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.     

Morphology and mineralogy of weathering crusts on highly porous oolitic limestones, a case study from Budapest

Black crusts are very common on limestones in polluted urban environments, but white crusts are less frequently developed. On the soft, porous and inherently weak oolitic limestone of Budapest both crusts are frequent, and indeed white ones are more common on the stone walls of the studied fortress. In this paper, black and white crusts and the host rock have been described using morphological criteria, mineralogical analyses (XRD, DTA), elements analyses (microprobe) and micro-morphological (SEM) tests. The analyses have shown that on white crusts the surface dissolution is combined with the precipitation of gypsum and calcite in the pores and accumulation of gypsum on the underside of the crust. Thin white crusts are removed by a combination of salt crystallisation (gypsum) and frost action while very thick stone layers scale off due to freeze-thaw cycles. Black crusts are enriched in gypsum relative to white crusts. Gypsum accumulates on the crust surface and signs of dissolution have not been observed. Airborne particulates (flyash, silt-sized quartz, and organic debris) adhere to the crust surface of sheltered black crusts. These particles are later incorporated into the expanding gypsum crystals, that are visible on the underside of the crust. The host rock also contains gypsum, but it is washed off the surface when the crust is removed. Further exposure of the host rock may lead to the dissolution of calcite crystals as it is observed by SEM. The micro-environment influences the crust formation and adherence of the crusts. On frequently wet and dry surfaces crust removal is more common. The crust serves as a protective layer on the stone surface, but this protection is temporary since trigger mechanisms such as salt crystallisation or frost action can cause rapid surface loss.Special Issue: Stone decay hazards     

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.     

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.     

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.     

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。     

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.     

The Angera stone: a challenging conservation issue in the polluted environment of Milan (Italy)

The Angera stone is a sedimentary Triassic dolostone mainly composed of dolomite, which was widely employed in the Lombard architecture. In the present work, the study of the Angera stone of the ‘Cortile del Richini’, a masterpiece of the Lombard baroque, is discussed as an example of a particularly challenging conservation issue. The courtyard suffered from a particularly troubled conservative history and the highly polluted urban environment of Milan provided very favourable conditions for the decay of such a delicate stone type. The last extensive conservative intervention was performed during the nineties due to massive black crust formation and granular disintegration of the stone. Almost 20 years later, a thorough study of the stone has been aimed at the definition of a long-term maintenance project. The Angera stone has been investigated in order to define an updated version of its state of conservation, as well as to track any changes in the degradation mechanisms due to the environmental variations of the Milan city centre. In particular, the soluble salts’ content of the stone substrate has been evaluated as an indicator of the damage level. The results highlighted that the stone is currently in critical condition: An extensive sulphation process is taking place, leading to the chemical transformation of the dolomitic substrate into gypsum. Moreover, the powder deposits affecting the stone surfaces have a similar composition to those generally found in the black crusts growing in urban environment. Therefore, they can be considered as precursor of this particularly dangerous decay mechanism.     

改性糯米灰浆的室内研究及在九寨沟钙华地质裂缝修复中的应用

我国有着大面积的钙华地区,国内外学者对钙华的形成及影响因素进行了大量的研究,但针对钙华地区地质裂缝生态修复材料及工艺还鲜有研究。文章以九寨沟风景区震后地质裂缝为研究对象,结合水文条件及钙华颗粒的性质,在传统糯米灰浆的基础上,通过掺入不同比例的原料、改性剂及一定级配的钙华颗粒,研制出一种性能优良的灌浆材料,并对其流动性、凝结时间、抗压强度及抗折强度进行测试。室内试验表明:该材料具有流动性好、凝结时间可控、强度高、可水下浇筑等特点;空气中养护试样的各项指标均优于水中养护的试样。优选裂缝修复配合比为:糯米浆0.6~0.64份、石膏1.19份、石灰0.29份、钙华颗粒1份、改性剂1# 0.07份、改性剂2# 1.19%份,浆液可泵期63~86 min,初凝时间74~98 min,终凝时间92~125 min。改性糯米灰浆在九寨沟修复裂缝、加固崖体现场修复试验中取得了良好的效果,将流水漏失量由原来的50%降低至3%,较好的恢复了瀑布景观。应用表明改性糯米灰浆与钙华颗粒具有较好的相容性,可改善钙华颗粒的原生孔隙结构,促进钙华景观的生长。     

Ferromanganese crusts as indicators for paleoceanographic events in the NE Atlantic

