Geochemical and mineralogical composition of black weathering crusts on limestones from seven different European countries

Twenty-seven samples of black weathering crust and host carbonates were studied from seven European countries (Germany, Hungary, Belgium, Czech Republic, France, Italy and Poland) representing 11 different sites. The samples were collected for sites for which long-term air pollution records are available. The mineralogical analyses (XRD, polarizing microscopy, SEM) have shown that despite decreasing SO₂ emissions crust samples are still very rich in gypsum. Further, in all host rock samples gypsum was also detected. Good correlations (R² > 0.9) were also found between water-soluble calcium and gypsum content and between sulphate and gypsum content both for black crusts and host rocks. The black gypsum crusts are four or five times richer in sulphate than the host rock. The conductivity of dissolved crust and host rock samples also shows a positive correlation with gypsum content of the samples. LA-ICP-MS analyses allowed the detection of high Pb-levels in black crusts and a negative shift in lead concentration at the crust/host rock transition. The lead content of the host rock is 2–5 mg/kg, while that of the crust is 3–25 mg/kg in the sample collected from Germany, while in the Belgian sample these values are 2–14 mg/kg and 80–870 mg/kg for the host rock and crust, respectively. The GC–MS technique allowed to detect the PAH content of black crusts and host rocks. The former one contains 0.6–15.6 (102.5) mg/kg, while in the host rock values between 0.2 and 2.4 mg/kg were found. The present study suggests that still large amounts of air pollution-related minerals and organic pollutants are found in the black weathering crusts of European carbonate buildings despite decreasing trends in air pollution.     

Urban and rural limestone weathering; the contribution of dust to black crust formation

A novel approach of studying dust, black crust and host limestones by using various techniques is presented in this paper. Samples were collected from limestone monuments located in rural, urban and industrial areas in Germany and Hungary. The paper focuses on differences in the mineralogical composition, major and trace element distribution of materials and their total polyaromatic hydrocarbons (PAH) concentration having different exposure to air pollutants. High concentration of gypsum was found in laminar and dendritic black crusts and even in the dust of both urban and rural areas, despite the low concentration of SO₂ in rural atmospheric environments. The black crusts show a typical microfabric with distinct layers of various gypsum–calcite mineral associations, silt-sized mineral fragments and black particle content. In dust, newly formed gypsum crystals were found along with mineral fragments, and siliceous and, less frequently, carbonaceous fly ash particles. High concentration of lead was found both in the samples of urban and rural areas of Germany and Hungary. Lead mostly accumulates in dust and also in the black crust. Highest lead concentrations were found not on the surface of the black crust, but close to the crust/limestone boundary according to LA-ICPMS analyses. It indicates that despite the ban of leaded petrol, lead is still present in the dust and the in the soiled zones of the built environment. Similarly to lead, no significant difference in the total PAH content of dust and crust samples were found in the two countries. Dusts are equally enriched in PAH in both countries, whereas black crusts contain fewer amounts. Most of the aqueous extracts of the samples were saturated with respect to sulphate, which also indicate the presence of gypsum, whilst in some German samples unsaturated conditions were detected. In summary, by using a combination of these analytical techniques, it was possible to distinguish rural and urban samples and to outline the role of dust in bringing pollutants to the stone surface. It is suggested that the analysed dust and stone samples indicate not only present, but also the past, pollution fluxes and as a consequence stones similar to sediments or surface waters can be used as environment indicators.     

Black crusts on travertine: factors controlling development and stability

The travertine buildings of Budapest show extensive black crust formation, which is related to high concentration of atmospheric pollution and a continental climate. Laminar black crusts, framboidal black crusts and leached white surfaces are compared. Physical properties (Schmidt hammer rebound, Duroscope rebound), mineralogical composition and elemental composition are measured. Framboidal black crusts contain more than 50% of acicular gypsum. The crust surface displays idiomorphic rosette-like gypsum crystals with particulates, calcite and gypsum crystal aggregates. The sulphur isotopic composition of the black crusts pinpoints the involvement of rain and dust in crust formation. Thick framboidal black crust has the lowest strength while thin laminar black crust and white dissolved surfaces show minor decrease in surface strength compared to unaltered travertine. The crusts adhere to the travertine surface and rarely show mechanical decay forms that are typical features of porous limestone ashlars in Budapest.     

