Lighting Effects on the Development and Diversity of Photosynthetic Biofilm Communities in Carlsbad Cavern, New Mexico.

Photosynthetic cave communities ("lampenflora") proliferate in Carlsbad Cavern and other show caves worldwide due to artificial lighting. These biofilms mar the esthetics and can degrade underlying cave surfaces. The National Park Service recently modernized the lighting in Carlsbad Cavern to a light-emitting diode (LED) system that allows adjustment of the color temperature and intensity. We hypothesized that lowering the color temperature would reduce photopigment development. We therefore assessed lampenflora responses to changes in lighting by monitoring photosynthetic communities over the course of a year. We measured photopigments using reflected-light spectrophotometric observations and analyzed microbial community composition with 16S and 18S rRNA gene amplicon sequencing. Reflected-light spectrophotometry revealed that photosynthetic biofilm development is affected by lighting intensity, color temperature, substrate type, and cleaning of the substrate. Gene sequencing showed that the most abundant phototrophs were Cyanobacteria and members of the algal phyla Chlorophyta and Ochrophyta At the end of the study, visible growth of lampenflora was seen at all sites. At sites that had no established biofilm at the start of the study period, Cyanobacteria became abundant and outpaced an increase in eukaryotic algae. Microbial diversity also increased over time at these sites, suggesting a possible pattern of early colonization and succession. Bacterial community structure showed significant effects of all variables: color temperature, light intensity, substrate type, site, and previous cleaning of the substrate. These findings provide fundamental information that can inform management practices; they suggest that altering lighting conditions alone may be insufficient to prevent lampenflora growth.IMPORTANCE Artificial lighting in caves visited by tourists ("show caves") can stimulate photosynthetic algae and cyanobacteria, called "lampenflora," which are unsightly and damage speleothems and other cave surfaces. The most common mitigation strategy employs bleach, but altering intensities and wavelengths of light might be effective and less harsh. Carlsbad Cavern in New Mexico, a U.S. National Park and UNESCO World Heritage Site, has visible lampenflora despite adjustment of LED lamps to decrease the energetic blue light. This study characterized the lampenflora communities and tested the effects of color temperature, light intensity, rock or sediment texture, and time on lampenflora development. DNA amplicon sequence data show a variety of algae and cyanobacteria and also heterotrophic bacteria. This study reveals microbial dynamics during colonization of artificially lit surfaces and indicates that while lowering the color temperature may have an effect, management of lampenflora will likely require additional chemical or UV treatment.

Climatic and environmental conditions in the Western Galilee, during Late Middle and Upper Paleolithic periods, based on speleothems from Manot Cave, Israel.

Early Ahmarian, Levantine Aurignacian and Post-Levantine Aurignacian archeological assemblages show that the karstic Manot Cave, located 5 km east of the Mediterranean coast in the Western Galilee region of Israel, was intensively occupied during the Early Upper Paleolithic. The coexistence of these rich archaeological layers with speleothems in Manot Cave provides a window of opportunity for determining the relationships between climatic conditions and the nature of human activity and mobility patterns in the Western Galilee region during the Early Upper Paleolithic period. This study, based on four stalagmites that grew almost continuously from ∼75 to 26.5 ka, covers most of the last glacial, and overlaps with the human occupation of the cave. The speleothems oxygen (δ18O) and carbon (δ13C) isotopic records indicate that climate and environmental conditions fluctuated during the last glacial, some of which correspond with Dansgaard-Oeschger (D-O) cycles 12, 10, 7 and Heinrich (H) events VI and V. Consistent with independent evidence from botanic and faunal remains, these climatic shifts brought about significant environmental changes in the region, ranging from dominant thick Mediterranean forest to more open landscape. A good correlation with less negative δ13C values is most pronounced during the Early Ahmarian time period, but there was also a change to less negative δ13C values during the Levantine Aurignacian and Post-Levantine Aurignacian industries in the Levant. These positive δ13C shifts suggest that environmental transformation towards a more open grassy landscape dominated by C4 vegetation might have played an important role in the development of these cultural entities (mainly the Early Ahmarian) in Manot Cave region.

