Calcite Rafts Research Articles

Determining the age and origin of a Tertiary karstic system by in situ U-Pb geochronology on speleothems

Abstract Dating the onset of ancient (>1 Ma) karstification is a challenge. One approach is to date the earliest calcite cements in speleothems. We show the benefits of in situ U-Pb dating directly on thin sections from ancient (ca. 30 Ma) thin (<1 mm) speleothems in the karstified Lower Oligocene lacustrine-palustrine carbonates of the Paris Basin (France), which cannot be dated using other methods. We dated 32 calcite rafts (a type of speleothem), one geopetal cement, and 10 calcite cements precipitated along the karstic walls. The ages of the calcite rafts and cements at 29 ± 1 Ma (Lower Oligocene) fall within the age range of the host deposits (≈29 Ma) previously deduced from palaeontological evidence. We demonstrate that cementation of the carbonate host rock, its dissolution, and the speleothem precipitation occurred within 2 m.y. after deposition. Ostracods and intraclasts trapped within Rupelian calcite rafts clearly indicate that the karst developed deep underground shortly before a phase of lacustrine-palustrine sedimentation at the surface. This very early dissolution episode is attributed to the uplift of the Paris Basin as a result of the far-field intraplate deformation induced by the alpine orogenesis. This study shows that in situ U-Pb geochronology on ancient calcite rafts is a promising technique for the indirect dating of karstification and, more broadly, for dating geodynamic events and diagenetic evolution of sedimentary basins.

Nature-inspired discontinuous calcium coatings on polyglycolic acid for orthopaedic applications

Non-union in spinal fusion surgeries (SF) is a key cause of failure. Demineralized bone matrix is used in SFs to facilitate bone growth throughout the segment, and polyglycolic acid (PGA) meshes are used for their containment. A discontinuous calcium mineral coating could transform the function of PGA meshes from passive to active, where dissolved calcium ions could act as a chemoattractant for bone cells or it could form a barrier to prevent hydrolytic degradation of the mesh to better align its degradation profile with the fusion process. Challenges to depositing a mineral coating on PGA include its low glass transition temperature (~ 35 °C) and hydrolytic degradation.Inspired by calcite rafts in limestone cave pools, calcite grains were deposited on PGA meshes at the air–solution interface of supersaturated Ca(HCO3)2 (33 °C 6 h). X-ray diffraction (XRD) and 3D confocal microscopy were performed to assess phase composition and coating morphology. Durability was qualitatively assessed by mechanical tests. In vitro incubation was performed to elucidate the dynamic interactions between coating dissolution and PGA degradation; pH and calcium concentration of the solution were measured.XRD confirmed that coated PGA meshes were comprised of PGA and crystalline calcite. 3D confocal microscopy showed that the coatings were discontinuous and comprised of rhombohedral microcrystals. Retention of the particles following ultrasonic treatment and flexure/tensile testing indicates durability. Notably, the grains were compliant as the mesh was contorted. The interaction effect between the incubation time and pH for the uncoated and coated samples was statistically significant (p < 0.05).Graphical

Calcite raft formation in abandoned technical adit (Moravian Karst)

Current knowledge about the formation of calcite rafts was summarized and expanded with new data from the environment of a technical adit excavated in the 1950s in the central part of the Moravian Karst (Czech Republic). The location is within the temperate zone with an average annual temperature of 7–8 °C and an annual precipitation of 550–650 mm. Two different types of calcite rafts were identified: fine floating rafts (FF rafts) and massive calcite crusts (MC rafts). The transition from the FF raft to the MC raft requires the raft to be anchored to the side bank of the water pool. Once the FF rafts are anchored, they can grow on both sides (top and bottom) of the original air-water interface to form MC rafts. A comparison of water evaporation with CO2 degassing under given conditions showed that just degassing has been the key factor in achieving adequate supersaturation of drip water for nucleation of calcite at the air-water interface and for subsequent crystal growth. The conceptual two-layer model was designed and discussed in terms of the partial pressures of CO2 in the air and water in the adit. The discussion of the role of rafts in speleogenesis and paleohydrological reconstruction is supported by examples from the Sloup-Šošůvka caves (Moravian Karst).