Hydrogenetic ferromanganese crusts reflect the chemical conditions of the sewater from which they formed. Fine-scale geochemical analysis of crust layers in combination with age determinations can therefore be used to investigate paleoceanographic changes which are recorded in geochemical gradients in the crusts. At Tropic seamount (off northwest Africa), uniform crust growth influenced by terrigenous input from the African continent occurred during approximately the past 12 Ma. Phosphatization of these crusts is minor. In contrast, crusts from Lion seamount, located between Madeira and the Portuguese coast, display a much more variable growth history. A pronounced increase in Ni, Cu, and Zn is observed in some intervals of the crusts, which probably reflects increased surface productivity. A thick older phosphatized generation occurs in many samples. Hydrographic profiles indicate that Mediterranean outflow water (MOW) may play an important role in the composition of these crusts.¹⁰Be dating of one sample confirms that the interruption of the MOW during the Messinian salinity crisis (6.2–5 Ma ago) resulted in changes in element composition. Sr-isotope dating of the apatite phase of the old crust generation has been carried out to obtain a minimum age for the older generation of Atlantic crusts and to determine whether crust phosphatization in the Atlantic can be related to phosphatization episodes recorded in Pacific crusts. The preliminary data show that the old phosphatized crust generation might be as old as approximately 30–40 Ma.     

Effects of iron black varnish on petrophysical properties of building sandstone

In zones washed by rain (façades, pinnacles, pilasters), fine siliceous sandstones are covered by a black varnish, which gives a dirty appearance to monuments. In composition, structure and areas covered by it, it differs from the usual black gypsum crust. Experiments carried out on blocks covered by black varnish show the modifications due to their growth. Results show that despite their low thickness and the coherence of the stone below, the accumulation of hydrophobic matters and the wetting-drying cycles modify the transfer properties of sandstones several centimeters below the surface. Thus, although sandstones seem to be protected by the black varnish, in the long run, a flake detachment process, in the areas covered by it, affects them. Therefore, damage to sandstones by black varnish can be explained by the fact that a wetting and drying cycle modifies the pore network.     

世界自然遗产-四川黄龙钙华景观的形成与演化

本文对作者十余年来在四川黄龙(世界遗产地)的钙华研究成果和最新的一些监测发现进行了综述, 目的是为公众更好地了解黄龙、保护黄龙提供科学基础。主要结果和结论是: (1)黄龙钙华的形成是由于地球深部高分压的CO2在碳酸盐岩补给区产生富含碳酸氢钙的地下水, 当其以泉的形式出露地表时, 由于泉水的CO2分压远远高于空气, 泉水中的CO2大量逸出, 结果导致碳酸钙过饱和而发生沉积; (2)黄龙钙华的颜色以黄色为主色调, 主要是在雨季因雨水冲刷土壤向水中混入泥沙的缘故; 而在旱季, 钙华主要形成于清亮干净的泉水, 因此, 钙华的颜色呈现出纯净碳酸钙沉积的本色-白色。这也是黄龙洞钙华剖面年层中出现黄-白相间亚层的原因; (3)高精度的铀-钍同位素测年表明, 黄龙钙华主体是全新世以来形成的; (4)地表水向地下河的漏失是黄龙地表水日益减少, 导致钙华体表面干涸, 从而气生蓝藻大量滋生, 致使某些钙华变黑的主要原因, 因此, 有必要尽早采取防渗补水措施; (5)旅游活动已对黄龙钙华景观产生影响, 包括上游人为践踏使下游钙华池淤塞, 以及磷酸盐污染使硅藻等过度繁殖和钙华沉积速率可能降低等, 因此, 必须尽早采取相应防控措施。     

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.     

新疆古尔班通古特沙漠生物结皮的土壤理化性质分析

古尔班通古特沙漠是我国第二大沙漠,广泛发育着地衣、苔藓和藻类等生物结皮,其分布状况与其自身生理生态特点和所处沙丘部位的环境条件密切联系着.结合野外调查和实验室样品分析结果,讨论了沙丘不同部位土壤理化性质与生物结皮分布、发育的关系.结果表明:不同类型生物结皮在沙丘上的分布和发育状况是不同的,从沙丘顶部的流动或半流动沙面上到沙丘两坡的中部、下部以及丘间低地,生物结皮的分布依次为微生物种类、藻类结皮、地衣结皮和苔藓结皮,从沙丘上部、中部至沙丘底部及丘间,生物结皮的类型、厚度及发育程度呈增强态势.生物结皮在沙丘不同部位的发育特点和分异变化与沙丘不同地貌部位的土壤理化性状、地表基质稳定性等生态条件有着密切的关系.     