Impact of climate change on the transition of Neanderthals to modern humans in Europe.

Two speleothem stable isotope records from East-Central Europe demonstrate that Greenland Stadial 12 (GS12) and GS10-at 44.3-43.3 and 40.8-40.2 ka-were prominent intervals of cold and arid conditions. GS12, GS11, and GS10 are coeval with a regional pattern of culturally (near-)sterile layers within Europe's diachronous archeologic transition from Neanderthals to modern human Aurignacian. Sterile layers coeval with GS12 precede the Aurignacian throughout the middle and upper Danube region. In some records from the northern Iberian Peninsula, such layers are coeval with GS11 and separate the Châtelperronian from the Aurignacian. Sterile layers preceding the Aurignacian in the remaining Châtelperronian domain are coeval with GS10 and the previously reported 40.0- to 40.8-ka cal BP [calendar years before present (1950)] time range of Neanderthals' disappearance from most of Europe. This suggests that ecologic stress during stadial expansion of steppe landscape caused a diachronous pattern of depopulation of Neanderthals, which facilitated repopulation by modern humans who appear to have been better adapted to this environment. Consecutive depopulation-repopulation cycles during severe stadials of the middle pleniglacial may principally explain the repeated replacement of Europe's population and its genetic composition.

Holocene ENSO-related cyclic storms recorded by magnetic minerals in speleothems of central China.

Extreme hydrologic events such as storms and floods have the potential to severely impact modern human society. However, the frequency of storms and their underlying mechanisms are limited by a paucity of suitable proxies, especially in inland areas. Here we present a record of speleothem magnetic minerals to reconstruct paleoprecipitation, including storms, in the eastern Asian monsoon area over the last 8.6 ky. The geophysical parameter IRMsoft-flux represents the flux of soil-derived magnetic minerals preserved in stalagmite HS4, which we correlate with rainfall amount and intensity. IRMsoft-flux exhibits relatively higher values before 6.7 ky and after 3.4 ky and lower values in the intervening period, consistent with regional hydrological changes observed in independent records. Abrupt enhancements in the flux of pedogenic magnetite in the stalagmite agree well with the timing of known regional paleofloods and with equatorial El Niño-Southern Oscillation (ENSO) patterns, documenting the occurrence of ENSO-related storms in the Holocene. Spectral power analyses reveal that the storms occur on a significant 500-y cycle, coincident with periodic solar activity and ENSO variance, showing that reinforced (subdued) storms in central China correspond to reduced (increased) solar activity and amplified (damped) ENSO. Thus, the magnetic minerals in speleothem HS4 preserve a record of the cyclic storms controlled by the coupled atmosphere-oceanic circulation driven by solar activity.

A new interpretation of Madagascar's megafaunal decline: The "Subsistence Shift Hypothesis".

Fundamental disagreements remain regarding the relative importance of climate change and human activities as triggers for Madagascar's Holocene megafaunal extinction. We use stable isotope data from stalagmites from northwest Madagascar coupled with radiocarbon and butchery records from subfossil bones across the island to investigate relationships between megafaunal decline, climate change, and habitat modification. Archaeological and genetic evidence support human presence by 2000 years Before Common Era (BCE). Megafaunal decline was at first slow; it hastened at ∼700 Common Era (CE) and peaked between 750 and 850 CE, just before a dramatic vegetation transformation in the northwest that resulted in the replacement of C3 woodland habitat with C4 grasslands, during a period of heightened monsoonal activity. Cut and chop marks on subfossil lemur bones reveal a shift in primary hunting targets from larger, now-extinct species prior to ∼900 CE, to smaller, still-extant species afterwards. By 1050 CE, megafaunal populations had essentially collapsed. Neither the rapid megafaunal decline beginning ∼700 CE, nor the dramatic vegetation transformation in the northwest beginning ∼890 CE, was influenced by aridification. However, both roughly coincide with a major transition in human subsistence on the island from hunting/foraging to herding/farming. We offer a new hypothesis, which we call the "Subsistence Shift Hypothesis," to explain megafaunal decline and extinction in Madagascar. This hypothesis acknowledges the importance of wild-animal hunting by early hunter/foragers, but more critically highlights negative impacts of the shift from hunting/foraging to herding/farming, settlement by new immigrant groups, and the concomitant expansion of the island's human population. The interval between 700 and 900 CE, when the pace of megafaunal decline quickened and peaked, coincided with this economic transition. While early megafaunal decline through hunting may have helped to trigger the transition, there is strong evidence that the economic shift itself hastened the crash of megafaunal populations.