Speleogenesis and depositional history of paleokarst phreatic caves/cavities; Podgrad, SW Slovenia

The studied paleokarst corresponds to an uplifted peripheral foreland bulge when Upper Cretaceous diagenetically immature eogenetic carbonates were subaerially exposed, karstified and subsequently overlain by upper Paleocene/lower Eocene palustrine limestone.Among the subsurface paleokarstic features, both vadose and phreatic forms occur. The phreatic caves/cavities include features characteristic of the mixing zone speleogenesis at the interface between freshwater (brackish water) lenses and the underlying seawater. They were found in various positions with respect to the paleokarstic surface, the deepest being about 75 m below the surface. Three indistinct horizons of cavities/caves and intermediate vugs were recognized. Subsequently, all cavities were completely filled with detrital sediments and speleothems in the phreatic and vadose zones. In general, the phreatic cavities of the lower two horizons are geopetally filled with mudstone derived from incomplete dissolution of the host rock and overlain by coarse-grained, blocky calcite. Shallower below the paleokarst surface, a large phreatic cave of the third horizon is filled with flowstone overlain by reddish micritic carbonate sediment with intercalated calcite rafts. In the upper part of the cave, sediments derived from the paleokarst surface are gradually becoming more abundant. Vadose channels, which may also intersect the cave sediments, are mainly filled with "pedogenic" material derived from the paleokarst surface. Immediately prior to marine transgression over the paleokarst surface, some cavities were filled with marine-derived microturbidites. In general, the diversity of cave fills and the amount of surface material decrease with distance from the paleokarst surface. Below the paleokarst surface, the δ13C and δ18O values of a host rock and cavity deposits show good correlation with trends significant for meteoric diagenesis. It is shown that deposits associated with phreatic caves can be of great importance for the study of the speleogenetic, geomorphological and hydrogeological evolution of certain paleokarst regions.

Seasonal trends in calcite-raft precipitation from cenotes Rainbow, Feno and Monkey Dust, Quintana Roo, Mexico: Implications for paleoenvironmental studies

Calcite-raft precipitation was monitored in three Yucatan cenotes (Rainbow, Feno and Monkey Dust) over a 2-year period. Site-specific variables including water temperature, relative humidity, water level and salinity were recorded as well as rainfall (Cozumel). Calcite-raft surface area was monitored through trail cameras that collected photographs every 60 min. Accumulation rates were recorded using sediment traps that were collected in May and December of each year. Calcite-raft surface area was calculated using an image segmentation procedure that identified the boundary of objects (edge detection) that share certain pixel characteristics, removed non-points of interest and measured the sum of the area covered by the raft material. Results show that large rainfall events have a regional effect on the meteoric water mass (i.e. salinity), as well as the precipitation of calcite rafts. The large rainfalls and increased inflows cause dilution of the CaCO3 supersaturated meteoric water mass and cause increased flow hindering calcite-raft precipitation for days to weeks after the rainfall. Raft precipitation gradually returns with deceasing flow after the event, and stagnation allows the recurrence of CaCO3 supersaturation and accumulation of nucleation particles. Small rainfalls did not seem to have the same effect, as slower percolation of rainwater through the epikarst would be more saturated and micro-topographic relief may isolate the water pools from the lower flow. The sediment trap data shows that calcite rafts accumulate relatively constantly throughout the year in all three sites. Sedimentation rates from Feno and Monkey Dust responded to seasonal changes in surface-water disturbance associated with rainfall (wet and dry), although Rainbow didn't show any seasonality likely due to other site-specific factors affecting water disturbance (e.g. bats, wind).