Mineralogical,geochemical and microfabric evidences of gypsum crusts: a case study from Budapest

High levels of SO₂ and particulate pollution enable the rapid development of gypsum-rich weathering crusts in Budapest. Two types of white crusts, thin and thick ones, and two forms of black crusts, laminar and framboidal ones, were studied in limestone buildings of the parliament and Citadella. The percentage of crust cover and damage categories were documented on selected walls. Petrographic, XRD, XRF and sulphur isotope analyses were performed under laboratory conditions to understand the mechanism of crust formation. White crusts found both on exposed and sheltered walls display a calcite-rich layer with gypsum, while black crusts are enriched with gypsum. The sulphur isotopic composition of white and black crusts overlaps, but the crusts are slightly enriched in heavy isotopes compared to rainwater. S content, Si/Al ratios and particulates in black crusts suggest that air pollution (SO₂, dust) contributes to black crust formation. The accumulation of sulphur and Zn enrichment of white crusts were also documented indicating that under high pollution levels, even these compound can accumulate on exposed facades.     

The effect of air pollution on stone decay: the decay of the Drachenfels trachyte in industrial, urban, and rural environments—a case study of the Cologne, Altenberg and Xanten cathedrals

Severe stone deterioration is evident at the Cologne cathedral. In particular, the “Drachenfels” trachyte, which was the building material of the medieval construction period, shows significant structural deterioration as well as massive formation of gypsum crusts. The present article investigates crust formation on limestone, sandstone, and volcanic rock from the Cologne cathedral as well as from the Xanten and Altenberg cathedrals. These three buildings, showing varying degrees of deterioration, are located in different areas and exposed to varying industrial, urban, and rural pollution. Thin laminar and black framboidal crusts form on calcareous as well as silicate stone. The lack of a significant intrinsic calcium and sulfur source for the formation of the gypsum crusts on the Drachenfels trachyte indicates major extrinsic environmental impact: a sufficient offer of SO _x from pollutant fluxes as well as external calcium sources (e.g., pollution, mortars, neighboring calcite stones). Chemical analyses reveal strong gypsum enrichment within the crusts as well as higher concentrations of lead and other pollutants (arsenic, antimony, bismuth, tin, etc.), which generally can be linked to traffic and industry. The formation of weathering crusts in an industrial environment is clearly distinguishable from that in rural areas. Scanning electron microscopy observations confirm that the total amount of pollution is less at the Altenberg cathedral than at the Cologne and Xanten cathedrals. XRF analyses show that the formation of gypsum occurs in lower amounts at Altenberg. This correlates well with the measured SO₂ content and the intensity of the decay at the different locations. Furthermore, the different types of crusts, e.g., framboidal and laminar, can be differentiated and assigned to the different locations. The black weathering crusts on the silicate Drachenfels trachyte contribute to the degradation of the historic building material. They enhance mechanical moisture-related deterioration processes and the decay by chemical corrosion of rock-forming minerals. Although SO₂ concentrations in air have shown a strong decrease over the past 30 years, degradation in connection with weathering crusts is still observed. This indicates that not only contemporary or recent emissions, but also past pollutant concentrations have to be considered.     

青藏高原古岩溶的存在及其与东邻地区岩溶的对比

青藏高原古岩溶属形成于土下环境,经刻蚀作用剥露地表后,以石林、岩墙等形式广泛存在于山顶夷平面的外围,并不同程度地叠置气下改造特征。根据青藏高原及东邻岩溶区覆盖型岩溶和红色风化壳的剥露情况及改造特征对比,作者认为上述地区覆盖型岩溶从东到西具有良好的一致性,是岩溶双层夷平面的组成部分,其现阶段的不同表现是不同程度刻蚀作用的结果。      

