Person:
Rossi Nieto, Carlos

First Name

Carlos

Last Name

Rossi Nieto

URI

https://hdl.handle.net/20.500.14352/75285

Affiliation

Universidad Complutense de Madrid

Faculty / Institute

Ciencias Geológicas

Department

Mineralogía y Petrología

Area

Petrología y Geoquímica

Identifiers

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Now showing 1 - 10 of 15

Manganese stromatolites in caves: El Soplao (Cantabria, Spain)
(Geology, 2010) Rossi Nieto, Carlos; Lozano, Rafael P.; Isanta, Nuria; Hellstrom, John
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 first 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 CaCO3 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.
Zaccagnaite-3R, a new Zn-Al hydrotalcite polytype from El Soplao cave (Cantabria, Spain)
(The American mineralogist, 2012) Lozano, Rafael Pablo; Rossi Nieto, Carlos; La Iglesia Fernández, Ángel; Matesanz, Emilio
We have recently discovered significant amounts of zaccagnaite, a natural Zn-Al-CO3 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) Å3 ; 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 (Zn2+/Al3+ = 1.6) than the hexagonal (2H) polytype (Zn2+/Al3+ = 2.0). The simplified chemical formula deduced from electron microprobe analysis is (Zn0.6Al0.4)(OH)2(CO3)0.2⋅0.5H2O, 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 CO3 groups was confirmed by thermogravimetric analysis coupled to mass spectroscopy, and by the analysis of the infrared spectrum.
Estromatolitos de manganeso en la cueva de El soplao (Cantabria)
(Enseñanza de las ciencias de la tierra, 2011) Rossi Nieto, Carlos; Lozano, Rafael Pablo; Isanta, Nuria
Replication and reinsertion of stalagmites sampled for paleoclimatic purposes
(International Journal of Speleology, 2018) Baeza, Eleuterio; Lozano, Rafael P.; Rossi Nieto, Carlos
Sampling stalagmites for paleoclimatic study can enter into conflict with preserving the beauty and integrity of caves. To minimize this impact, a variety of sampling strategies have been used by researches aware of cave-conservation issues. Based on our experience in two caves (El Soplao and La Buenita, Cantabria, N Spain), we propose to apply molding and casting laboratory techniques to create replicas of stalagmites, placing the replicas back in the original cave locations so that the impact of sampling to the cave is severely reduced. We provide detailed descriptions of the molding and casting methods, which vary depending on stalagmite size. For relatively small specimens (less than ~35 cm tall), we use a single-piece mold and two jackets. For larger stalagmites (~40-70 cm tall), we use a two-piece mold and two jackets. In a first casting step, we obtain a master piece in dental plaster that is preserved. In a subsequent casting step, we use epoxy resin to generate the replica that will be placed in the cave. We use extra-hard plaster coated with epoxy resin to fix the replicas to their original substrates. Both the epoxy resin and plaster are carefully dyed to match the original surface texture and color of the sampled stalagmites. Once in place, the stalagmite replicas are almost indistinguishable from the natural specimens.
Limited thermochemical sulfate reduction in hot, anhydritic, sour gas carbonate reservoirs: The Upper Jurassic Arab Formation, United Arab Emirates
(Marine and Petroleum Geology, 2019) Morad, Daniel; Nader, Fadi H.; Morad, Sadoon; Rossi Nieto, Carlos; Gasparrini, Marta; Alsuwaidi, Mohammad; Al Darmaki, Fatima; Hellevang, Helge
Limited thermochemical sulfate reduction (TSR) in hot (130–160°C) and anhydrite-rich sour gas reservoir carbonates of the Arab Formation (Upper Jurassic) is manifested by rare calcitization of anhydrite with slightly lower δ13CVPDB values (−3.2 to −0.1‰) than calcite precipitated in equilibrium with Late Jurassic seawater. Fluid inclusion microthermometry of calcite that has replaced anhydrite indicates that TSR occurred between 130°C and 160°C. The lack of evidence for extensive TSR, despite the suitable current temperatures and abundant sulfates in the gas reservoir, coupled with the relatively more common TSR-related calcite in the flanks (water zone) than crest (gas zone), indicate that: (1) gas emplacement while the reservoir was buried at shallower depth slowed down or inhibited TSR in the crest even when it subsequently reached depths where extensive TSR would occur, and (2) H2S (up to 38 vol%) has migrated from the underlying Permo-Triassic and/or Jurassic sulfate-carbonate deposits. This study demonstrates that constraining the timing of hydrocarbon emplacement within the context of burial-thermal history is crucial for a better understanding of the origin and distribution of H2S in hot, anhydrite-rich, sour gas reservoirs.