Calcite raft geochemistry as a hydrological proxy for Holocene aquifer conditions in Hoyo Negro and Ich Balam (Sac Actun Cave System), Quintana Roo, Mexico

Two cores from calcite rafts deposits located in Cenote Ich Balam and Hoyo Negro were dated and analyzed for 87Sr/86Sr, δ18O, δ13C, Sr/Ca and Cl/Ca. The geochemical records show changing aquifer salinity spanning the last ∼ 8.5 cal kyrs BP and interrelationships with Holocene climate trends (wet and dry periods). During the wet mid-Holocene, the salinity of the meteoric Water Mass (WM; at 7.8–8.3 cal kyrs BP) was relatively high at 1.5–2.7 ppt and then became less saline (1.0–1.5 ppt) during the last ∼ 7000 yrs as climate became progressively drier. High salinity of the meteoric WM during the wet mid-Holocene is attributed to increased turbulent mixing between the meteoric and underlying marine WM. Increased precipitation, in terms of amount, frequency, and intensity (e.g. hurricanes) causes higher flow of meteoric water towards the coast and mixing at the halocline, a phenomenon recorded with recent instrumental monitoring of the aquifer. Conversely, during dry periods reduced precipitation and flow in the meteoric WM would result in lower salinity. Karst properties and Holocene sea-level rise also seem to have an effect on the aquifer. When the regionally extensive network of shallow cave passages (∼ 10–12 m water depth) are flooded at ∼ 8000 cal yrs BP, there is a rapid shift in salinity. This study demonstrates that calcite raft deposits can be used as paleo-environmental recorders documenting the effects of sea level and climate change on aquifer condition.

The influence of human exploration on the microbial community structure and ammonia oxidizing potential of the Su Bentu limestone cave in Sardinia, Italy.

The bacterial diversity in the Su Bentu Cave in Sardinia was investigated by means of 16S rRNA gene-based analysis. This 15 km long cave, carved in Jurassic limestone, hosts a variety of calcite speleothems, and a long succession of subterranean lakes with mixed granite and carbonate sands. The lower level is occasionally flooded by a rising groundwater level, but with only scarce input of organic remains (leaves and charcoal fragments). On the quiet cave pools there are visible calcite rafts, whereas walls are locally coated with manganese deposits. In the drier upper levels, where organic input is much more subdued, moonmilk—a hydrated calcium-magnesium carbonate speleothem—can be found. Relative humidity approaches 100% and the measured mean annual cave air temperature is 14.8°C. Samples were obtained in 2014 from calcite rafts, moonmilk, manganese oxide deposits and soil (limestone and granite grains). Microclimatic conditions in the cave near the sampling sites, sample properties, physico-chemical parameters of water, and sediment composition were determined. The microbial community of this system is predominately composed of the phyla Proteobacteria, Actinobacteria, Acidobacteria, Nitrospirae, and Firmicutes. Sampling sites near the entrance of the cave and in close proximity of the underground campsite–located 500 meters deep into the cave—revealed the highest diversity as well as the highest number of human associated microorganisms. Two samples obtained in very close proximity of each other near the campsite, indicate that the human impact is localized and is not distributed freely within the system. Analysis of the abundance of bacterial and archaeal amoA genes revealed a far greater abundance of archaeal amoA genes compared to bacterial representatives. The results of this study highlight that human impact is confined to locations that are utilized as campsites and that exploration leaves little microbial trails. Furthermore, we uncovered a highly specialized microbiome, which is perfectly adapted to survive and thrive in an environment with low nutrient availability.