Pliocene reversal of late Neogene aridification.

The Pliocene epoch (5.3-2.6 Ma) represents the most recent geological interval in which global temperatures were several degrees warmer than today and is therefore considered our best analog for a future anthropogenic greenhouse world. However, our understanding of Pliocene climates is limited by poor age control on existing terrestrial climate archives, especially in the Southern Hemisphere, and by persistent disagreement between paleo-data and models concerning the magnitude of regional warming and/or wetting that occurred in response to increased greenhouse forcing. To address these problems, here we document the evolution of Southern Hemisphere hydroclimate from the latest Miocene to the middle Pliocene using radiometrically-dated fossil pollen records preserved in speleothems from semiarid southern Australia. These data reveal an abrupt onset of warm and wet climates early within the Pliocene, driving complete biome turnover. Pliocene warmth thus clearly represents a discrete interval which reversed a long-term trend of late Neogene cooling and aridification, rather than being simply the most recent period of greater-than-modern warmth within a continuously cooling trajectory. These findings demonstrate the importance of high-resolution chronologies to accompany paleoclimate data and also highlight the question of what initiated the sustained interval of Pliocene warmth.

Application of Scanning Electron Microscopy/Energy-Dispersive X-Ray Spectroscopy for Characterization of Detrital Minerals in Karst Cave Speleothems.

Micro-scale observations in karst caves help to identify different processes that shaped local morphology. Scanning electron microscopy/energy-dispersive X-ray spectroscopy inspection of speleothems from two karst caves in Slovenia, Predjama and Crna Jama, confirmed the presence of sub-angular to sub-rounded detrital fragments of clay minerals, feldspars, quartz, Fe-oxides/hydroxides, rutile and Nb-rutile, xenotime, kassite, allanite, fluorapatite, epidote, ilmenite, monazite, sphene, and zircon, between 2 and 50 µm across. These occur in porous layers separating calcite laminae in the clayey coating on the layer below the surface of the speleothems, and are also incorporated within actual crystals. It is likely that they are derived from the weathered rocks of the Eocene flysch. Probably they were first transported into the caves by floodwaters forming cave sediments. Later, depending upon the climate conditions, they were moved by air currents or by water to the surface of active speleothems. They might also be redeposited from overlying soils enriched with wind-transported minerals from the flysch, or from higher passages filled with weathered flysch sediment, by drip water percolating through the fissured limestone. As some of the identified minerals are carriers of rare earth elements, Ti and Zr, their presence could affect any palaeoclimatic interpretations that are based upon the geochemical composition of the speleothems.

Impact of water exhaled out by visitors in show caves: a case study from the Moravian Karst (Czech Republic).