贵州中三叠统上部垄头组的沉积性质——再论其钙结壳的成因

钙结壳是土壤层之下的岩石在出露地表渗流带环境内受大气雨水的溶解,并通过上覆土壤层的淋滤而成的产物。由于雨水的不断的溶解,使原始的岩石或沉积物发生破裂,从而形成各种大小的砾块或砾石。随着雨水不断的溶解,雨水逐渐增加 CaCO_3的含量。这些富含碳酸钙的雨水,当它流到位于潜水面之上的下渗流带时,就在土壤层之下、原来岩石之上沉积了特殊的、层纹状方解石胶结物。它们往往覆盖岩石表面或沿着砾石的外缘、呈包覆状沉积,从而形成典型的层纹状钙结壳。渗滤豆粒的外皮也属于层纹状钙结壳的性质,这些外皮有向下方加厚的趋势,这表明渗流带的含碳酸钙的雨水,受重力作用影响下,具有往下悬垂现象,类似于洞穴内的钟乳石。豆粒之间的相互衔接呈多边形构造,也表明它是受重力作用而形成的构造。     

微地域搬运——碳酸盐岩红色风化壳形成过程的一种方式

由于差异溶蚀作用,由碳酸盐岩强烈风化形成的红色风化壳通常表现出独特的剖面构型:风化壳发育深厚、下伏基岩面强烈起伏波动、溶沟和石牙相间展布。以黔中岩溶台地之上发育的红色风化壳——平坝剖面为例,通过宏观地质、地球化学、粒度分析以及矿物学等方法,并以邻近的两个石灰土剖面(罗吏剖面和龙洞堡剖面)作对比,对碳酸盐岩红色风化壳的形成过程进行了讨论,论证了微地域搬运是碳酸盐岩红色风化壳尤其是厚层红色风化壳形成过程的一种方式。溶沟部位的风化壳,从风化前锋向上的一定深度范围内,为原位残积风化的产物(残积层);在此深度以上的部分,为地势较高的相邻石牙部位不同风化程度的残积物的搬运堆积(堆积层),也是导致风化指标随深度呈锯齿状波动的直接原因。后者一般组成剖面的主体。风化壳的年代地层学表现为,在残积层,从风化前锋向上,风化年龄由新到老;在堆积层,从下到上,风化年龄由老到新。风化前锋是一个重要的地球化学作用场所,在这一狭窄的界面上,伴随碳酸盐矿物的快速淋失,残余酸不溶物开始了明显分解。而风化壳的后期演化是一个缓慢而长期的过程。达到重力平衡的剖面(即风化壳表面平缓、不发生微地域搬运的剖面),在由表及里的风化作用下,从地表向下的一定深度范...     

Structure, chemistry and origins of gypsum crusts in southern Tunisia and the central Namib Desert

Gypsum crusts are broadly defined as accumulations at or within about 10 m of the land surface from 0.10m to 5.0 m thick containing more than 15% by weight gypsum (CaSO₄·2H₂O) and at least 5.0% by weight more gypsum than the underlying bedrock. The deposits are often, but not invariably, consolidated owing to cementation by gypsum. The crusts are found in many of the world's deserts where mean monthly potential evaporation exceeds mean monthly precipitation throughout the year. Using structural, fabric and textural criteria, three main types of crust may be distinguished:(1) bedded crusts, found either at or beneath the land surface, which are made up of discrete horizontal strata up to 0.10 m thick, each showing a gradation in gypsum crystal size from less than 50 μm at the top to more than 0.50 mm at the base; (2) subsurface crusts, of which there are two forms, one made up of large, lenticular crystals (up to 0.50 m in diameter)—the desert rose crusts—and the other, a mesocrystalline form, with gypsum crystals up to about 1.0 mm in diameter; and (3) surface crusts, which are subdivided into columnar, powdery and cobble forms, all of which are made up of predominantly alabastrine gypsum (crystallites less than 50 μm in diameter). In southern Tunisia and the central Namib Desert, bedded crusts are found around ephemeral lakes and lagoons. They are characterized by size-graded beds, gypsum contents of 50–80% by weight and comparatively high concentrations of sodium, potassium, magnesium and iron. They are interpreted as shallow-water evaporites which accumulate when saline pools evaporate to dryness. Desert rose crusts or croûtes de nappe generally contain 50–70% by weight gypsum, and have higher sodium concentrations than the second subsurface form. Texturally they are characterized by poikilitic inclusion of clastic material within large lenticular crystals. They are interpreted as hydromorphic accretions, which precipitate in host sediments at near-surface water tables through the evaporation of groundwater. The second form of subsurface crust—the mesocrystalline—often occurs in close association with the various surface forms. Unlike the hydromorphic crusts, they are not restricted to low-lying terrain. They are characterized by gypsum contents reaching 90% by weight, and have a close chemical and textural similarity to columnar surface crusts. This mesocrystalline form represents an illuvial accumulation; the surface forms—excluding the bedded crusts—are exhumed examples at various stages of solutional degradation. Subsurface precipitation of gypsum from meteoric waters containing salts leached from the surface, results in displacive gypsum accumulation in the soil zone. In southern Tunisia, the gypsum is derived from sand and dust deflated from evaporitic basins; in the central Namib, salts dissolved in fog water are the most likely source. Where other salts are present, differential leaching may form two-tiered crusts, calcrete—gypsum or gypsum—halite, if rainfall is sufficient to mobilize the less soluble salt yet insufficient to flush the more soluble. Gypsum crust genesis is restricted to arid environments, and if their susceptibility to post-depositional alteration is acknowledged, they can provide valuable palaeoclimatic indicators.     

