Sedimentological,mineralogical and geochemical characteristics of the ooids in Cleopatra (Sedir Island,Gökova Bay,SW Turkey) and Alexandria (NW Egypt) Beach sediments: A comparison and reality of myth of the love

According to the myth, ooid-rich sediments in Cleopatra Beach (Sedir Island, Turkey) were brought by ships from Alexandria Beach (Egypt) by the Roman leader, Marcus Antonius, for his lover Cleopatra. Ooids of both beaches have been compared in terms of sedimentology, mineralogy and geochemistry to determine reality of the myth of love. Sieve analyses exhibit that sediments of Cleopatra Beach are slightly better sorted than Alexandria Beach sediments, and have relatively smaller sized ooids, interpreted to represent a relatively less agitated environment. All ooids are composed mainly of aragonite characterized by high Sr contents (>8600 mg/kg). Hierarchical Cluster Analysis, the cross-plot of δ¹⁸Oaragonite versus δ¹³C_aragonite values of ooids, and the presence of detrital grains such as gneiss and schist hint on two distinct groups of samples that correspond to the Cleopatra and Alexandria Beach ooids. These results suggest that the myth may not be realistic, and the ooids on the shore of Sedir Island were formed in-situ, e.g., during the Late Holocene.     

The characteristics of the chemical flow within the Motru catchment area, south — west Romania

The present paper, with reference to the Motru catchment area, contributes to the hydrochemical studies at an international level and to the completion of the characteristics regarding the chemical flow in Romania. In this regard, it emphasizes once again the dependence between the content of dissolved salts (fixed residue — mg/l) on the one hand and the lithological conditions, human activity, flow and the surface of the catchments on the other hand. The calculation and the analysis of the chemical flow for the Motru catchment area (located in the south-west of Romania) was performed on the basis of two parameters: the average flow of dissolved chemical substances (mg/s) and specific average chemical flow (t/kmp year) recorded at the monitoring stations on the Motru River and its tributaries during the period 2005–2009. The values obtained (for example: 2.63 mg/s and 47.7 t/km² year, at the Fata Motrului station, on the Motru River, in 2009) confirm the importance of the areal factors of natural background in the analysis of chemical flow as a morpho-dynamic process and implicitly for the chemical quality of surface waters.     

Geological, mineralogical and geochemical characteristics of the Radzimowice Au–As–Cu deposit from the Kaczawa Mountains (Western Sudetes, Poland): an example of the transition of porphyry and epithermal style