The anthropogenic impact of the water and CO2 exhaled by visitors was studied in the show caves of the Moravian Karst (Czech Republic), especially in the Balcarka and Výpustek Caves. Two alternative models based on (1) the known/presumed composition of the breathed air and physical activity of visitors and (2) the detailed monitoring microclimatic data were proposed. The CO2 fluxes of 2.4 × 10-4 and (2.0-3.9) × 10-4 mol person-1 s-1 and the water vapor fluxes of (3.2-8.9) × 10-3 and (0.6-1.2) × 10-2 g person-1 s-1 were found for a slightly increased physical load. The total attendance and cave tour duration were the main driving factors. For the available data on attendance and accessibility periods, the total mass of water vapor exhaled by visitors in all show caves in the Moravian Karst was estimated between 9.6 × 106 and 4.3 × 108 g with significant seasonality. According to the geochemical model, this mass of water is capable of dissolving 1280 to 59,038 g of calcite, assuming a mean winter and summer CO2 concentration in the cave air of 1000 and 3000 ppmv. The larger extent of water condensation can lead to the so-called condensation corrosion, whereas the lower extent of condensation probably causes a recrystallization of calcite on the surface of speleothems and rocks.

Connecting molecular biomarkers, mineralogical composition, and microbial diversity from Mars analog lava tubes.

Lanzarote (Canary Islands, Spain) is one of the best terrestrial analogs to Martian volcanology. Particularly, Lanzarote lava tubes may offer access to recognizably preserved chemical and morphological biosignatures valuable for astrobiology. By combining microbiological, mineralogical, and organic geochemistry tools, an in-depth characterization of speleothems and associated microbial communities in lava tubes of Lanzarote is provided. The aim is to untangle the underlying factors influencing microbial colonization in Earth's subsurface to gain insight into the possibility of similar subsurface microbial habitats on Mars and to identify biosignatures preserved in lava tubes unequivocally. The microbial communities with relevant representativeness comprise chemoorganotrophic, halophiles, and/or halotolerant bacteria that have evolved as a result of the surrounding oceanic environmental conditions. Many of these bacteria have a fundamental role in reshaping cave deposits due to their carbonatogenic ability, leaving behind an organic record that can provide evidence of past or present life. Based on functional profiling, we infer that Crossiella is involved in fluorapatite precipitation via urea hydrolysis and propose its Ca-rich precipitates as compelling biosignatures valuable for astrobiology. In this sense, analytical pyrolysis, stable isotope analysis, and chemometrics were conducted to characterize the complex organic fraction preserved in the speleothems and find relationships among organic families, microbial taxa, and precipitated minerals. We relate organic compounds with subsurface microbial taxa, showing that organic families drive the microbiota of Lanzarote lava tubes. Our data indicate that bacterial communities are important contributors to biomarker records in volcanic-hosted speleothems. Within them, the lipid fraction primarily consists of low molecular weight n-alkanes, α-alkenes, and branched-alkenes, providing further evidence that microorganisms serve as the origin of organic matter in these formations. The ongoing research in Lanzarote's lava tubes will help develop protocols, routines, and predictive models that could provide guidance on choosing locations and methodologies for searching potential biosignatures on Mars.

Polycyclic aromatic hydrocarbon record in an urban secondary carbonate deposit over the last three centuries (Paris, France).

Preserving water resources and limiting pollution are central environmental issues in the current context of intense anthropization. Among organic pollutants, polycyclic aromatic hydrocarbons (PAHs) are commonly analysed as part of water quality assessments. After being emitted into the atmosphere, these persistent organic pollutants are deposited on the continental surface, where they are transported to the aquatic environment by run-off and infiltration waters. Mainly due to anthropogenic emissions, PAHs can therefore be considered as a proxy for human activities. Urban secondary carbonate deposits (USCDs), similar to cave speleothems, have recently been studied for their potential as natural archives of water quality. However, USCDs have never been used to trace water organic pollution and only a few studies on PAHs in speleothems are available. This study focuses on a well-dated USCD covering the last 300 years from the Great Aqueduct of Belleville (north-east of Paris, France). The aim is to determine the nature and variation of trapped organic compounds over time and to discuss their origin, transport, and link with changes in soil occupation due to human activities. To do so, high-resolution solid-phase UV fluorescence imaging analyses were combined with chemical analyses of PAHs and organic carbon carried out on low-weight samples. The results show that PAHs have been present in urban surface water for 300 years. Over the last few decades, a 7-fold increase is observed, accompanied by a change in the pollution source, enriched in high-molecular-weight PAHs, probably linked to urban dust. This study also reveals modes of transport directly influenced by changes in the soil occupation that are very different from those usually encountered in natural environments. This work thus paves the way for a better long-term understanding of the impact of human activity on the transfer of pollutants to sub-surface waters.