Growth and development of spring towers at Shiqiang, Yunnan Province, China

Throughout the world, high artesian pressures in hydrothermal areas have led to the growth of tall spring towers that have their vents at their summits. The factors that control their development and formative precipitates are poorly understood because these springs, irrespective of location, are mostly inactive. Spring towers found at Shiqiang (Yunnan Province, China), which are up to 4m high and 3m in diameter, are formed largely of calcite and aragonite crystal bushes, euhedral calcite crystals and coated grains with alternating Fe-poor and Fe-rich zones, calcite rafts, and cements formed of various combinations of calcite, aragonite, strontianite, Mg-Si reticulate, needle fiber calcite, calcified and non-calcified microbes, diatoms, and insects. Collectively, the limestones that form the towers can be divided into (1) Group A that are friable, porous and form the cores of the towers and have δ18OSMOW values of +15.7 to +19.7‰ (average 17.8‰) and δ13CPDB values of +5.1 to +6.9‰ (average 5.9‰), and (2) Group B that are hard and well lithified and found largely around the vents and the tower sides, and have δ18OSMOW values of +13.0 to +22.0‰ (average 17.6‰) and δ13CPDB values of +1.4 to +3.6‰ (average 2.6‰). The precipitates and the isotopic values indicate that these were thermogene springs. Growth of the Shiqiang spring towers involved (1) Phase IA when precipitation of calcite and aragonite bushes formed the core of the tower and Phase IB when calcite, commonly Fe-rich, was precipitated locally, (2) Phase II that involved the precipitation of white cements, formed of calcite, aragonite, strontianite, and Mg-Si reticulate coatings in cavities amid the Phase I precipitates, and (3) Phase III, which formed probably after spring activity ceased, when needle-fiber calcite was precipitated and the mounds were invaded by microbes (some now calcified), diatoms, and insects. At various times during this complex history, pore waters mediated dissolution of the calcite and aragonite and sometimes partial alteration of the aragonite. The diverse array of precipitates, depositional fabrics and diagenetic changes clearly indicate that the composition of the spring water changed frequently. Growth of the spring towers at Shiqiang continued until there was insufficient artesian pressure to lift the water above the top of the tower vent.

Mushroom Speleothems: Stromatolites That Formed in the Absence of Phototrophs

Unusual speleothems resembling giant mushrooms occur in Santa Catalina Cave, Cuba. Although these mineral buildups are considered a natural heritage, their composition and formation mechanism remain poorly understood. Here we characterize their morphology and mineralogy and present a model for their genesis. We propose that the mushrooms, which are mainly comprised of calcite and aragonite, formed during four different phases within an evolving cave environment. The stipe of the mushroom is an assemblage of three well-known speleothems: a stalagmite surrounded by calcite rafts that were subsequently encrusted by cave clouds (mammilaries). More peculiar is the cap of the mushroom, which is morphologically similar to cerebroid stromatolites and thrombolites of microbial origin occurring in marine environments. Scanning electron microscopy investigations of this last unit revealed the presence of fossilized extracellular polymeric substances (EPS) – the constituents of biofilms and microbial mats. These organic microstructures are mineralized with Ca-carbonate, suggesting that the mushroom cap formed through a microbially-influenced mineralization process. The existence of cerebroid Ca-carbonate buildups forming in dark caves (i.e., in the absence of phototrophs) has interesting implications for the study of fossil microbialites preserved in ancient rocks, which are today considered as one of the earliest evidence for life on Earth.

Reconstructing water level in Hoyo Negro, Quintana Roo, Mexico, implications for early Paleoamerican and faunal access

The skeletal remains of a Paleoamerican (Naia; HN5/48) and extinct megafauna were found at −40 to −43 mbsl in a submerged dissolution chamber named Hoyo Negro (HN) in the Sac Actun Cave System, Yucatan Peninsula, Mexico. The human remains were dated to between 12 and 13 Ka, making these remains the oldest securely dated in the Yucatan. Twelve sediment cores were used to reconstruct the Holocene flooding history of the now phreatic cave passages and cenotes (Ich Balam, Oasis) that connect to HN. Four facies were found: 1. bat guano and Seed (SF), 2. lime Mud (MF), 3. Calcite Rafts (CRF) and 4. Organic Matter/Calcite Rafts (OM/CRF) which were defined by their lithologic characteristics and ostracod, foraminifera and testate amoebae content. Basal radiocarbon ages (AMS) of aquatic sediments (SF) combined with cave bottom and ceiling height profiles determined the history of flooding in HN and when access was restricted for human and animal entry. Our results show that the bottom of HN was flooded at least by 9850 cal yr BP but likely earlier. We also found, that the pit became inaccessible for human and animal entry at ≈8100 cal yr BP, when water reaching the cave ceiling effectively prevented entry. Water level continued to rise between ≈6000 and 8100 cal yr BP, filling the cave passages and entry points to HN (Cenotes Ich Balam and Oasis). Analysis of cave facies revealed that both Holocene sea-level rise and cave ceiling height determined the configuration of airways and the deposition of floating and bat derived OM (guano and seeds). Calcite rafts, which form on the water surface, are also dependent on the presence of airways but can also form in isolated air domes in the cave ceiling that affect their loci of deposition on the cave bottom. These results indicated that aquatic cave sedimentation is transient in time and space, necessitating extraction of multiple cores to determine a limit after which flooding occurred.