Superficial alteration and soluble salts in the calcarenite weathering. case study of almohade monuments in Rabat: Morocco

This work analyzes the stone superficial deterioration of some monuments in Rabat city. The rock is a calcarenite with porous texture, rich in calcium carbonates and fossils. The techniques used to study the surfaces altered by blackening or black crusts, are the SEM equipped with EDX microprobe, the X-ray diffraction, and the analysis of the soluble salts by ionic chromatography for anions and flame spectrometer for cations. They reveal significant contents of calcium sulphates, mainly gypsum, often associated with sodium chlorides. These salts known to have a destructive effect on the calcareous stones seem to be originated from the contamination by atmospheric pollutants, particularly sulfur dioxide, and by the marine sprays.     

Origin and evolution of major salts in the Darling pans,Western Cape,South Africa

Sediment and water samples from 12 saline pans on the semi-arid west coast of South Africa were analysed to determine the origin of salts and geochemical evolution of water in the pans. Pans in the area can be subdivided into large, gypsiferous coastal pans with 79–150 g/kg total dissolved salt (TDS), small inland brackish to saline (2–64 g/kg TDS) pans and small inland brine (168-531 g/kg TDS) pans that have a layer of black sulphidic mud below a halite crust. The salinity of coastal pan waters varies with the seasonal influx of dilute runoff and dissolution of relict Pleistocene marine evaporite deposits. In contrast, inland pans are local topographic depressions, bordered on the north by downslope lunette dunes, where solutes are concentrated by evaporation of runoff, throughflow and groundwater seepage. The composition of runoff and seepage inflow waters is determined by modification of coastal rainfall by weathering, calcite precipitation and ion exchange reactions in the predominantly granitic catchment soils. Evaporation of pan waters leads to precipitation of calcite, Mg–calcite, dolomite, gypsum and halite in a distinct stratigraphic succession in pan sediments. Bicarbonate limits carbonate precipitation, Ca limits gypsum precipitation and Na limits halite precipitation. Dolomitisation of calcite is enhanced by the high Mg/Ca ratio of brine pan waters. Brine pan waters evolve seasonally from Na–Cl dominated brines in the wet winter months to Mg–Cl dominated brines in the dry summer months, when 5–20 cm thick halite crusts cover pan surfaces. Pan formation was probably initiated during a drier climate period in the early Holocene. More recent replacement of natural vegetation by cultivated land may have accelerated salt accumulation in the pans.     

