Jo De Waele

Trace element and stable isotope data from a flowstone in a natural cave of the mining district of SW Sardinia (Italy): evidence for Zn²⁺-induced aragonite precipitation in comparatively wet climatic conditions

INTRODUCTION Many natural caves in the Lower Cambrian limestones and dolostones of SW Sardinia (Italy) have been discovered during mine excavations in several Pb-Zn sulphide deposits. These “mine caves” host a wide variety of speleothems, both from a morphological and mineralogical point of view. Besides the rather uncommon cave minerals such as hemimorphite, hydrozincite, barite and cerussite, most of the speleothems are composed of aragonite and calcite. Another anomaly of the region is that aragonite is found here, in the stability field of calcite, in much larger quantities than in normal karstic settings. Many authors agree that the principal cause of metastable precipitation of aragonite in cave environments is related to the presence of Mg2+ in the percolating fluids (Hill & Forti, 1997 and references

Geomorphosites and Natural Hazards: Teaching the Importance of Geomorphology in Society

Geomorphosites and geological landscapes are among the most important tourist attractions of rural and mountain areas. In the past decades, especially thanks to several research and cultural projects on geological heritage, many regional and local authorities have started inventorying and publicising their landscapes and sites of geological and geomorphological interest publishing booklets, geotouristic maps and equipping their territories with explanatory panels. Nevertheless, geology and geomorphology are able to occupy the head titles of the major newspapers or make the breaking news on TV channels only when natural hazards hit the population. Making the processes that shape the morphologies at the Earth’s surface understandable to a wider public and helping people to “read” the wide variety of signs and remnants of recent or remote natural disasters might help to retain society’s memory of these phenomena and therefore minimise human and material losses. The geomorphological scars in the landscape that remind, if adequately interpreted, past natural and or human-induced disasters are ideal spots for geo-environmental education and should therefore be the subject of a scientific programme able to exploit their didactic value. This paper reports some interesting examples of such sites in Italy.

Microbial mediation of complex subterranean mineral structures

Helictites—an enigmatic type of mineral structure occurring in some caves—differ from classical speleothems as they develop with orientations that defy gravity. While theories for helictite formation have been forwarded, their genesis remains equivocal. Here, we show that a remarkable suite of helictites occurring in Asperge Cave (France) are formed by biologically-mediated processes, rather than abiotic processes as had hitherto been proposed. Morphological and petro-physical properties are inconsistent with mineral precipitation under purely physico-chemical control. Instead, microanalysis and molecular-biological investigation reveals the presence of a prokaryotic biofilm intimately associated with the mineral structures. We propose that microbially-influenced mineralization proceeds within a gliding biofilm which serves as a nucleation site for CaCO3, and where chemotaxis influences the trajectory of mineral growth, determining the macroscopic morphology of the speleothems. The influence of biofilms may explain the occurrence of similar speleothems in other caves worldwide, and sheds light on novel biomineralization processes.

Gypsum caves as indicators of climate-driven river incision and aggradation in a rapidly uplifting region

Detailed geomorphological analysis has revealed that subhorizontal gypsum caves in the Northern Apennines (Italy) cut across bedding planes. These cave levels formed during cold periods with stable river beds, and are coeval with fluvial terraces of rivers that flow perpendicular to the strike of bedding in gypsum monoclines. When rivers entrench, renewed cave formation occurs very rapidly, resulting in the formation of a lower level. River aggradation causes cave alluviation and upward dissolution (paragenesis) in passages nearest to the river beds. The U-Th dating of calcite speleothems provides a minimum age for the formation of the cave passage in which they grew, which in turn provides age control on cave levels. The ages of all speleothems coincide with warmer and wetter periods when CO 2 availability in the soils covering these gypsum areas was greater. This climate-driven speleogenetic model of epigenic gypsum caves in moderately to rapidly uplifting areas in temperate regions might be generally applicable to karst systems in different geological and climatic conditions.

Hypogene Karst Regions and Caves of the World

Signs of hypogenic speleogenesis have been detected in a number of caves of the Murcia Region (SE Spain), in some cases revealing active speleogenetic mechanisms rarely observed in hypogene cavities elsewhere in the world. Here, we investigate the hypogenic morphologies and speleothems of four caves in this region, namely Sima de la Higuera, Sima Destapada, Cueva del Agua and Cueva del Puerto. Also, other ten caves showing evidence for hypogenic speleogenesis has been preliminary described. Processes related to ancient and current hydrothermal activity, the discordance of permeability structures in the adjacent beds and the spatial arrangement of the regional hydrogeology have given rise to maze patterns and typical subaqueous hypogenic morphologies. These include spongework mazes, rising wall channels and shafts, feeders, bubble trails, solution pockets, megascallops and rising of chains cupolas, among others. Carbonic acid speleogenesis is responsible for the formation of most of these cave features; however, evidence of sulfuric acid speleogenesis (SAS) has been observed in Cueva del Puerto and Sima del Pulpo, which host massive secondary gypsum deposits. Speleothems typically linked to hydrothermal water upwelling and CO2 degassing close to the water table are present in most of these cavities, including folia, calcite spar crystals, cave clouds, calcite rafts deposits and several types of cave raft cones. The wide variety of hypogenic speleogenesis indicators and speleothems whose genesis is unconnected to meteoric water seepage reveals that the hydrothermal field of the Murcia Region hosts one of the densest active hypogenic subterranean networks in the world.