Genesis of folia in a non-thermal epigenic cave (Matanzas, Cuba)

Folia are an unusual speleothem type resembling inverted cups or bracket fungi. The mechanism of folia formation is not fully understood and is the subject of an ongoing debate. This study focuses on an occurrence of folia present in Santa Catalina Cave, a non-thermal epigenic cave located close to Matanzas (Cuba). The sedimentology, morphology, petrology, permeability and geochemistry of these folia have been studied to gain new insight on the processes leading to their development. It is concluded that folia in Santa Catalina Cave formed at the top of a fluctuating water body, through CO2-degassing or evaporation, which may have been enhanced by the proximity to cave entrances. Two observations strongly support our conclusions. (1) When compared to other subaqueous speleothems (e.g. cave clouds) present in the same rooms, folia occur exclusively within a limited vertical interval that likely represents an ancient water level. Folia occur together with calcite rafts and tower cones that developed, respectively, on top of and below the water level. This suggests that a fluctuating interface is required for folia formation. (2) The measured permeability of the folia is too high to trap gas bubbles. Thus, in contrast to what has been proposed in other studies, trapped bubbles of CO2 cannot be invoked as the key factor determining the genesis and morphology of folia in this subaqueous environment.

Reconstructing a Miocene pitfall trap: Recognition and interpretation of fossiliferous Cenozoic palaeokarst

The middle Miocene cave deposit at AL90 Site in the Riversleigh World Heritage Area of Queensland, Australia, is the largest excavated palaeokarst deposit within the extensive Cenozoic freshwater limestones of the region. Stratigraphic relationships between various lithological components of the cave deposit indicate a dynamic, complex depositional history including dissolution, infill and reworking of cave materials. Euhedral spar, shelf-stone, calcite rafts and desiccation cracks on cave sediments suggest standing water was variably present in the cave environment. The AL90 Local Fauna is moderately diverse comprising at least 20 vertebrate families and 32 species, yet is taphonomically biased towards large marsupial herbivores (families Diprotodontidae, Macropodidae, and Balbaridae) and cave-dwelling hipposiderid bats. Fossil material is generally exceptionally well-preserved with, in many cases, articulated skeletons recovered. The cave entrance appears to have acted as a natural pit-fall trap. The complex (unconformable) depositional structure and lithology, vertebrate taphonomy and faunal composition at AL90 Site are typical of deposits and assemblages formed in the inner environment of the upper vadose zone. In the past, some similar unroofed cave deposits have been interpreted as clastic fluvio-lacustrine sedimentary deposits formed by surface processes. Analysis of characteristic palaeokarst features at AL90 Site has enabled the identification of other less well-preserved, poorly-exposed or relict cave deposits at Riversleigh and has facilitated interpretation of the depositional and palaeoenvironmental history of those deposits. The findings presented here confirm earlier interpretations that specific, highly-fossiliferous early Miocene to early Pliocene fossil deposits at Riversleigh represent relict caves whose roofs and walls are no longer intact.