Paleo-watertable definition using cave ferromanganese stromatolites and associated cave-wall notches (Sierra de Arnero, Spain)
(Geomorphology, 2016) Rossi Nieto, Carlos; Villalaín, Juan José; Lozano, Rafael P.; Hellstrom, John C.
The steeply-dipping-dolostone-hosted caves of the Sierra de Arnero (N Spain) contain low-gradient relict canyons with up to ten mapped levels of ferromanganese stromatolites and associated wall notches over a vertical range of 85 m, the highest occurring ~460 m above base level. Despite a plausible speleogenetic contribution by pyrite oxidation, and the irregular cave-wall mesomorphologies suggestive of hypogenic speleogenesis, the Arnero relict caves are dominantly epigenic, as indicated by the conduit pattern and the abundant allogenic sediments. Allogenic input declined over time due to a piracy-related decrease in the drainage area of allogenic streams, explaining the large size of the relict Arnero caves relative to the limited present-day outcrop area of the karstified carbonates. Allogenic-sediment input also explains the observed change from watertable canyons to phreatic conduits in the paleo-downstream direction. Stromatolites and notches arguably formed in cavestream passages at the watertable. The best-defined paleo-watertables show an overall slope of 1.7°, consistent with the present-day relief of the watertable, with higher-slope segments caused by barriers related to sulfide mineralization. The formation of watertable stromatolites favored wall notching by the combined effect of enhanced acidity by Mn–Fe oxidation and shielding of cave floors against erosion. Abrasive bedload further contributed to notch formation by promoting lateral mechanical erosion and protecting passage floors. The irregular wallrock erosional forms of Arnero caves are related partly to paragenesis and partly to the porous nature of the host dolostones, which favored irregular dissolution near passage walls, generating friable halos. Subsequent mechanical erosion contributed to generate spongework patterns. The dolostone porosity also contributes to explain the paradox that virtually all Arnero caves are developed in dolostone despite being less soluble than adjacent limestone. U-series dating of carbonate speleothems and paleomagnetic data from ferromanganese stromatolites and clastic sediments indicate that the paleo-watertables recorded ~320 m above the presentday watertable formed during the Matuyama Chron but prior to ~1.5 Ma, implying long-term base- evellowering rates from ~125 to ~213 m/Ma. To our knowledge, this is the first attempt of paleomagnetic dating of cave ferromanganese stromatolites. These deposits are excellent geomagnetic recorders and offer a direct way to delineate and date paleo-watertables, especially in caves developed in dolostone.
The Messinian marine to nonmarine gypsums of Jumilla (Northern Betic Cordillera, SE Spain): Isotopic and Sr concentration constraints on the origin of parent brines
(Sedimentary Geology, 2015) Rossi Nieto, Carlos; Vilas Minondo, Lorenzo; Arias, Consuelo
The origin of the Messinian Hoya de la Sima (HS) gypsum (Betic foreland) is constrained using 87Sr/86Sr, δ34S, Sr concentration, and petrographic data. The Lower and Middle HS units consist of subaqueous vertically-aligned and stromatolitic selenites, the latter containing unusual microbial depositional textures. The Upper Unit consists of very-shallow-water bioturbated lenticular gypsum with Paracamelus ichnites. 87Sr/86Sr and δ34S indicate precipitation from predominantly marine waters, with upward increasing continental influence. Mixing models between Messinian seawater and continental water that dissolved Triassic evaporites show that the percentages of seawater required to explain the measured 87Sr/86Sr are analogous to the percentages obtained using δ34S, supporting precipitation from such mixtures. 