2,773 μg kg−1. (La/Pr)N-local rock ratios range from 0.93 to 1.35, and Light REE over Heavy REE (LREE/HREE)N-local rock ratios vary from 0.71 to 0.95. These same parameters vary in relation to significant changes in phreatic activity; in particular, the (La/Pr)N-local rock ratio increases as phreatic activity increases, while that of (LREE/HREE)N-local rock decreases when phreatic activity increases. REE concentrations and their ratios were compared with the variations of major elements and physico-chemical parameters of the lake. Calcium versus (La/Pr)N-local rock and versus (LREE/HREE)N-local rock ratios show different trends compared to the other major elements (Na, K, Mg, Al, Fe, SO4, and Cl). Moreover, a higher loss of Ca (up to 2,835 ppm) in lake water was found with respect to the loss of Al, K, and Na. This loss of Ca is argued to be due to gypsum precipitation, a process corroborated by the mass balance calculation simulating the precipitation of gypsum and the contemporaneous removal of REE from the lake water. The observed relations between REE, changes in phreatic activity, and the parameters commonly used for the monitoring of hyperacid volcanic lakes encourage investigating more on the temporal and cause-effect relationship between REE dynamics and changes in phreatic activity at crater lake-bearing volcanoes.

Temperature and elemental sulfur shape microbial communities in two extremely acidic aquatic volcanic environments

Aquatic environments of volcanic origin provide an exceptional opportunity to study the adaptations of microbial communities to early planet life conditions such as high temperatures, high metal concentrations, and low pH. Here, we characterized the prokaryotic communities and physicochemical properties of seepage sites at the bottom of the Poas Volcano crater and the Agrio River, two geologically related extremely acidic environments located in the Central Volcanic mountain range of Costa Rica. Both locations hold a very low pH (pH 1.79−2.20) and have high sulfate and iron concentrations (Fe = 47−206 mg/L, SO42- = 1170-2460 mg/L measured as S), but significant differences in their temperature (90.0−95.0°C in the seepages at Poas Volcano versus 19.1−26.6 °C in Agrio River) and in the abundance of elemental sulfur. Based on the analysis of 16S rRNA gene sequences, we determined that Sulfobacillus spp., sulfur-oxidizing bacteria, represented more than half (58.4−78.4%) of the sequences in Poas Volcano seepage sites, while Agrio River was dominated by the iron− and sulfur−oxidizing Leptospirillum (7.4−55.5%) and members of the archeal order Thermoplasmatales (16.0−58.2%). Both environments share some chemical characteristics and part of their microbiota, however the temperature and the presence of reduced sulfur are likely the main distinguishing feature ultimately shaping their microbial communities. Our data suggest that in the Poas Volcano-Agrio River system there is a common metabolism but with specialization of species that adapt to the physicochemical conditions of each environment.