The sheeted quartz–sulfide veins of the Radzimowice Au–As–Cu deposit in the Kaczawa Mountains are related to Upper Carboniferous post-collisional potassic magmatism of the composite Zelezniak porphyry intrusion. Multiple intrusive activity ranges from early calc-alkaline to sub-alkaline and alkaline rocks and is followed by multiple hydrothermal events. Early crustally derived dacitic magma has low mg# (<63) and very low concentrations of mantle-compatible trace elements, high large-ion lithophile elements (LILE), moderate light rare-earth elements (LREE), and low high-field-strength elements (HFSE). Later phases of more alkaline rocks have higher mg# (60–70), and LILE, LREE, and HFSE characteristics that indicate mafic magma contributions in a felsic magma chamber. The last episode of the magmatic evolution is represented by lamprophyre dikes which pre-date ore mineralization and are spatially related to quartz–sulfide–carbonate veins. The dikes consist of kersantite and spessartite of calc-alkaline affinity with K₂O/Na₂O ratios of 1.1–1.9, mg# of 77–79, and high abundances of mantle-compatible trace elements such as Cr, Ni, and V. They have high LILE, low LREE, and low HFSE contents suggesting a subduction-related post-collisional arc-setting. The mineralization started with arsenopyrite that was strongly brecciated and overprinted by multiple quartz–carbonate phases associated with base-metal sulfides and Au–Ag–Bi–Te–Pb±S minerals. The sulfur isotope composition of sulfides ranges from –1.1 to 2.8 ³⁴S and suggests a magmatic source. At least two generations of gold deposition are recognized: (1) early refractory, and (2) subsequent non-refractory gold mineralization of epithermal style. Co-rich arsenopyrite with refractory gold and pyrite are the most abundant minerals of the early stage of sulfide precipitation. Early arsenopyrite formed at 535–345°C along the arsenopyrite–pyrrhotite–loellingite buffer and late arsenopyrite crystallized below 370°C along the arsenopyrite–pyrite buffer. Non-refractory gold associated with base-metal sulfides and with Bi–Te–Ag–Pb–S mineral assemblages has an average fineness of about 685, and is represented by electrum of two generations, and minor maldonite (Au₂Bi). Fluid inclusions from various quartz generations co-genetic with base-metal sulfides and associated with carbonates, tellurides and non-refractory gold indicate fluids with moderate salinity (9–15 wt% NaCl equiv.) and a temperature and pressure drop from 350 to 190°C and 1.2 to 0.8 kbar, respectively. According to the result of the sulfur isotope fractionation geothermometer the temperature of base-metal crystallization was in the range from 322 to 289°C. Preliminary results of oxygen isotope studies of quartz from veins indicate a gradual increase in the proportion of meteoric water in the epithermal stage. The gold to silver ratio in ore samples with >3 ppm Au is about 1:5 (geometric mean). Hydrothermal alteration started with sericitization, pyritization, and kaolinitization in vein selvages followed by alkaline hydrothermal alteration of propylitic character (illitization and chloritization), albitization and carbonatization. The mineralization of the Radzimowice deposit is considered as related to alkaline magmatism and is characterized by the superposition of low-sulfidation epithermal mineralization on higher-temperature and deeper-seated mesothermal/porphyry style.Editorial handling: B. Lehmann     

Petrology and geochemistry of the 2014–2015 Holuhraun eruption,central Iceland: compositional and mineralogical characteristics,temporal variability and magma storage

The 2014–2015 Holuhraun fissure eruption provided a rare opportunity to study in detail the magmatic processes and magma plumbing system dynamics during a 6-month-long, moderate- to large-volume basaltic fissure eruption. In this contribution, we present a comprehensive dataset, including major and trace elements of whole-rock and glassy tephra samples, mineral chemistry, and radiogenic and oxygen isotope analyses from an extensive set of samples (n?=?62) that were collected systematically in several field campaigns throughout the entire eruptive period. We also present the first detailed chemical and isotopic characterization of magmatic sulfides from Iceland. In conjunction with a unique set of geophysical data, our approach provides a detailed temporal and spatial resolution of magmatic processes before and during this eruption. The 2014–2015 Holuhraun magma is compositionally indistinguishable from recent basalts erupted from the Bárðarbunga volcanic system, consistent with seismic observations for magma ascent close to the Bárðarbunga central volcano, followed by dyke propagation to the Holuhraun eruption site. Whole-rock elemental and isotopic compositions are remarkably constant throughout the eruption. Moreover, the inferred depth of the magma reservoir tapped during the eruption is consistently 8?±?5 km, in agreement with geodetic observations and melt inclusion entrapment pressures, but inconsistent with vertically extensive multi-tiered magma storage prior to eruption. The near constancy in the chemical and isotopic composition of the lava is consistent with the efficient homogenization of mantle-derived compositional variability. In contrast, occurrence of different mineral populations, including sulfide globules, which display significant compositional variability, requires a more complex earlier magmatic history. This may include sampling of heterogeneous mantle melts that mixed, crystallized and finally homogenized at mid- to lower-crustal conditions.     