87Sr/86Sr and δ34S of Lower HS selenites resemble those of the Primary Lower Gypsum (PLG) of the Messinian Salinity Crisis (MSC), in both cases indicating precipitation from seawater–continental water mixtures in which most Sr and SO4 were supplied by Messinian seawater. In the Lower HS selenites, Sr concentrations indicate contributing continental waters with Sr/Ca ratios similar to seawater. However, Sr concentrations of PLG selenites from other Betic basins (Bajo Segura, Sorbas indicate parent waters with Sr/Ca ratios lower than seawater. If the Sr contents of the betic PLG selenites are representative, it is unlikely that the Lower HS selenites represent the PLG. However, we cannot completely discard that option since different LPG subbasins could have had variable Sr/Ca. The HS gypsums formed coevally to diapirism of Triassic evaporites, in a restricted lagoonal basin developed during or slightly after a phase of strike-slip faulting in the Betic Cordillera. More general implications of this work are that Sr concentrations, combined with 87Sr/86Sr and δ34S data, provide key constraints on the origin of parent brines, and using Sr concentrations as paleosalinity proxy in gypsum precipitated from seawater–continental water mixtures is inconclusive because they largely depend on the initial Sr/Ca ratio of the brine. This study also illustrates that the electron microprobe is ideal to obtain reliable, spatially-resolved, Sr concentration data in selenitic gypsum. These data, in combination with fluorescence petrography, provide valuable criteria to discriminate primary depositional from diagenetic gypsum, a critical step in the interpretation of geochemical data.
Younger Dryas to Early Holocene paleoclimate in Cantabria (N Spain): Constraints from speleothem Mg, annual fluorescence banding and stable isotope records
(Quaternary Science Reviews, 2018) Rossi Nieto, Carlos; Bajo, Petra; Lozano, Rafael P.; Hellstrom, John
The Younger Dryas (YD) stadial represents the most abrupt climate change of the Earth's recent history. Thus, understanding its causes and different local responses is relevant for Quaternary paleoclimatology. We present a speleothem high-resolution proxy record of the Lateglacial to Early Holocene paleoclimate of the Cantabrian Cordillera (N Spain), a strategic location to evaluate the influence of North Atlantic events such as the YD on South-Western Europe. Fluorescence lamination, growth-rate, stable-isotope, and [Mg] records from stalagmite SIR-1 were dated using an age-depth model constrained by U-Th dates and annual-lamina counting. The YD is recorded as a prominent positive δ13C excursion whose chronology (12.95 ± 0.14 to 11.62 ± 0.16 ka) and shape closely agree with the GS-1 stadial as defined in Greenland ice, supporting the event synchronicity in both areas. A colder and drier YD climate limited soil productivity and dripwater availability, leading to higher δ13C and [Mg], reduced growth rate, and virtually absent fluorescence lamination. The early YD record (until ∼12.5 ka) reflects increasing aridity, whereas the late YD (from ∼12.2 ka on) shows the opposite trend. At the YD boundaries, temperature changes influenced the [Mg] record by modifying the Mg partition into calcite. However, this effect was superseded by major changes in dripwater Mg/Ca linked to rainfall variations. During the Early Holocene, the Arnero Sierra was forested and had a relatively warm and humid seasonal climate, indicated in SIR-1 by higher growth rates, lower δ13C and [Mg], and well-developed fluorescent lamination. Similar to other high-resolution stalagmitic records of the Cordillera, from ∼8.5 to 8.0 ka SIR-1 reflects a temporary trend of increasing aridity.
Hydrochemical controls on aragonite versus calcite precipitation in cave dripwaters
(Geochimica et Cosmochimica Acta, 2016) Rossi Nieto, Carlos; Lozano, Rafael P.
Despite the paleoclimatic relevance of primary calcite to aragonite transitions in stalagmites, the relative role of fluid Mg/Ca ratio, supersaturation and CO3 2 concentration in controlling such transitions is still incompletely understood. Accordingly, we have monitored the hydrochemistry of 50 drips and 8 pools that are currently precipitating calcite and/or aragonite in El Soplao and Torca Ancha Caves (N. Spain), investigating the mineralogy and geochemistry of the CaCO3 precipitates on the corresponding natural speleothem surfaces. The data reveal that, apart from possible substrate effects, dripwater Mg/Ca is the only obvious control on CaCO3 polymorphism in the studied stalagmites and pools, where calcite- and aragonite-precipitating dripwaters are separated by an initial (i.e. at stalactite tips) Mg/Ca threshold at 1.1 mol/mol. Within the analyzed ranges of pH (8.2–8.6), CO3 2 concentration (1–6 mg/L), supersaturation (SIaragonite: 0.08–1.08; SIcalcite: 0.23–1.24), drip rate (0.2–81 drops/min) and dissolved Zn (6–90 lg/L), we