Abstract. Unique bell-shaped underwater speleothems were recently reported from the deep (∼ 55 m) meromictic El Zapote sinkhole (cenote) on the Yucatán Peninsula, Mexico. The local diving community has termed these speleothems as Hells Bells because of their shape and appearance in a dark environment in ∼ 28–38 m water depth above a sulfidic halocline. It was also suggested that Hells Bells form under water, yet the mystery of their formation remained unresolved. Therefore, we conducted detailed hydrogeochemical and geochemical analyses of the water column and Hells Bells speleothems including stable carbon isotopes. Based on the comprehensive results presented in this study we deduce that both biogeochemical processes in the pelagic redoxcline and a dynamic halocline elevation of El Zapote cenote are essential for Hells Bells formation. Hells Bells most likely form in the redoxcline, a narrow 1–2 m thick water layer immediately above the halocline where a pelagic chemolithoautotrophic microbial community thrives from the upward diffusion of reduced carbon, nitrogen and sulfur species released from organic matter degradation in organic-rich debris. We hypothesize that chemolithoautotrophy, in particular proton-consuming nitrate-driven anaerobic sulfide oxidation, favors calcite precipitation in the redoxcline and hence Hells Bells formation. A dynamic elevation of the halocline as a hydraulic response to droughts, annual tidal variability and recharge events is further discussed, which might explain the shape of Hells Bells as well as their occurrence over a range of 10 m water depth. Finally, we infer that highly stagnant conditions, i.e., a thick halocline, a low-light environment and sufficient input of organic material into a deep meromictic cenote are apparent prerequisites for Hells Bells formation. This might explain their exclusivity to only a few cenotes in a restricted area of the northeastern Yucatán Peninsula.

Hydrothermal vents are a source of many trace metals to the oceans. Compared to mid-ocean ridges, hydrothermal vent systems at arcs occur in shallower water depth and are much more diverse in fluid composition, resulting in highly variable water column trace metal concentrations. However, only few studies have focused on trace metal dynamics in hydrothermal plumes at volcanic arcs. During R/V Sonne cruise SO253 in 2016/2017, hydrothermal plumes from two hydrothermally active submarine volcanoes along the Kermadec arc in the Southwest Pacific Ocean were sampled: (1) Macauley, a magmatic dominated vent site located in water depths between 300 and 680 m, and (2) Brothers, located between 1,200 and 1,600 m water depth, where hydrothermalism influenced by water rock interactions and magmatically influenced vent sites occur near each other. Surface currents estimated from satellite-altimeter derived currents and direct measurements at the sites using lowered acoustic Doppler current profilers indicate the oceanic regime is dominated by mesoscale eddies. At both volcanoes, results indicated strong plumes of dissolved trace metals, notably Mn, Fe, Co, Ni, Cu, Zn, Cd, La, and Pb, some of which are essential micronutrients. Dissolved metal concentrations commonly decreased with distance from the vents, as to be expected, however, certain element/Fe ratios increased, suggesting a higher solubility of these elements and/or their stronger stabilization (e.g., for Zn compared to Fe). Our data indicate that at the magmatically influenced Macauley and Brothers cone sites, the transport of trace metals is strongly controlled by sulfide nanoparticles, while at the Brothers NW caldera wall site iron oxyhydroxides seem to dominate the trace metal transport over sulfides. Solution stabilization of trace metals by organic complexation appears to compete with particle adsorption processes. As well as extending the generally sparse data set for hydrothermal plumes at volcanic arc systems, our study presents the first data on several dissolved trace metals in the Macauley system, and extends the existing plume dataset of Brothers volcano. Our data further indicate that chemical signatures and processes at arc volcanoes are highly diverse, even on small scales.

<p><strong>Abstract.</strong> Unique bell-shaped underwater speleothems were recently reported from the deep (~ 55 m) meromictic El Zapote sinkhole (cenote) on the Yucatán Peninsula, Mexico. The local diving community has termed these speleothems as Hells Bells because of their shape and appearance in a lightless environment in ~ 28–38 m water depth above a sulfidic halocline. It was also suggested that Hells Bells form under water, yet the mystery of their formation remained unresolved. Therefore, we conducted detailed hydrogeochemical and geochemical analyses of the water column and Hells Bells speleothems including stable carbon isotopes. Based on the comprehensive results presented in this study we deduce that both, biogeochemical processes in the pelagic redoxcline and a dynamic halocline elevation of El Zapote cenote, are essential for Hells Bells formation. Hells Bells most likely form in the redoxcline, a narrow 1–2 m thick water layer immediately above the halocline where a pelagic chemolithoautotrophic microbial community thrives from the upward diffusion of reduced carbon, nitrogen and sulfur species released from organic matter degradation in organic-rich debris. We hypothesize that chemolithoautotrophy, in particular the proton consuming nitrate-driven anaerobic sulfide oxidation, favors calcite precipitation in the redoxcline and hence Hells Bells formation. A dynamic elevation of the halocline as a hydraulic response to recharge events, e.g. hurricanes, is further discussed, which might explain the shape of Hells Bells as well as their occurrence over a range of 10 m water depth. Finally, we infer apparent prerequisites for Hells Bells formation considering the exclusivity of these underwater speleothems to only a few cenotes of a restricted area of the northeastern Yucatán Peninsula.</p>

Back-arc spreading centres and related volcanic structures are known for their intense hydrothermal activity. The axial volcanic edifice of Maka at the North Eastern Lau Spreading Centre is such an example, where fluids of distinct composition are emitted at the Maka hydrothermal field (HF) and at Maka South in 1,525–1,543 m water depth. At Maka HF black smoker-type fluids are actively discharged at temperatures of 329°C and are characterized by low pH values (2.79–3.03) and a depletion in Mg (5.5 mmol/kg) and SO4 (0.5 mmol/L) relative to seawater. High metal (e.g., Fe up to ∼6 mmol/kg) and rare Earth element (REE) contents in the fluids, are indicative for a rock-buffered hydrothermal system at low water/rock ratios (2–3). At Maka South, venting of white smoke with temperatures up to 301°C occurs at chimneys and flanges. Measured pH values range from 4.53 to 5.42 and Mg (31.0 mmol/kg), SO4 (8.2 mmol/L), Cl (309 mmol/kg), Br (0.50 mmol/kg) and Na (230 mmol/kg) are depleted compared to seawater, whereas metals like Li and Mn are typically enriched together with H2S. We propose a three-component mixing model with respect to the fluid composition at Maka South including seawater, a boiling-induced low-Cl vapour and a black smoker-type fluid similar to that of Maka HF, which is also preserved by the trace element signature of hydrothermal pyrite. At Maka South, high As/Co (>10–100) and Sb/Pb (>0.1) in pyrite are suggested to be related to a boiling-induced element fractionation between vapour (As, Sb) and liquid (Co, Pb). By contrast, lower As/Co (<100) and a tendency to higher Co/Ni values in pyrite from Maka HF likely reflect the black smoker-type fluid. The Se/Ge ratio in pyrite provides evidence for fluid-seawater mixing, where lower values (<10) are the result of a seawater contribution at the seafloor or during fluid upflow. Sulphur and Pb isotopes in hydrothermal sulphides indicate a common metal (loid) source at the two vent sites by host rock leaching in the reaction zone, as also reflected by the REE patterns in the vent fluids.