Geomorphology and geomorphological heritage of the Ifrane–Azrou region (Middle Atlas,Morocco)

Geomorphological heritage is a widely used term in European and North-American countries, but is still scarcely mentioned in Africa. Nevertheless, the attractiveness of the African countries is often intimately connected to its breathtaking and endless geological landscapes. Morocco is one of those countries that has the widest diversity in landscapes and landforms, ranging from the Mediterranean and Atlantic coasts over the Rif, Middle Atlas, High Atlas and Anti-Atlas mountain chains to the great rocky and sandy deserts in the South. A wide variety of geological units hosting different types of important economic mineral deposits cover a temporal range from Late Precambrian to Quaternary. A detailed geomorphological study has been carried out in the region of Ifrane and Azrou (Middle Atlas, Central Morocco) using a combination of high resolution satellite data and direct field observations integrated by geological maps and scientific literature. In order to describe and evaluate the geomorphological heritage of this area, 40 geomorphosites have been selected comprising springs, karst landforms (polje, dolines, caves, sinkholes, stone forests, cryptokarstic dolines), carbonate depositional landforms (travertines and waterfalls), fluvial landforms (meanders, canyons, palaeo-valleys, etc.), structural landforms (triangular facets, hogbacks, cuestas, residual outcrops, etc.) and volcanic landforms (volcanoes, caldeira, pyroclastic cones, lava tube). The results of this research have been summarised in a thematic map, representing the geomorphosites related to various landscape units.     

Development characteristics and mechanisms of the Taigu–Qixian earth fissure group in the Taiyuan basin,China

Since the 1980s, increasing human activity and continuing over-exploitation of groundwater resources have caused the earth fissures in the rift basin in Shanxi, China, to enter an active phase. Buildings along these earth fissures have been seriously damaged. Four massive earth fissures that developed in the Taigu and Qixian areas of the eastern Taiyuan basin endanger the operational safety of the high-speed railway that passes through this region. Using field observations, measurements, and exploration, we determined that the four earth fissures are parallel to each other, have a northeast trend, and are separated by approximately equal distances. The rupture zones of these earth fissures are generally 10–50 m wide and are formed by the main fissures and secondary fissures. The width of the zone affected by the earth fissures is 20–50 m based on deformation and the damage done to buildings. These fissures formed on the Earth’s surface; their hanging walls are lower than their foot walls, forming normal faults; and the ground surface around the fissures exhibits ridges and depressions. The fissures are connected to deep hidden faults. The fault displacement increases with increasing depth, which is characteristic of syn-sedimentary faults. These earth fissures are characterized by vertical displacement, and their average annual activity rate is 1–3 cm. We believe that the formation of this large-scale fissure group may be related to the tectonic structure of the hidden faults in the basin and may also be affected by the continuous regional extensional stress of the basin. The current increased level of activity could be caused by the over-exploitation of groundwater in the area.     

Paleontological,mineralogical and chemical studies of syngenetic and epigenetic Pb–Zn–Ba–P mineralizations at the stratotype of the K/P boundary (El Kef area,Tunisia)

The El Kef area, Tunisia, is host of the official stratotype of the K/P boundary and of a complex metallic and non-metallic mineralization at Djebel Sekarna, encompassing syn(dia)genetic shale- and carbonate-hosted Zn–P and epigenetic Pb–Zn–Ba ore mineralizations. Micropaleontological, geological, mineralogical, and chemical studies (major and minor elements, C- and O-isotopes) of Upper Santonian to Lower Eocene calcareous-siliciclastic sediments resulted in a subdivision of this mineralization into eight mineralizing stages. Stages 1 and 2 (late Cretaceous–early Paleogene) are representative of syn(diagenetic) shale- and carbonate-hosted sulfidic and siliceous (Fe)–Zn–P mineralization deposited in shallow marine to slightly brackish sediments. Stages 3–5 (early Eocene respectively—pre- and post-Nummulites involutus-exilis zones) are representatives of epigenetic sulfidic and sulfatic (Fe)–Zn–Pb–Ba mineralizations at temperatures as high as 170/200°C and stages 6 and 7 (early Eocene respectively—post-Alveolina oblonga zone) cover the non-sulfidic Zn–(Pb) mineralization at temperatures as high as 60°C which is transitional from hypogene into supergene mineralization (“epithermal calamine deposits”). Stage 8 represents alteration of the pre-existing mineral assemblages in course of the Holocene weathering. The Cretaceous through Paleogene aquatic system is characterized by a poisoning of the sea with base metals, mainly Zn, and the atmosphere was chocked with clouds of fine-grained volcanic ejecta. Both processes contributed to the build-up of Zn–(Pb) deposits and vast, but uneconomic bentonitic clay deposits around the K/P boundary. Ore mineralization in the El Kef area is a multiple-phase process which reached its climax during the early Eocene as indicated by the large foram zones. These inorganic concentration processes resulting in the formation of mineral deposits had obviously also a negative effect on the long-term course of regional Earth’s biological history during the late Cretaceous–early Eocene period with lethal consequences for some species. The joint studies of inorganic and organic data reveal that such extraordinary metallogenetic processes close to the K/P boundary in its stratotype area in Tunisia were “strictly terrestrial”.     

