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We have recently discovered significant amounts of zaccagnaite, a natural Zn-Al-CO 3 hydrotalcite in the El Soplao cave (north Spain). The El Soplao zaccagnaite is speleothemic, i.e., formed in the cave, and therefore it represents a new cave mineral. The origin of El Soplao zaccagnaite is related to the diagenesis of Zn-and Al-rich ferromanganese speleo-stromatolites, where it occurs as a porefilling cement that likely precipitated at low temperature (≤ ~11 °C). In some stromatolite layers, the abundance of zaccagnaite crystals is large enough to enable their physical separation. This has allowed us to obtain its X-ray powder-diffraction pattern, infrared spectrum, and differential thermal/ thermogravimetric profiles.The cell parameters of the El Soplao zaccagnaite, refined from X-ray powder diffraction data are: a = 3.06616(1) and c = 22.6164(1) Å [α = β = 90°, γ = 120°; V = 184.139(1) Å 3 ; Z = 3], consistent with a new trigonal polytype of zaccagnaite: zaccagnaite-3R. Besides, the El Soplao zaccagnaite shows some features previously unknown in natural hydrotalcites, such as octahedral-like morphologies and fluorescence zoning. Electron microprobe analyses revealed that the El Soplao zaccagnaite-3R has an unusual chemistry for natural hydrotalcites, as it is significantly more rich in Al (Zn 2+ /Al 3+ = 1.6) than the hexagonal (2H) polytype (Zn 2+ /Al 3+ = 2.0). The simplified chemical formula deduced from electron microprobe analysis is (Zn 0.6 Al 0.4 )(OH) 2 (CO 3 ) 0.2 ⋅0.5H 2 O, where C and water were calculated by stoichiometry. The carbon content calculated by stoichiometry (2.2 wt%) is in good agreement with that measured with the electron microprobe on gold-coated samples (2.5 wt%). The presence of interlayer water and CO 3 groups was confirmed by thermogravimetric analysis coupled to mass spectroscopy, and by the analysis of the infrared spectrum.

In the dark regions of caves, the formation of stromatolites is virtually unknown. Although Mn oxide crusts presumably induced by bacteria have been described in some caves, they lack stromatolite features, and the evidence of microbial origin is normally inconclusive. Here we describe for the fi rst time the occurrence of extensive Mn oxide stromatolites formed in the deep interior of a cave. The stromatolites are of decimeter thickness and kilometer extent and show features extremely similar to typical CaCO 3 stromatolites. However, unlike most stromatolites, their biogenicity is supported by the exceptional abundance of fossil microbes. Our data support that the stromatolites were mainly induced by chemolithotrophic Mn-oxidizing microbes, and were formed in a low-gradient water-table stream passage at least ~1 m.y. ago. The El Soplao stromatolites (Cantabria, Spain) may contribute to increasing our understanding of microbial life in extreme environments, as well as the role of bacteria in the genesis of modern and ancient Mn deposits.

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