observe no unequivocal influence of these parameters on CaCO3 mineralogy. Despite the almost complete overlapping supersaturations of calcite- and aragonite-precipitating waters, the latter are on average less supersaturated because the waters having Mg/Ca above 1.1 have mostly achieved such high ratios by previously precipitating calcite. Both calcite and aragonite precipitated at or near oxygen isotopic equilibrium, and Mg incorporation into calcite was consistent with literature-based predictions, indicating that in the studied cases CaCO3 precipitation was not significantly influenced by strong kinetic effects. In the studied cases, the calcites that precipitate at 11 C from dripwaters with initial Mg/Ca approaching 1.1 incorporate 5 mol% MgCO3, close to the published value above which calcite solubility exceeds aragonite solubility, suggesting that aragonite precipitation in high-relative-humidity caves is favored from a solubility viewpoint. We also show that unaccounted CaCO3 precipitation in intermediate sampling containers and splash effects may in cases result in underestimating dripwater Ca concentration and alkalinity, potentially leading to incorrect conclusions regarding the role of fluid Mg/Ca ratio and supersaturation on CaCO3 mineralogy. A simple way to elude the first effect is by taking water samples directly from stalactites and by titrating alkalinity in the same containers used to collect dripwaters.
Exceptional preservation of Mn-oxidizing microbes in cave stromatolites (El Soplao, Spain)
(Sedimentary Geology, 2012) Lozano Fernández, Rafael; Rossi Nieto, Carlos
Many ferromanganese stromatolites of El Soplao Cave (N Spain) are characterized for the exceptional preservation and high diversity of ferromanganese stromatolites , probably representing the best example of microbial preservation described in ferromanganese deposits so far. The El Soplao stromatolites are mainly formed by polymetallic Mn-rich oxides with subordinate and variable amounts of detrital material, and consist of both dendritic and laminar microfacies. In both microfacies, microbial forms are abundant in the relatively pure Mn-oxide rich material, whereas they are scarce in areas with significant detrital material. Microbial forms are observed either in cross section, completely embedded in the Mn-oxide-rich matrix, or in three dimensions lining the walls of pores. Based on their morphology, we have separated the most abundant microbial forms into six main morphotypes and six additional submorphotypes, most of which can be assigned to bacteria. Most morphotypes consist of coccoid, coccobacilus, or filamentous forms. Therefore they are not diagnostic of any particular bacterial group. However, the ovoid cells of morphotype B show cylindrical polar protuberances typical of prosthecate alpha-Proteobacteria. On the basis of characteristic morphological features, three submorphotypes of morphotype B can be assigned to three alpha-Proteobacteria genera: Hyphomicrobium, Pedomicrobium, and Caulobacter. This ascription is supported by the well known Mn-oxidizing behavior of both Pedomicrobium and Caulobacter, and by the common presence of Hyphomicrobium in ferromanganese deposits elsewhere. The excellent microbial preservation is partly related to the origin of the ferromanganese oxides, i.e. extracellular precipitation induced by microbial metabolism. Other factors contributing to the good microbial preservation are the relatively low degree of diagenetic alteration, and the relatively high accretion rates of stromatolites compared to other ferromanganese deposits. The generally low degree of diagenesis is likely because the stromatolites have remained relatively stable and at a rather low temperature since they were formed at least 1 Ma ago. Still, some stromatolites have suffered diagenetic alteration (partial dissolution and replacement by calcium carbonates and Fe-rich oxides), obscuring or even obliterating their bioforms. The El Soplao case represents an example of how easily biogenic Mn oxides can be altered, and their bioforms blurred, in a relatively short geological time span in spite of being in a relatively stable, alkaline, and low-temperature setting. A geological implication is that the absence of bioforms in other ferromanganese deposits, including rock varnish and Precambrian iron formations, does not disprove their possible biogenic origin, since the high chemical reactivity of biogenic manganese oxides makes them highly vulnerable to diagenesis.