Biomineralization in Cave Bacteria-Popcorn and Soda Straw Crystal Formations, Morphologies, and Potential Metabolic Pathways.

Caves are extreme, often oligotrophic, environments that house diverse groups of microorganisms. Many of these microbes can perform microbiologically induced carbonate precipitation (MICP) to form crystalline secondary cave deposits known as speleothems. The urease family is a group of enzymes involved in MICP that catalyze the breakdown of urea, which is a source of energy, into ammonia and carbonate. Carbonate anions are effluxed to the extracellular surface of the bacterium where it then binds to environmental calcium to form calcium carbonate which then continues to grow in crystal form. Here, we studied bacterial communities from speleothems collected from the Iron Curtain Cave (ICC) in Chilliwack, B.C., Canada, to characterize these organisms and determine whether urease-positive (U+) bacteria were present in the cave and their potential impact on speleothem formation. The ICC is a carbonate cave located on the northside of Chipmunk Ridge, presenting a unique environment with high iron content sediment and limestone structures throughout. With six pools of water throughout the cave, the environment is highly humid, with temperatures ranging between 4 and 12°C depending on the time of year. Ninety-nine bacterial strains were isolated from popcorn (PCS) and soda straw (SSS) speleothems. These isolates were screened for urease enzymatic activity, with 11 candidates found to be urease-positive. After incubation, species-specific crystal morphologies were observed. Popcorn speleothem provided more bacterial diversity overall when compared to soda straw speleothem when examined under a culture-based method. Nearly twice as many U+ isolates were isolated from popcorn speleothems compared to soda straw speleothems. The U+ candidates were identified to the genus level by 16S rRNA analysis, and two isolates underwent whole-genome sequencing. Two novel species were identified as Sphingobacterium sp. PCS056 and Pseudarthrobacter sp. SSS035. Both isolates demonstrated the most crystal production as well as the most morphologically dissimilar crystal shapes in broth culture and were found to produce crystals as previously observed in both agar and broth media. The results from this study are consistent with the involvement of urease-positive bacteria isolated from the ICC in the formation of cave speleothems. 16S rRNA sequencing revealed a diverse set of microbes inhabiting the speleothems that have urease activity. Whole-genome sequencing of the two chosen isolates confirmed the presence of urease pathways, while revealing differences in urease pathway structure and number. This research contributes to understanding microbial-associated cave formation and degradation, with applications to cave conservation, microbiota composition, and their role in shaping the cave environment.

Insights into the microbial life in silica-rich subterranean environments: microbial communities and ecological interactions in an orthoquartzite cave (Imawarì Yeuta, Auyan Tepui, Venezuela).