Origin of double-tower raft cones in hypogenic caves

In the present paper, we describe the genetic mechanism that causes the precipitation of raft cones in caves. These speleothems usually form in a hydrothermal and epiphreatic environment where dripwater, dripping repeatedly over the same spot, sinks calcite rafts that were floating on the water surface of a cave pool. In particular, the paper describes a new variety of raft cones that were recently discovered in the Paradise Chamber of the Sima de la Higuera Cave (Murcia, south-eastern Spain) based on their morphological and morphometric characteristics. These speleothems, dubbed ‘double-tower cones’, have a notch in the middle and look like two cones, one superimposed over the other. The genetic mechanism that gave rise to the double-tower cones must include an intermediate stage of rapid calcite raft precipitation, caused by a drop in the water table and by changes in cave ventilation leading to greater carbon dioxide (CO2) degassing and evaporation over the surface of the thermal lake where these speleothems formed. Calcite rafts were deposited in Paradise Chamber, completely covering many of the cones. Later, conditions for slower calcite raft precipitation were restored and some of the cones continued to grow at the same points. When the water table finally fell below the level of Paradise Chamber, the tower cones became exposed, as the incongruent deposits of calcite rafts were dissolved and mobilized to lower cave levels. Copyright © 2013 John Wiley & Sons, Ltd.

Sea level controls sedimentation and environments in coastal caves and sinkholes

Quaternary climate and sea-level research in coastal karst basins (caves, cenotes, sinkholes, blueholes, etc.) generally focuses on analyzing isotopes in speleothems, or associating cave elevations prior sea-level highstands. The sediments in coastal karst basins represent an overlooked source of climate and sea-level information in the coastal zone, but to accurately interpret these sediments first requires an understanding of the forcing mechanisms that emplace them. In this study, we hypothesize that coastal karst basins transition through vadose, littoral, anchialine, and finally into submarine environments during sea-level rise because groundwater and sea level oscillate in near synchrony in the coastal zone, causing each environment to deposit a unique sedimentary facies. To test this hypothesis, the stratigraphy in twelve sediment cores from a Bermudian underwater cave (Green Bay Cave) was investigated and temporally constrained with twenty radiocarbon dates. The results indicate that we recovered the first succession spanning the entire Holocene from an underwater cave (~ 13 ka to present). The sediments were characterized with X-radiography, fossil remains, bulk organic matter, organic geochemistry (δ 13C org, C:N), and grain size analysis. Four distinct facies represent the four depositional environments: (i) vadose facies (> 7.7 ka, calcite rafts lithofacies), (ii) littoral facies (7.7 to 7.3 ka: calcite rafts and mud lithofacies), (iii) anchialine facies (7.3 to 1.6 ka: slackwater and diamict lithofacies), and (iv) submarine facies (< 1.6 ka: carbonate mud and shell hash lithofacies). The onset and duration of these sedimentary depositional environments are closely linked to Holocene sea-level rise in Bermuda, indicating that sea level controls environmental development in coastal karst basins. Finally, we present a conceptual model for interpreting the sediments and environments in coastal karst basins as a result of sea-level change.

Biotic versus abiotic calcite formation on prehistoric cave paintings: the Arcy-sur-Cure ‘Grande Grotte’ (Yonne, France) case

Abstract The ‘Grande Grotte’ cave at Arcy-sur-Cure (Yonne, France) with its prehistoric paintings shows important calcite concretions. Two types of calcite have been observed on the wall: translucent yellowish layers and opaque white or grey layers that completely obstruct the paintings. Other calcite types are present in the lakes of the cave (floating calcite rafts at the surface of the lake and soft calcite at the bottom of the lake). The morphology of the different calcites was observed at different scales by optical microscopy with normal and polarized light, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The elemental composition was measured by using particle-induced X-ray emission (micro-PIXE) and the structure by X-ray diffraction (XRD), infrared (FT-IR) and Raman spectroscopy. The bacterial diversity and its role in calcite formation were assessed by culture and 16S-SSCP in order to distinguish and to assess various abiotic and biotic formation mechanisms. The investigation of calcite characteristics enables conclusions on the formation mechanism and on a biotic or abiotic origin of the calcites. The change of calcite types on the walls reveals changes of the environmental cave parameters. In addition, interactions of calcites with the prehistoric paint layer could be evaluated.