Rapid facies changes in Holocene fissure ridge hot spring travertines, Rapolano Terme, Italy

Holocene hot water travertine continues to form at Terme San Giovanni, near Rapolano Terme, central Italy, although artificial diversion of the water has reduced deposition. Mesothermal water (≈38–39 °C) emerging from fault-controlled vents located on a hilltop has created a linear fissure ridge 240 m long and up to 10 m high. Active parts of the ridge crest are covered by small cones; inactive parts are locally neotectonically fissured and have small pools. Ridge deposits include crystalline crust, paper-thin raft and shrub lithotypes. The ridge has both smooth and terraced marginal slopes, dominated by crystalline crusts with small shrubs in terrace pools. At the base of the ridge, there is a rapid transition to lateral flats and depressions, where water from the ridge collects and deposits shrub, irregular pisoid, reed, paper-thin raft and fine-grained and organic-rich travertines. Water channelled to nearby valley sides deposits thick crystalline crusts on valley slopes and waterfall overhangs, locally with small pools filled by smooth spherical pisoids. On the valley floor, mixing of waters forms varied stream-fill deposits that include micritic reed, paper-thin raft and coated bubble travertines. The diversity of travertine facies observed results from the location of the Terme San Giovanni hot springs on a hill crest, thus providing a wide array of downslope locations for further deposition. The abrupt facies transitions observed are characteristic of hot spring carbonates and result from a combination of rapid decrease in precipitation away from vents, variations in local surface topography and the feedback effect of travertine deposition itself, which dams and diverts water flow.     

Microbial dolomite crusts from the carbonate platform off western India

Abstract The occurrence of Late Pleistocene dolomite crusts that occur at 64 m depth on the carbonate platform off western India is documented. Dolomite is the most predominant mineral in the crusts. In thin section, the crust consists of dolomitized microlaminae interspersed with detrital particles. Under scanning electron microscopy, these laminae are made up of tubular filaments or cellular structures of probable cyanobacterial origin. Dolomite crystals encrust or overgrow the surfaces of the microbial filaments and/or cells; progressive mineralization obliterates their morphology. Well-preserved microbial mats, sulphide minerals (pyrrhotite and marcasite) and the stable isotope composition of dolomite in the crusts indicate hypersaline and anoxic conditions during dolomite formation. The crusts are similar to dolomite stromatolites, and biogeochemical processes related to decaying microbial mats under anoxic conditions probably played an important role in dolomite precipitation. The dolomite is therefore primary and/or very early diagenetic in origin. The dolomite crusts are interpreted to be a composite of microbial dolomite overprinted by early burial organic dolomite. The results of this study suggest that a microbial model for dolomite formation may be relevant for the origin of ancient massive dolomites in marine successions characterized by cryptalgal laminites. The age of the crusts further suggests that the platform was situated at shallow subtidal depths during the Last Glacial Maximum.     

Global occurrence of tellurium-rich ferromanganese crusts and a model for the enrichment of tellurium