Petrology of recent caliche pisolites, spherulites, and speleothem deposits from central Texas

Recent caliche, including nodules, pisolites, crusts, internal sediment, speleothem deposits, and spherulites, has formed within the dolomitic Cretaceous Edwards Formation of central Texas. As weathering altered the host strata, rhombic crystals of calcite were precipitated concomitantly with dissolution of the dolomite, thereby forming nodules. The highly altered dolomite (i.e. pulverulite) was then removed and spar, internal sediment, and travertine accumulated in the internodular voids. Nodular masses of calcite and dolomite are the most prominent constituent of the caliche. Some of the nodules have a well developed concentric structure as well as other characteristics similar to hypersaline pisolites. Features which appear to be useful in distinguishing caliche from hypersaline pisolites are: regional geological setting, association with other caliche and palaeosoil deposits, types of fossils present, and the presence of rhombic calcite and/or bladed sparry calcite with triangular shaped cross-section. A brick-like calcite texture and relict aragonite rays characterize hypersaline pisolites. Incipient neomorphism of the nodules and pisolites has resulted in the development of a radial pattern of spar within these structures. Geopetal deposits of internal sediment, including terra rossa soil, inhibited spar growth in the upward direction; consequently, spar is much better developed on the undersides of pisolites. Crusts and travertine flowstone (speleothem) deposits are intimately associated with the nodular masses and internal sediment. The brecciated thin crusts and travertine flowstone are end products of the same processes. The crusts formed during times of periodic desiccation of the growing surface while the flowstone formed when water was relatively abundant. Spherulitic bodies within the caliche, commonly 1–2 mm in diameter, display a radial texture and yet are composed of single crystals of calcite. The structures are the product of neomorphosed Microcodium or Microcodium-like globular bodies.     

Environmental impact on the Roman monuments of Tarragona,Spain

The extant remains of the Roman monuments of Tarragona, Spain are made of different types of Miocenic rocks from the quarries surrounding the city, which vary from calcarenite to bioclastic limestones, showing different degrees of dolomitization, depending on their diagenetic evolution. The decay of these monuments is highly dependent on the mineralogy and the fabric of the stone as well as on the environmental conditions to which the monument subjected. As a consequence, different forms of decay are observed on these monuments, namely, granular disintegration, differential erosion between sparitic and micritic areas of the rock, and development of black crust and orange patinas, some of them attributed to a sulfation process. A number of processes have been established as being responsible for the decay forms observed: sulfation on sheltered areas of the building in the urban environment; differential dilatation because of the NaCl of the marine spray that crystallizes inside the porosity; hydric and thermal expansion of the stone, both related to the amount and crystallinity of the clay minerals forming the rock matrix; and biocolonization on the stone surface. An empirical model is proposed to explain the decay forms studied in relation to these factors (rock and environment).     

翡翠的皮壳组成及其与内部玉石质量关系初步研究

在对广东南海平洲、广州花都国际翡翠展销会等翡翠原料集散地大量现场考察的基础上,选取了具有黄色色调、白色和灰黑色皮壳的翡翠原石样品,经肉眼和偏光显微镜观察、X射线粉末衍射和电子探针测试,研究了不同颜色系列翡翠原石皮壳的矿物组成和化学成分特征。结果表明,不同颜色翡翠皮壳的主要矿物均为硬玉,次要矿物则有所不同。黄色皮壳含高岭石、三水铝石、软锰矿和赤铁矿等,白色皮壳含高岭石和水钙铝榴石,黑色皮壳则含高岭石和绿泥石类矿物。与内部玉石成分相比,皮壳中的主要化学成分硼（Na2O）和w（SiO2）有所降低,而w（CaO）和w（MgO）及Fe的质量分数则相对增加;黄色皮壳翡翠中Fe的质量分数越高,则皮壳的黄色色调越深,但皮壳的化学成分受环境影响较大,难以用于判断其内部玉石质量。仅初步总结了翡翠皮壳矿物组成与其内部玉石质量的关系。     