An environmental model of fluvial tufas in the monsoonal tropics, Barkly karst, northern Australia

Spring-fed streams that deposit tufa (ambient temperature freshwater calcium carbonate deposits) in the tropics of northern Australia are influenced strongly by perennially warm water temperatures, high evaporation rates, and monsoon driven high-magnitude floods. This paper presents an environmental model that will aid interpretation of fossil fluvial tufas throughout monsoonal Australia. In the Barkly karst, northern Australia, tufas form in dam, cascade and pool/waterhole geomorphic environments. Each environment is represented in the morphostratigraphical record by a specific combination of tufa geomorphic units and facies associations. A diverse array of tufa facies is present, including microphytic, larval, calcite raft, macrophytic and allochthonous types. Preservation of particular Barkly karst tufa facies is thought to reflect the strength of monsoonal floods. A strong monsoon is represented by an abundance of flood indicators such as the allochthonous phytoclastic, lithoclastic and intraclastic tufa facies. Conversely, evidence of weak monsoons or a prolonged absence of floods may include oncoids, calcite rafts and thick accumulations of fine carbonate sediments. The history of the Australian monsoon is not fully understood. However, fossil tufa deposits, which record terrestrial climate information, have been preserved throughout northern Australia and hold great potential for reconstructing the region's climate history. Fossil tufa sequences at two Barkly karst sites have been interpreted using the new model. It can be applied to other Barkly karst fossil tufas as well as those in similar environments elsewhere in the world.

The formation and environmental significance of calcite rafts in tropical tufa‐depositing rivers of northern Australia

AbstractSpring‐fed rivers of the Barkly karst in tropical northern Australia form an array of tufa and related freshwater carbonate deposits. One of these deposits, calcite rafts, is precipitated at the water–air interface principally as a consequence of CO2 degassing and evaporation. Calcite rafts have been reported in cave environments but have not been described in detail from fluvial systems. Observations using scanning electron microscopy coupled with water chemistry data reveal that they form by a combination of physical, chemical and biological processes. They grow downwards into the water column and form a dentate lower surface, while a flat upper surface occurs at the water–air interface. The rafts are readily inhabited by microorganisms, particularly diatoms, which frequently become entombed by calcite as the rafts develop. The decay of the biological material leaves voids, creating a pock‐marked texture. The rafts are subject to secondary calcite growth along the crystal edges. Once they become submerged in the water column after disturbance of the water surface, they may become completely covered by this overgrowth, creating a homogeneous veneer. The rafts form in quiescent settings, principally behind tufa dams in large, lake‐like water bodies along each river. Therefore, they can be used in conjunction with adjacent exposures of other tufa facies to decipher palaeohydrological conditions. Although the rafts are extremely thin and fragile, they are readily preserved within fossil waterhole facies, and their occurrence has been identified in rocks from the Quaternary to the Tertiary.

Are current models of tufa sedimentary environments applicable to tropical systems? A case study from the Gregory River

Tufa formation in the Gregory River, tropical northern Australia, is strongly influenced by high evaporation rates, perennially warm water temperatures, construction behaviour of aquatic insect larvae, and regular high magnitude floods. These conditions contrast with those of the cool temperate tufa-depositing streams for which sedimentary models have already been developed. Gregory River tufas occur as multiple series of dams separated by waterholes, indicating that under all climatic conditions there is a persistence of hydraulic factors in controlling the dam-pool sequence in fluvial tufa systems. However, at the scale of individual tufa deposits and facies, the Gregory River system displays a deviation away from current models. Tufa domes, upstream-dipping ramps, calcite rafts and larval facies are all common and important features in both modern and fossil tufas of the Gregory River, but they are not included in current tufa models. Thus, specific sedimentary models need to be developed for seasonally humid tropical tufa systems to understand their formation and interpret them correctly in the rock record.