Genesis of the Assif El Mal Zn–Pb (Cu,Ag) vein deposit. An extension-related Mesozoic vein system in the High Atlas of Morocco. Structural,mineralogical, and geochemical evidence

The Assif El Mal Zn–Pb (Cu–Ag) vein system, located in the northern flank of the High Atlas of Marrakech (Morocco), is hosted in a Cambro-Ordovician volcaniclastic and metasedimentary sequence composed of graywacke, siltstone, pelite, and shale interlayered with minor tuff and mudstone. Intrusion of synorogenic to postorogenic Late Hercynian peraluminous granitoids has contact metamorphosed the host rocks giving rise to a metamorphic assemblage of quartz, plagioclase, biotite, muscovite, chlorite, amphibole, chloritoid, and garnet. The Assif El Mal Zn–Pb (Cu–Ag) mineralization forms subvertical veins with ribbon, fault breccia, cockade, comb, and crack and seal textures. Two-phase liquid–vapor fluid inclusions that were trapped during several stages occur in quartz and sphalerite. Primary inclusion fluids exhibit T _h mean values ranging from 104°C to 198°C. Final ice-melting temperatures range from −8.1°C to −12.8°C, corresponding to salinities of ∼15 wt.% NaCl equiv. Halogen data suggest that the salinity of the ore fluids was largely due to evaporation of seawater. Late secondary fluid inclusions have either Ca-rich, saline (26 wt.% NaCl equiv.), or very dilute (3.5 wt.% NaCl equiv.) compositions and homogenization temperatures ranging from 75°C to 150°C. The δ¹⁸O and δD fluid values suggest an isotopically heterogeneous fluid source involving mixing between connate seawater and black-shale-derived organic waters. Low δ¹³C_VPDB values ranging from −7.5‰ to −7.7‰ indicate a homogeneous carbon source, possibly organic matter disseminated in black shale hosting the Zn–Pb (Cu–Ag) veins. The calculated δ³⁴S_H2S values for reduced sulfur (22.5‰ to 24.3‰) are most likely from reduction of SO₄ ²⁻ in trapped seawater sulfate or evaporite in the host rocks. Reduction of sulfate probably occurred through thermochemical sulfate reduction in which organic matter was oxidized to produce CO₂ which ultimately led to precipitation of saddle dolomite with isotopically light carbon. Lead isotope compositions are consistent with fluid–rock interaction that leached metals from the immediate Cambro-Ordovician volcaniclastic and metasedimentary sequence or from the underlying Paleo-Neoproterozoic crustal basement. Geological constraints suggest that the vein system of Assif El Mal formed during the Jurassic opening of the central Atlantic Ocean.     