鄂尔多斯盆地西部奥陶系风化壳岩溶作用模式

鄂尔多斯盆地下古生界马家沟组顶部遭受长期风化剥蚀,形成了以膏云岩为主的风化壳岩溶储层。通过偏光显微和超微扫描电镜深入观察了（含）膏云岩的孔隙类型及充填规律,分析了其岩溶作用特点,研究了以膏云岩为主的岩溶作用特征与传统碳酸盐岩岩溶作用特征的区别,探讨了膏云岩发育区的岩溶作用模式。结果表明:硬石膏结核和石膏晶体以其强亲水性和远高于白云石、方解石的溶解度,极易率先吸水发生溶解形成组构选择性溶蚀孔隙,导致膏云岩层蜂窝状溶孔的形成。硬石膏的高溶解度和力学不稳定性使得研究区以膏云岩、白云岩和灰云岩互层的风化壳储层以膏模孔、扩溶膏模孔及与之伴生的胀缩微裂缝为主要储集空间,孔隙大小具有明显的自限性。岩性—（含）膏云岩和沉积微相—海平面低位期潮上带（含）膏云坪沉积是储层形成的先天物质基础和环境条件,并因此直接导致（含）膏云岩储层的成层分布特征。表层膏云岩首先遭受淡水淋滤形成蜂窝状溶孔,多层成层分布膏云岩这种独特的物理化学性质使风化壳内的岩溶水以弥散性渗透为主,这是膏云岩发育区岩溶作用特征和模式与碳酸盐岩产生重要差异的根本原因。     

Change of black shale organic material surface area during oxidative weathering: Implications for rock-water surface evolution

Black shale oxidative weathering plays a significant role in a variety of processes including acid mine drainage and atmospheric CO₂ control. The modeling of weathering is highly dependent on reactive surface area. In this study it is shown that black shale oxidative weathering is regulated mainly by the external, geometrical surface area of rock polyhedrons and the organic matter’s (OM) internal surface area. The internal rock surface area decreases dramatically during OM dissolution from ∼15 m²/g to ∼5 m²/g. A linear relationship was found between the decrease of internal rock surface area and quantity of OM dissolved. Optical roughness analyses of black and bleached shale surface area reveal the formation of macropores due to the dissolution of mesoporous and probably microporous OM. However, due to deconsolidation, the geometrical external rock polyhedron surface area increases during weathering. Black shale polyhedrons show a doubling of their external surface area as OM decreases. This provokes an increase of the shale volume which is easily accessible by fluids. The increase of the external rock surface area seems to be self-accelerating during weathering. The upscaling of external and internal rock surface area evolution during weathering presented in this study demonstrates the possible application of these results to the improved understanding of a chemical transport in a variety of natural systems.     

Origin of subaerial Holocene calcareous crusts: role of algae, fungi and sparmicritisation

The Pleistocene Miami Limestone that crops out on the lower Florida Keys is overlain by thin (16 cm or less), discontinuous, Holocene calcareous crusts (caliche) that are usually laminated, composed dominantly of calcite micrite and may or may not incorporate part of the underlying limestone. Both allochems and sparry calcite cement in the former unit contain endolithic algae and fungi, borings and unicellular algae. Biogenic structures identical to those in the Miami Limestone also occur in the calcareous crusts but are somewhat less abundant in the latter unit versus the former unit. The calcareous crusts were formed in the vadose diagenetic environment. Some of the CaCO₃ necessary for the micrite that comprises the bulk of the crusts was probably derived from solution of carbonate from a soil cover and some from wind blown salt spray. Most of the micrite, however, was formed by replacement of the uppermost portions of the Miami Limestone. Replacement involved micritisation of allochems and a previously unreported process, sparmicritisation, the degrading recrystallization of sparry calcite to micrite. Minor sparmicritisation was caused by micrite calcification of endolithic fungi or algae within sparry calcite cement or by micrite precipitation in empty borings within such cement. Most sparmicritisation took place by dissolution of sparry calcite and concomitant precipitation of micrite in the space occupied previously by the dissolved spar. Such sparmicritisation is interpreted to be caused by chemical reactions involving the crystals, pore water which is moving slowly but steadily and organic compounds released during bacterial decomposition of fungi, algae or both. It is recognized that sparmicritisation occurs in the marine diagenetic environment and is not, therefore, necessarily indicative of vadose diagenesis. Incomplete sparmicritisation is responsible for some of the clotted textures typically found within calcareous crusts and may explain such textures in many other carbonate rock types. A combination of sparmicritisation and micritisation has probably greatly influenced the porosity of many reefs and, in some cases, led to the formation of ‘micritic reefs’.     