Detrital Origin of a Sedimentary Fill, Lechuguilla Cave, Guadalupe Mountains, New Mexico

AbstractLechuguilla Cave is a hypogene cave formed by oxidation of ascending hydrogen sulfide from the Delaware Basin. A unique sediment deposit with characteristics suggesting derivation from the land surface, some 285 m above, was investigated. At this location, the observed stratigraphy (oldest to youngest) was: bedrock floor (limestone), cave clouds (secondary calcite), calcite-cemented silstone, finely laminated clay, and calcite rafts. Grain-size analysis indicates that the laminated clay deposits are composed of 59-82% clay-size minerals. The major minerals of the clay were determined by X-ray diffraction analysis and consist of interstratified illite-smectite, kaolinite, illite, goethite, and quartz. Scanning electron microscopy observations show that most of the clay deposit is composed of densely packed irregularshaped clay-size flakes. One sample from the top of the deposit was detrital, containing well-rounded, silt-size particles.Surface soils are probably the source of the clay minerals. The small amount of sand- and silt-size particles suggests that detrital particles were transported in suspension. The lack of endellite and alunite is evidence that the clays were emplaced after the sulfuric-acid dissolution stage of cave formation. Fossil evidence also suggests a previously existing link to the surface.

Carbon and oxygen isotope study of the active water-carbonate system in a karstic Mediterranean cave: Implications for paleoclimate research in semiarid regions

In a semiarid climatic zone, such as the Eastern Mediterranean region, annual rainfall variations and fractionation processes in the epikarst zone exert a profound influence on the isotopic compositions of waters seeping into a cave. Consequently, the isotopic compositions of speleothems depositing from cave waters may show complex variations that need to be understood if they are to be exploited for paleoclimate studies. This is confirmed by a four-year study of the active carbonate-water system in the Soreq cave (Israel). The δ 18O (SMOW) values of cave waters range from −6.3 to −3.5%.. The highest δ 18O values occur at the end of the dry season in waters dripping from stalactites, and reflect evaporation processes in the epikarst zone, whereas the lowest values occur in rapidly dripping (fast-drip) waters at the peak of the rainy seasons. However, even fast-drip waters are about 1.5%. heavier than the rainfall above the cave, which is taken to reflect the mixing of fresh with residual evaporated water in the epikarst zone. δ 13C (PDB) values of dissolved inorganic carbon (DIC) vary from −15.6 to −5.4%., with fast-drip waters having lower δ 13C values (mostly −15.6 to −12%.) and higher DIC concentrations relative to pool and stalactite-drip water. The low δ 13C values of fast-drip waters and their supersaturation with respect to calcium carbonate indicates that the seepage waters have dissolved both soil-CO 2 derived from overlying C 3-type vegetation and marine dolomite host rock. The δ 18O (PDB) values of various types of present-day low-magnesium calcite (LMC) speleothems range from −6.5 to −4.3%. and δ 13C values from −13 to −5.5%. and are not correlated with speleothem type. An analysis of δ 18O values of present-day calcite rafts and pool waters shows that they form in oxygen isotope equilibrium. Similarly, the measured ranges of δ 13C and δ 18O values for all types of present-day speleothems are consistent with equilibrium deposition at cave temperatures. The δ 13C– δ 18O range of contemporary LMC thus reflects the variations in temperatures and isotopic compositions of the presentday cave waters. The 10%. variation in the δ 13C values in waters can be modeled by a simple Rayleigh calculation of the carbon isotope fractionation accompanying CO 2-degassing and carbonate precipitation. These variations may obscure the differences in the carbon isotopic composition of speleothems that could arise when vegetation cover changes from C 3 to C 4-type plants. This consideration emphasizes that it is necessary to characterize the full range of δ 13C values associated with contemporaneous speleothems in order to clarify the effects of degassing from those due to differing vegetation types. Isotopic studies of a number of different types of fossil LMC speleothems show many of them to exhibit isotopic trends that are similar to those of present-day LMC, but others show both higher and lower δ 18O ranges. In particular, the higher δ 18O range has been shown by independent age-measurements to be associated with a period of drier conditions. The results of the study thus indicate that it is necessary to work on a well calibrated cave system in semiarid climates and that the fossil speleothem record should be obtained from different types of contemporaneous deposit in order to fully characterize the δ 18O–δ 13C range representative of any given climatic period.