The upper Cenomanian–lower Turonian carbonate platform of the Preafrican Trough,Morocco: Biostratigraphic,paleoecological and paleobiogeographical distribution of ostracods

The upper Cenomanian–lower Turonian paleoenvironments of the Preafrican Trough carbonate platform is characterized by analyzing the structure of the ostracod assemblages and the information provided by other groups, and also by linking together the paleontological and geochemical data (detrital influx-redox-paleoproductivity proxies, δ¹³C curve). Two different domains (eastern and western) can be recognized on the platform during the late Cenomanian, before the onset of the OAE2. The western domain corresponds to a low-energy environment developed on a mid and/or outer ramp with hypoxic waters, low detrital influx and low paleoproductivity. The paleoecological assemblages show limited specific diversity but variable density. The ostracods are opportunistic and unspecialized (r strategists), being associated with Buliminidae, surface and intermediate-water planktonic foraminifera, and fishes. The eastern domain corresponds to an inner ramp and/or peritidal environment with oxic waters, low detrital influx and low paleoproductivity, developed in a higher energy environment with paleoecological assemblages showing high diversity but variable density. The ostracods are more specialized (K strategists), being represented by diverse and constant assemblages associated with diversified benthic foraminifera, calcareous sponges and echinoderms, as well as intermediate- and deep-water planktonic foraminifera. The onset of the OAE2 has no influence on the western ostracod assemblages, but leads to the decline of the ostracod fauna and the disappearance of the deep-water planktonic foraminifera in the eastern domain. During the early Turonian, after the OAE2, the platform becomes an outer ramp with increased paleoproductivity, but is associated with a decrease of taxonomic diversity in hypoxic waters. The ostracods are very sparse and unspecialized, associated with siliceous sponges, Buliminidae, surface-living planktonic foraminifera, fishes and pelagic crinoids. Marine paleobiogeographic communication is relatively easy across the carbonate platforms between the Preafrican Trough and other Moroccan regions, as well as between Morocco and different parts of the South Tethyan and East Atlantic margins belonging to the Cenomanian–Turonian South Tethyan Ostracod Province (STOP). Thirteen new species are described: Cytherella tazzouguertensis n. sp., Bairdiacypris chaabetensis n. sp., Bythocypris amelkisensis n. sp., Pontocypris tadighoustensis n. sp., Procytherura? elongatissima n. sp., Loxoconcha akrabouensis n. sp., Hemiparacytheridea sagittaemucronata n. sp., Rehacythereis errachidiaensis n. sp., Rehacythereis zizensis n. sp., Veenia (Nigeria) tardaensis n. sp., Veenia (Nigeria) mediacostarobusta n. sp., Xestoleberis? preafricanensis n. sp., and Xestoleberis circinatus n. sp.     

The mineralogical,isotope (K–Ar), structural,and textural features of the Jurassic siliciclastic complex in various tectonic environments (Greater Caucasus,Chechnya, and Georgia)

The variations in the structural, textural, mineralogical, and geochemical (isotope) features of Lower to Middle Jurassic siliciclastic sediments along the Chanty-Argun River in Mountainous Chechnya and Georgia are discussed. This profile transects areas with various types of deformed sediments, from the northern comparatively weakly deformed and altered zone, to the southern zone of intense deformation and cleavage. Southward along the profile, these alterations are accompanied by the evolution of clay mineral assemblages, as well as polytypic modifications of micas and their crystallinity index. Increasing intensity of rock alteration and cleavage leads to a change of the K–Ar system, which results in a substantially rejuvenated isotope age of the sediments with a simultaneous increase of their stratigraphic age.     

Iron–titanium sands of the Atlantic beaches between Tan-Tan and Tarfaya (southwest Morocco): Characterisation and origin