Microbial communities inhabiting caves in quartz-rich rocks are still underexplored, despite their possible role in the silica cycle. The world's longest orthoquartzite cave, Imawarì Yeuta, represents a perfect arena for the investigation of the interactions between microorganisms and silica in non-thermal environments due to the presence of extraordinary amounts of amorphous silica speleothems of different kinds. In this work, the microbial diversity of Imawarì Yeuta was dissected by analyzing nineteen samples collected from different locations representative of different silica amorphization phases and types of samples. Specifically, we investigated the major ecological patterns in cave biodiversity, specific taxa enrichment, and the main ecological clusters through co-occurrence network analysis. Water content greatly contributed to the microbial communities' composition and structures in the cave leading to the sample clustering into three groups DRY, WET, and WATER. Each of these groups was enriched in members of Actinobacteriota, Acidobacteriota, and Gammaproteobacteria, respectively. Alpha diversity analysis showed the highest value of diversity and richness for the WET samples, while the DRY group had the lowest. This was accompanied by the presence of correlation patterns including either orders belonging to various phyla from WET samples or orders belonging to the Actinobacteriota and Firmicutes phyla from DRY group samples. The phylogenetic analysis of the dominant species in WET and DRY samples showed that Acidobacteriota and Actinobacteriota strains were affiliated with uncultured bacteria retrieved from various oligotrophic and silica/quartz-rich environments, not only associated with subterranean sites. Our results suggest that the water content greatly contributes to shaping the microbial diversity within a subterranean quartzite environment. Further, the phylogenetic affiliation between Imawarì Yeuta dominant microbes and reference strains retrieved from both surface and subsurface silica- and/or CO2/CO-rich environments, underlines the selective pressure applied by quartz as rock substrate. Oligotrophy probably in association with the geochemistry of silica/quartz low pH buffering activity and alternative energy sources led to the colonization of specific silica-associated microorganisms. This study provides clues for a better comprehension of the poorly known microbial life in subsurface and surface quartz-dominated environments.

Urbanization impact on sulfur content of groundwater revealed by the study of urban speleothem-like deposits: Case study in Paris, France.

Speleothem-like deposits that develop underground in urban areas are an archive of the environmental impact of anthropic activities that has been little studied so far. In this paper, the sulfate content in shallow groundwater from northern Paris (France) is compared with the sulfur content in two 300-year-old urban carbonate deposits that grew in a historical underground aqueduct. The present-day waters of the aqueduct have very high sulfur and calcium contents, suggesting pollution from gypsum dissolution. However, geological gypsum levels are located below the water table. Sulfur content was measured by micro-X-ray fluorescence in these very S-rich carbonate deposits (0.5 to 1% of S). A twofold S increase during the second half of the 1800s was found in both samples. These dates correspond to two major periods of urbanization above the site. We discus three possible S sources: anthropic sources (industries, fertilizers…), volcanic eruptions and input within the water through gypsum brought for urbanization above the studied site (backfill with quarry waste) since the middle of the 19th century. For the younger second half of the studied section, S input from gypsum brought during urbanization was confirmed by the study of isotopic sulfur composition (δ34S=+15.2‰ at the top). For the oldest part, several sulfur peaks could be related to early industrial activity in Paris, that caused high local air pollution, as reported in historical archives but also to historical gypsum extraction. This study provides information on the origin and timing of the very high SO42- levels measured nowadays within the shallow groundwater, thus demonstrating the interest in using carbonate deposits in urban areas as a proxy for the history of urbanization or human activities and their impact on water bodies.

Laser-induced breakdown spectroscopy for elemental characterization of calcitic alterations on cave walls.

Cave walls are affected by different kinds of alterations involving preservative issues in the case of ornate caves, in particular regarding the rock art covering the walls. In this context, coralloids correspond to a facies with popcorn-like aspect belonging to the speleothem family, mostly composed of calcium carbonate. The elemental characterization indicates the presence of elements that might be linked to the diagenesis and the expansion of the alterations as demonstrated by prior analyses on stalagmites. In this study, we report the use of laser-induced breakdown spectroscopy (LIBS) to characterize the elemental composition of one coralloid sample with a portable instrument allowing punctual measurements and a laboratory mapping setup delivering elemental images with spatial resolution at the micrometric scale, being particularly attentive to Mg, Sr, and Si identified as elements of interest. The complementarity of both instruments allows the determination of the internal structure of the coralloid. Although a validation based on a reference technique is necessary, LIBS data reveal that the external layer of the coralloid is composed of laminations correlated to variations of the LIBS signal of Si. In addition, an interstitial layer showing high LIBS signals for Fe, Al, and Si is interpreted to be a detrital clay interface between the external and the internal part of the coralloid. These preliminary results sustain a possible formation scenario of the coralloid by migration of the elements from the bedrock.