Groundwater salinization of the Sfax superficial aquifer,Tunisia

Groundwater salinization has become a crucial environmental problem worldwide and is considered the most widespread form of groundwater contamination. The origin of salinity in the coastal aquifer of the Sfax Basin, Tunisia was investigated by means of chemical analyses of groundwater samples from 65 wells. The groundwater samples present a clear gradation from calcium sulphate salinization to that of sodium chloride. The saturation indices for calcite and gypsum, and binary diagrams of different ions, together with multivariate analysis, indicate the existence of various salinization processes such as: dissolution of gypsum and calcite dispersed through the reservoir rock; ion exchange; intensive agricultural practices that produce effluents that infiltrate to the saturated zone; and sea-water intrusion, enhanced by excessive withdrawal of groundwater.     

Formation of helictite in the cave Dragon Belly (Sardinia,Italy)—Microstructure and incorporation of Mg,Sr, and Ba

In the Dragon Belly cave helictites, a special type of irregular speleothem, are found, which grew on stalactites in all vertical and horizontal directions without any affinity to gravity. Microstructural and mineralogical analyses of this stalactite–helictite system indicate that its evolution is initiated by clogging of the central stalactite channel at its tip, probably when the cave was flooded by muddy water. Clogging caused the formation of secondary channels (≈0.2 mm in diameter) for water passage through the outer surface of the stalactite, where helictites start to grow. The secondary channel passes into the central channel of the helictite.The helictites consist of stacked idiomorphic calcite crystals with uniform orientation. Growth of calcite is essentially controlled by water transfer through the central channel and via canalicules (narrow channels of ≈0.05 mm in diameter) following the crystal boundaries of the calcite mesocrystal induced by capillary hydrostatic forces. At straight parts of the helictites calcite crystals are almost uniform in size, but at bended parts crystals are significantly smaller inside (≤0.1 mm in length) than outside of the bend (≤0.5 mm). It is proposed that the difference in calcite volume (larger crystals) vs. the inside of the bend leads to a helix form, which explains the origin of the term helictite.The Sr and Ba concentrations measured by laser ablation along helictites can be explained by cation incorporation during calcite precipitation close to equilibrium. Dilution effects caused by seasonality control the elemental distribution in the helictite, which result in a positive correlation between Sr and Ba. Variability of Mg is unrelated with Sr and Ba, and is probably due to the incongruent dissolution of Mg–calcite from the host rock.     

Evinosponges in the Triassic Esino Limestone (Southern Alps): documentation of early lithification and late diagenetic overprint

A carbonate buildup of Middle Triassic age, the Esino Limestone, outcrops in the Southern Calcareous Alps of Lombardy (N Italy). Along its margin and within the open subtidal facies, the Esino Limestone contains calcite cement-filled cavities of cm to m size. These features, known as evinosponges, may form pervasive networks within the host rock. The filling consists of concentric, isopachous layers of fibrous low-Mg calcite crystals characterized by strong undulose extinction and bent cleavages. The cement crusts are non-luminescent under cathodoluminescence, but both cements and host rock are cross-cut by micro-fractures filled with bright-luminescent calcite, related to late void-filling sparite. Mixing of different carbonates is reflected in stable isotope data. On the hand specimen scale, the oxygen and carbon isotope compositions of cements and host rock show little variation. When compared on a regional scale, the values cover a broad range from δ¹⁸O(PDB)=?5‰ to ?12‰ and from δ¹³O =0‰ to +3‰. The linear covariant trends defined by the oxygen and carbon isotope data for different sampling regions reflect the admixture of late, isotopically depleted calcite with an isotopically enriched non-luminescent calcite of early diagenetic origin. The Esino Limestone fibrous cements, which were probably precipitated in the marine or marine-meteoric phreatic environment, were affected by late diagenetic processes that caused mineral deformation and isotopic depletion through recrystallization and the admixture of a later calcite. These later calcites precipitated from penetrative fluids possibly related to Late Triassic volcanic activity and/or to the Late Cretaceous/Early Palaeogene alpine orogeny.