In Morocco, the most important placers of ferrotitanium minerals are found along the Laâouina–Cape Juby Atlantic coastline, where they accumulate in the upper parts of the foreshores. The heavy minerals would come from the dismantling of the acidic to intermediate magmatic rocks of the Precambrian Anti-Atlasic buttonholes and from the Meseta basement where crystallophyllous rocks predominate. The sands emanating from this erosion, once ejected by the rivers in the Atlantic, are transported by the littoral drift in the direction of the south before being trapped at the level of the great virgation of the shoreline of Laâouina–Cape Juby. The wind deflation, in its turn, reinforces this sorting by carrying away the white sands towards the continent and also the black sands sometimes. The cliffs along the coast of Laâouina–Sidi Akhfenir are, however, barriers against wind loss unlike the sector of Sidi-Akhfenir–Cape Juby where the continuous migration of sands to the hinterland is facilitated by the absence of cliffs. The conjunction of these factors has the consequence of weakening the retention of sands' ferrotitanium in the sector Sidi Akhfenir–Cape Juby compared with its counterpart of Laâouina–Sidi Akhfenir. In general, the Laâouina–Cape Juby coastline can be considered a morphological and hydrodynamic trap whose concentrations in ferrotitanium minerals are likely to earn the quality of a mining district despite its seasonal instability and the difficulty of estimating reserves. Indeed, in this supposed district, heavy minerals total about 95 % of the raw sediments and ilmenite predominates and its alteration state is only superficial.     

Tectonic–karstic origin of the alleged “impact crater” of Lake Isli (Imilchil district,High Atlas,Morocco)

The scenic lakes Tislit and Isli of the Imilchil area in the central High Atlas of Morocco have been recently promoted to the rank of “dual impact crater” by a group of geoscientists. This was promptly denied by a group of meteorite specialists, but the first team reiterated their impact crater interpretation, now restricted to Lake Isli. This alleged 40-kyr-old impact crater would be associated with the Agoudal meteorite recognized further in the southeast. Here, we show that the lake formed during the Lower–Middle Pleistocene in a small Pliocene (?) pull-apart basin through additional collapsing due to karst phenomena in the underlying limestones. This compares with the formation of a number of lakes of the Atlas Mountains. None of the “proofs” produced in support of a meteoritic origin of Lake Isli coincides with the geology of the area.     

The evolution characteristics and fractionation mechanism of carbon isotopes in the process of “multi-stage hydrocarbon generation”

The Jiyang Sag and the Liaohe Basin are the two important areas where immature oil resources are distributed in China. From these two areas immature-low mature to mature oil samples were collected for carbon isotopic analysis. The extracts of source rocks are dominant in the Jiyang Sag while crude oils are dominant in the Liaohe Basin. The maturity index, Ro, for source rocks varies from 0.25%(immature) to 0.65% (mature). Studies have shown that within this range of Ro values the extracts of source rocks and crude oils, as well as their fraction components, have experienced observable carbon isotope fractionation. The carbon isotopic values tend to increase with burial depth, the oils become from immature-low mature to mature, and the rules of evolution of oils show a three-stage evolution pattern, i. e. ,light→heavy→light→heavy oils. Such variation trend seems to be related to the occurrence of two hydrocarbon-generating processes and the main hydrocarbon-forming materials being correspondingly non-hydrocarbons and possessing MAB characteristics, lower thermodynamic effects and other factors. In the process towards the mature stage, with increasing thermodynamic effects, the thermal degradation of kerogens into oil has become the leading factor, and correspondingly the bond-breaking ratio of ^12C-^13C also increases,making the relatively ^12C-rich materials at the low mature stage evolve again towards ^13C enrichment.     

The mantle rock (“laterite”) of the Gold Coast and its origin

Zusammenfassung Der Verwitterungsmantel (Laterit s. l.) der südlichen Goldküste besteht aus Horizonten, die sowohl verschiedene Entstehungsart als verschiedenes Alter haben. Brekzien oder Steinschichten sind unter aridem Klima als Wüstenpflaster entstanden. Zonen chemisch verwitterten Felses, Horizonte von lehmigem Sand (an deren Aufbau Termiten wesentlich beteiligt sind) und Konkretionen haben sich unter feuchtem Klima gebildet. Harte limonitische Oberflächen-Krusten deuten auf progressive Austrocknung hin. Unter diesen drei klimatischen Bedingungen gebildete Horizonte wiederholen sich mehrfach im Verwitterungsmantel der Goldküste. Ein junger, unvollständiger Zyklus ist weit verbreitet, ein älterer Zyklus tritt nur in begrenzten Vorkommen auf, und ein dritter Zyklus ist fast nur noch in aufgearbeiteten, limonitisierten Bruchstücken erhalten. Die wiederholten Klimaschwankungen machen es wahrscheinlich, daß der Verwitterungsmantel zeitlich dem größeren Teil des Quartärs entspricht. Wahrscheinlich können die Ergebnisse auf weit größere Gebiete angewandt werden.     