Sources of sulphate minerals in limestone cave-a possible evidence of anthropogenic activity: a case study in Crna Jama Cave (Slovenia).

In the caves, the formation of cave minerals is a consequence of a variety of chemical reactions, some of them also due to human activity. There are many caves in Slovenia, but sulphate minerals are not very often reported and analysed. In this study, the presence of sulphate minerals is detected by SEM/EDS analysis of speleothems from Crna Jama, a cave near Kocevje (southern Slovenia). The cave is characterised by its dark, almost black colour on cave walls, floor and speleothems. Anthropogenic influence in the cave is still visible, including the remains of a fireplace, some inscriptions on the walls and wooden containers. The analyses of some of the black-coated speleothems reveal the presence of calcium sulphate, confirmed by XRD as gypsum. Gypsum crystals are around 50 µm in size, and they occur in thin crusts. Additionally, some rare authigenic baryte crystals a few micrometres in size are detected. The sulphates δ34S value in gypsum found on dark coloured speleothems is + 10.4‰ Vienna Canyon Diablo Troilite (VCDT), while the sulphate δ34S of the bedrock is + 8.6‰ VCDT. The more likely source of sulphate ions is thus biomass burning rather than bedrock. Also, bedrock and biomass ash are a very probable source of calcium and barium. The highly probable pyrogenous origin of sulphates draws attention to human impact on cave mineralogy.

In situ Raman characterization of minerals and degradation processes in a variety of cultural and geological heritage sites.

We test the capabilities of in situ Raman spectroscopy for non-destructive analysis of degradation processes in invaluable masterpieces, as well as for the characterization of minerals and prehistoric rock-art in caves. To this end, we have studied the mechanism of decay suffered by the 15th-century limestone sculptures that decorate the retro-choir of Burgos Cathedral (N Spain). In situ Raman probe detected hydrated sulfate and nitrate minerals on the sculptures, which are responsible for the decay of the original limestone. In addition, in situ Raman analyses were performed on unique speleothems in El Soplao Cave (Cantabria, N Spain) and in the Gruta de las Maravillas (Aracena, SW Spain). Unusual cave minerals were detected in El Soplao Cave, such as hydromagnesite (Mg5(CO3)4(OH)2·4H2O), as well as ferromanganese oxides in the black biogenic speleothems recently discovered in this cavern. In the Gruta de las Maravillas, gypsum (CaSO4·2H2O) was identified for the first time, as part of the oldest cave materials, so providing additional evidence of hypogenic mechanisms that occurred in this cave during earlier stages of its formation. Finally, we present preliminary analyses of several cave paintings in the renowned "Polychrome Hall" of Altamira Cave (Cantabria, N. Spain). Hematite (Fe2O3) is the most abundant mineral phase, which provides the characteristic ochre-reddish color to the Altamira bison and deer paintings. Thus, portable Raman spectroscopy is demonstrated to be an analytical technique compatible with preserving our cultural and natural heritage, since the analysis does not require physical contact between the Raman head and the analyzed items.

Characterization of bacterial diversity associated with calcareous deposits and drip-waters, and isolation of calcifying bacteria from two Colombian mines.

Bacterial carbonate precipitation has implications in geological processes and important biotechnological applications. Bacteria capable of precipitating carbonates have been isolated from different calcium carbonate deposits (speleothems) in caves, soil, freshwater and seawater around the world. However, the diversity of bacteria from calcareous deposits in Colombia, and their ability to precipitate carbonates, remains unknown. In this study, conventional microbiological methods and molecular tools, such as temporal temperature gradient electrophoresis (TTGE), were used to assess the composition of bacterial communities associated with carbonate deposits and drip-waters from two Colombian mines. A genetic analysis of these bacterial communities revealed a similar level of diversity, based on the number of bands detected using TTGE. The dominant phylogenetic affiliations of the bacteria, determined using 16S rRNA gene sequencing, were grouped into two phyla: Proteobacteria and Firmicutes. Within these phyla, seven genera were capable of precipitating calcium carbonates: Lysinibacillus, Bacillus, Strenotophomonas, Brevibacillus, Methylobacterium, Aeromicrobium and Acinetobacter. FTIR and SEM/EDX were used to analyze calcium carbonate crystals produced by isolated Acinetobacter gyllenbergii. The results showed that rhombohedral and angular calcite crystals with sizes of 90µm were precipitated. This research provides information regarding the presence of complex bacterial communities in secondary carbonate deposits from mines and their ability to precipitate calcium carbonate from calcareous deposits of Colombian mines.