Hydrogenetic ferromanganese oxyhydroxide crusts (Fe-Mn crusts) precipitate out of cold ambient ocean water onto hard-rock surfaces (seamounts, plateaus, ridges) at water depths of about 400 to 4000 m throughout the ocean basins. The slow-growing (mm/Ma) Fe-Mn crusts concentrate most elements above their mean concentration in the Earth’s crust. Tellurium is enriched more than any other element (up to about 50,000 times) relative to its Earth’s crustal mean of about 1 ppb, compared with 250 times for the next most enriched element.We analyzed the Te contents for a suite of 105 bulk hydrogenetic crusts and 140 individual crust layers from the global ocean. For comparison, we analyzed 10 hydrothermal stratabound Mn-oxide samples collected from a variety of tectonic environments in the Pacific. In the Fe-Mn crust samples, Te varies from 3 to 205 ppm, with mean contents for Pacific and Atlantic samples of about 50 ppm and a mean of 39 ppm for Indian crust samples. Hydrothermal Mn samples have Te contents that range from 0.06 to 1 ppm. Continental margin Fe-Mn crusts have lower Te contents than open-ocean crusts, which is the result of dilution by detrital phases and differences in growth rates of the hydrogenetic phases.Correlation coefficient matrices show that for hydrothermal deposits, Te has positive correlations with elements characteristic of detrital minerals. In contrast, Te in open-ocean Fe-Mn crusts usually correlates with elements characteristic of the MnO₂, carbonate fluorapatite, and residual biogenic phases. In continental margin crusts, Te also correlates with FeOOH associated elements. In addition, Te is negatively correlated with water depth of occurrence and positively correlated with crust thickness. Q-mode factor analyses support these relationships. However, sequential leaching results show that most of the Te is associated with FeOOH in Fe-Mn crusts and ≤10% is leached with the MnO₂.Thermodynamic calculations indicate that Te occurs predominantly as H₅TeO₆⁻ in ocean water. The speciation of Te in ocean water and charge balance considerations indicate that Te should be scavenged by FeOOH, which is in agreement with our leaching results. The thermodynamically more stable Te(IV) is less abundant by factors of 2 to 3.5 than Te(VI) in ocean water. This can be explained by preferential (not exclusive) scavenging of Te(IV) by FeOOH at the Fe-Mn crust surface and by Fe-Mn colloids in the water column. We propose a model in which the extreme enrichment of Te in Fe-Mn crusts is likely the result of an oxidation reaction on the surface of FeOOH. A similar oxidation process has been confirmed for Co, Ce, and Tl at the surface of MnO₂ in crusts, but has not been suggested previously to occur in association with FeOOH in Fe-Mn crusts. Mass-balance considerations indicate that ocean floor Fe-Mn deposits are the major sink for Te in the oceans. The concentration and redox chemistry of Te in the global ocean are likely controlled by scavenging on Fe-Mn colloids in the water column and Fe-Mn deposits on the ocean floor, as is also the case for Ce.     

A specific type of Fe-Mn mineralization on the Arctic seafloor

Three samples of Fe-Mn crusts overgrown on the surface of rocks are studied from the Mendeleev submarine rise located in the northern subpolar part of the Chukchi Sea. A massive crust up to 4–5 cm thick consists of an upper dense and lower denser layers similar in composition to the main one and contains 31–37% FeO and 11–13% MnO. Thin crusts and films are depleted in both components. Fe-vernadite is a major mineral of the crusts. The comparison of the major and trace element composition of the crusts with oceanic and marine nodules and hydrothermal crusts shows that they are mostly similar in composition to the nodules of the Bering Sea and are significantly distinct from the oceanic hydrothermal crusts. A small inclusion of the Pt-, Pd-, and Ru-rich (up to 1–2%) rock in one of the thin crusts points to the possible role of igneous rocks as a source of precious metals.     

Monitoring of playa evaporites as seen with optical remote sensing sensors: case of Chott El Jerid,Tunisia, from 2003 to present

Chott El Jerid in the Zone of Chotts of Tunisia is one of the largest endorheic basins in the world. During the dry period, from May to August, it is generally covered by continental evaporites which result from the desiccation of the lake formed after a flooding event. This lake comprises runoff water from the surrounding relief and also water resurgence. In order to map and monitor these evaporitic surfaces (mineral composition and evolution in space and time), optical multisource, multispectral, and multidate satellite data have been used. Landsat 4–5 TM, Landsat 8 OLI, SPOT 6, and Landsat Surface Reflectance (LSR) constitute the main data set. The central part of the Chott, north and south of the road crossing the Chott over 70 km from Tozeur to Kebili, has been particularly studied, because it corresponds to the major evaporite accumulation zone. These evaporites precipitated as concentric layers (a relatively rare pattern), mainly north of the road, after several recent flooding events during the last 15 years. Winds can play a significant role in the development of the evaporite layers. Image interpretation associated with field data shows that after the final desiccation of the playa lake, the mineralogy of the salt crust comprised an assemblage dominated by halite south of the road and by gypsum north of the road. Halite and gypsum are the only minerals to be identified using satellite remote sensing data. Sulfates such as gypsum can be identified thanks to a drop in reflectance in the short-wave infrared (SWIR) range caused by vibrations of the SO₄ group. Gypsum crusts are more widely distributed than halite crusts. LSR data are particularly suitable for multitemporal comparison because they are calibrated and atmospherically corrected. The classical bull’s eye pattern characterizing evaporitic deposits (from carbonates along the rims to halite, gypsum, and finally potassium-magnesium minerals in the center of the basin) is deeply disturbed by the road crossing Chott El Jerid.     

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.