Natural and anthropic perturbations to the chemical composition of the Colorado River (Tucumán,Argentina)

Economic and urban development in the province of Tucumán is closely associated with its hydrological network. In spite of the regulatory efforts to preserve the quality of the water resources, the lower basins of the majority of the rivers are contaminated with organic effluents derived from sugar-mill and citrus industry. In this paper, the conditions of the Colorado River basin are described. At its headwater, the lithology and geology determine the chemical composition. Calcite and gypsum dissolution and silicate influence water composition, which is slightly perturbed a few kilometers downstream by geothermal waters discharged by a tributary. Close to the discharge into the Salí River, the Colorado River receives a high organic matter load from the highly polluted Calimayo stream, which produces an increase in the organic matter and depletion of dissolved oxygen with redox conditions that promote the reduction of sulfate to sulfide.     

The composition of Alpine marine sediments (Bündnerschiefer Formation,W Alps) and the mobility of their chemical components during orogenic metamorphism

The Bündnerschiefer of the Swiss-Italian Alps is a large sedimentary complex deposited on the Piemonte–Liguria and Valais oceans and associated continental margins from the upper Jurassic to Eocene. It is made of a large variety of sequences associated or not with an ophiolitic basement. The Bündnerschiefer makes an accretionary prism that developed syn-tectonically from the onset of alpine subduction, and it records orogenic metamorphism following episodes of HP metamorphism. The Bündnerschiefer shares important similarities with the Otago schists of New Zealand and with the Wepawaug schists of Connecticut, both of which form accretionary prisms and have an orogenic metamorphic imprint.With the aim of testing the hypothesis of mobility of chemical components as a function of metamorphic grade, in this work I present fifty-five bulk chemical analyses of various lithological facies of the Bündnerschiefer collected along the well-studied field gradient of the Lepontine dome of Central Switzerland, in the Prättigau half window of East Switzerland, and in the Tsaté Nappe of Valle d'Aosta (Italy). The dataset includes the concentration of major components, large ion lithophile elements (Rb, Sr, Ba, Cs), high field strength elements (Zr, Ti, Nb, Th, U, Ta, Hf), fluid-mobile light elements (B, Li), volatiles (CO₂, S), REEs, and Y, V, Cr, Co, Sn, Pb, Cu, Zn, Tl, Sb, Be, and Au. These data are compared against the compositions of the global marine sediment reservoir, typical crustal reservoirs, and against the previously measured compositions of Otago and Wepawaug schists. Results reveal that, irrespective of their metamorphic evolution, the bulk chemical compositions of orogenic metasediments are characterized by mostly constant compositional ratios (e.g., K₂O/Al₂O₃, Ba/Al₂O₃, Sr/CaO, etc.), whose values in most cases are undistinguishable from those of actual marine sediments and other crustal reservoirs. For these rocks, only volatile concentrations decrease dramatically as a function of metamorphic temperature, and significant deviations from the reservoir signatures are evident for SiO₂, B, and Li. These results are interpreted as an indication of residual enrichment in the sediments, a process taking place during syn-metamorphic dehydration from the onset of metamorphism in a regime of chemical immobility. Residual enrichment increased the absolute concentrations of the chemical components of these rocks, but did not modify significantly their fundamental ratios. This poor compositional modification of the sediments indicates that orogenic metamorphism in general does not promote significant mass transfer from accretionary prisms. In contrast, mass transfer calculations carried out in a shear zone crosscutting the Bündnerschiefer shows that significant mass transfer occurs within these narrow zones, resulting in gains of H₂O, SiO₂, Al₂O₃, K₂O, Ba, Y, Rb, Cu, V, Tl, Mo, and Ce during deformation and loss of Na₂O, CO₂, S, Ni, B, U, and Pb from the rock. These components were presumably transported by an aquo-carbonic fluid along the shear zone. These distinct attitudes to mobilize chemical elements from orogenic sediments may have implications for a potentially large number of geochemical processes in active continental margins, from the recycling of chemical components at plate margins to the genesis of hydrothermal ore deposits.     