Analytical pyrolysis and stable isotope analyses reveal past environmental changes in coralloid speleothems from Easter Island (Chile).

This study comprises an innovative approach based on the combination of chromatography (analytical pyrolysis and pyrolysis compound-specific isotope analysis (Py-CSIA)), light stable isotopes, microscopy and mineralogy analyses to characterize the internal layering of coralloid speleothems from the Ana Heva lava tube in Easter Island (Chile). This multidisciplinary proxy showed that the speleothems consist of banded siliceous materials of low crystallinity with different mineralogical compositions and a significant contribution of organic carbon. Opal-A constitutes the outermost grey layer of the coralloids, whereas calcite and amorphous Mg hydrate silicate are the major components of the inner whitish and honey-brown layers, respectively. The differences found in the mineralogical, elemental, molecular and isotopic composition of these distinct coloured layers are related to environmental changes during speleothem development. Stable isotopes and analytical pyrolysis suggested alterations in the water regime, pointing to wetter conditions during the formation of the Ca-rich layer and a possible increase in the amount of water dripping into the cave. The trend observed for δ(15)N values suggested an increase in the average temperature over time, which is consistent with the so-called climate warming during the Holocene. The pyrolysis compound-specific isotope analysis of each speleothem layer showed a similar trend with the bulk δ(13)C values pointing to the appropriateness of direct Py-CSIA in paleoenvironmental studies. The δ(13)C values for n-alkanes reinforced the occurrence of a drastic environmental change, indicating that the outermost Opal layer was developed under drier and more arid environmental conditions.

Three centuries of heavy metal pollution in Paris (France) recorded by urban speleothems.

The first record of urban speleothems used to reconstruct the history of heavy metal pollution of shallow groundwaters is presented. Two speleothems grew during the last 300 years in an underground aqueduct in the north-eastern part of Paris. They display high Pb, Mn V, Cu, Cd and Al concentrations since 1900 due to the urbanization of the site which triggered anthropogenic contamination of the water feeding the speleothems. Surprisingly, these heavy metal concentrations are also high in the oldest part. This early pollution could come from the use of Parisian waste as fertilizers in the orchards and vineyards cultivated above the aqueduct before urbanization. Lead isotopes were measured in these carbonates as well as in lead artifacts from the 17th-18th centuries ((206)Pb/(207)Pb=1.180+/-0.003). The mean (206)Pb/(207)Pb ratio, for one of the speleothems is 1.181+/-0.003 unvarying with time. These lead signatures are close to those of coal and old lead from northern European mines, lower than the natural background signature. It confirms that the high metal concentrations found come from anthropogenic pollution. Conversely, the lead isotopic composition of the second speleothem presents two temporal trends: for the oldest levels, the mean value (1.183+/-0.003) is similar to the first speleothem. For the youngest part, a lower value (1.172+/-0.005) is recorded, evidencing the contribution of a new lead source at the beginning of the industrial revolution. Pb isotopes were also measured in recent samples from a nearby superficial site. The first sample is a recent (AD 1975+/-15 years) deposit ((206)Pb/(207)Pb=1.148+/-0.003), and the second, a thin subactual layer ((206)Pb/(207)Pb=1.181+/-0.002). These data are compatible with the adding of anthropogenic sources (leaded gasoline and industrial lead from Rio Tinto ore).