Rossiantonite, Al3(PO4)(SO4)2(OH)2(H2O)10•4H2O, a new hydrated aluminum phosphate-sulfate mineral from Chimanta massif, Venezuela: Description and crystal structure

Abstract Rossiantonite, ideally Al3(PO4)(SO4)2(OH)2(H2O)10·4H2O, triclinic (space group P1̄), a = 10.3410(5), b = 10.9600(5), c = 11.1446(5) Å, a = 86.985(2), b = 65.727(2), g = 75.064(2)°, V = 1110.5(1) Å3, Z = 2, is a new mineral from the Akopan-Dal Cin cave system in the Chimanta massif (Guyana Shield, Venezuela). The mineral occurs as small (≤0.15 mm) and transparent crystals in a white to slightly pink fine-grained sand, filling spaces between boulders of weathered quartz sandstone. Associated phases are gypsum, sanjuanite, rare alunite, quartz and micro-spherules of amorphous silica. Rossiantonite is colorless with a white streak and vitreous luster. The mineral is brittle with irregular to sub-conchoidal fracture and it shows a poorly developed cleavage. Rossiantonite is biaxial and not pleochroic, with mean refractive index of 1.504. The calculated density is 1.958 g/cm3. Electron microprobe analyses, with H2O measured by thermogravimetric analysis, provided the following empirical formula based on 28 O apfu: Al2.96Fe0.03P1.01S2H30.02O28. The five strongest lines in the X‑ray powder diffraction pattern, expressed as d (Å), I, (hkl) are: 4.647, 100, (210); 9.12, 56, (100); 4.006, 53, (220); 8.02, 40, (110); 7.12, 33, (011). The crystal structure, refined using 3550 unique reflections to R = 0.0292, is built of PO4 and AlO6 polyhedral rings, creating complex chains parallel b by sharing the OH-OH edge belonging to the Al(3) polyhedron. Three symmetrically independent Al sites can be identified, namely: Al(1), Al(2), and Al(3). Tetrahedral sites, occupied by P, share all their apexes with AlO6 octahedra. Unshared octahedral apexes are occupied by water molecules. Four additional water molecules are placed in between the previously identified chains. Two oxygen tetrahedra, occupied by S atoms, are connected along the chains by means of weak hydrogen bonding. The rossiantonite structure shows similarities with minerals belonging to the sanjuanite-destinezite group.

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.

Evaporite karst in Italy: a review

*jo.dewaele@unibo.it Citation:

Evolution of karst in Messinian gypsum (Monferrato, Northern Italy)

In the Tertiary Basin of Piedmont (Northern Italy) a 100-150 m thick Messinian sedimentary succession crops out, composed of pre-evaporitic clays, gypsum beds and post-evaporitic lacustrine-marine fine-grained sediments. In the Monferrato area the thickness of the evaporite sequence is highly variable (0-140 m) due to an important erosion surface formed at the end of the evaporite cycle and carved in the gypsum beds. Epigenic caves probably formed during this short intra-Messinian phase of emersion. Cave sediments contain benthonic and planctonic foraminiferal associations ranging in age from Burdigalian to Upper Pliocene. These sediments have probably been deposited in recent times, although it cannot be completely ruled out that they accumulated in caves developed in Upper Messinian times. The formation of the most important caves of this area probably started at the end of the Messinian under epigenic conditions. Possibly, those inherited caves enlarged slowly during the Quaternary in an intrastratal and confined hypogene karst system.

Petrographical and geochemical changes in Bosnian stalagmites and their palaeo-environmental significance

Detailed petrographic observations have been coupled with trace element and δ13C - δ18O analyses in order to investigate their dynamics in two Holocene Bosnian speleothems. The potential of this multiproxy approach in providing a means to extract palaeo-environmental information from stalagmites whose stable isotope signals are noisy and without obvious trends has been tested. The studied stalagmites are mostly characterized by columnar microcrystalline fabric. At the sub-millimetre scale of lamination, different microcrystalline columnar sub-types (open and closed) have been detected and classified on the basis of the observed porosity and the crystallite size. The presence of variations in crystallite arrangement at the lamina scale suggests the occurrence of small-scale environmental changes recorded in the studied samples. A positive correlation was found found between Mg concentration, δ13C and fabric variations, while a negative correlation relates those parameters with Sr concentration. Both δ13C and fabric changes appear to be directly related to changes in hydrology. The detailed observation of calcite fabrics combined with stable isotope and trace element profiles allowed for the interpretation of the conditions under which the speleothems were deposited.