The “Calamines” and the “Others”: The great family of supergene nonsulfide zinc ores

“Nonsulfides” is a term, which comprises a series of oxidized Zn(Pb)-ore minerals. It has also been used to define a special deposit type, mainly considered as derived from the weathering of Zn(Pb) sulfide concentrations. However, nonsulfide zinc deposits have been distinguished between supergene and hypogene, according to their mineralogy, geological characteristics and genetic setting. The supergene deposits formed by weathering and oxidation at ambient temperatures, whereas the hypogene ones are considered hydrothermal, or associated with metamorphic processes on primary sulfide ores.In this review paper, a comparison between a number of several nonsulfide deposits has been carried out: typical “Calamines”, peculiar “Calamines” and “Others”. The whole group comprises deposits of typical supergene origin, mixed supergene–hypogene mineralizations, and oxidized concentrations characterized by different metals only locally associated with zinc. The Zn–Pb nonsulfide concentrations hosted in carbonate rocks, which are mainly attributed to “wall-rock replacement” and “direct-replacement” supergene processes, are the typical “Calamines” (Liège district, Belgium; Iglesias district, Italy; Silesia–Cracow district, Poland). Peculiar “Calamine” deposits are those mineralizations that have been generally considered as supergene, but which are instead genetically related, at least partly, to hypogene processes (e.g. Angouran, Iran; Jabali, Yemen), though mineralogically and texturally similar to supergene nonsulfide deposits. The “Others” are prevailingly supergene nonsulfide zinc deposits not hosted in carbonate rocks (Skorpion, Namibia; Yanque, Peru), or characterized by other metals as main commodities, like lead (Magellan, Australia), silver (Sierra Mojada, Mexico; Wonawinta, Australia) or vanadium (Otavi Mountainland, Namibia).Minerals of current economic importance in most “Calamine” deposits are smithsonite, hydrozincite, and cerussite. This mineralogical association is generally simple but, when the “Calamines” are dolomite-hosted, one of the consequences of the “wall-rock replacement” process is the generation of a series of economically useless Zn- and Mg-bearing mixed carbonate phases. Secondary deposits hosted in silicatic (sedimentary or volcanic) rocks mainly contain hemimorphite and/or sauconite. Lead-, Ag- and V-rich nonsulfide ores are characterized by a more complex mineralogical association: mixed Pb-carbonates, Pb-sulfates, Pb-phosphates, Pb-arsenates, various Ag-sulfosalts, and Zn–Pb–Cu-vanadates.Carbon and oxygen stable isotope studies allow distinguishing between supergene and hypogene nonsulfide deposits, evaluating the effects of oxidative heating and even gaining indirect paleoclimatic information. The oxygen-isotope variation of the individual carbonate minerals within a deposit is relatively small, indicating constant formation temperatures and a single, meteoric fluid source. Carbon-isotope values are highly variable, thus suggesting several isotopically distinct carbon sources.Periods of paleoclimatic switch-overs from seasonally humid/arid to hyperarid have been considered as the most favorable conditions for the formation and preservation of supergene nonsulfide deposits. However, while several recent nonsulfide deposits throughout the world are positioned between 15° and 45° N latitude, thus pointing to a warm and humid weathering climate, others have been deposited in sub-Arctic regions.The economic value of the nonsulfide Zn(Pb–Ag–V) ores is highly variable, because more than in the case of metallic sulfide deposits, it resides not only on the geological setting, but also on their mineralogy that can directly influence processing and metallurgy.