Ore mineralization related to geological evolution of the Karkonosze–Izera Massif (the Sudetes,Poland) — Towards a model

The Karkonosze–Izera Massif is a large tectonic unit located in the northern periphery of the Bohemian Massif. It includes the Variscan Karkonosze Granite (about 328–304 Ma) surrounded by the following four older units:

• -Izera–Kowary (the Early Paleozoic continental crust of the Saxothuringian Basin),
• -Ještĕd (the Middle Devonian to Lower Viséan sedimentary succession deposited on the NE passive margin of the Saxothuringian Terrane), out of the present study area,
• -Southern Karkonosze (metamorphosed sediments and volcanics filling the Saxothuringian Basin), out of the present study area,
• -Leszczyniec (Early Ordovician, obducted fragment of Saxothuringian Basin sea floor).

The authors present a genetic model of ore mineralization in the Karkonosze–Izera Massif, in which ore deposits and ore minerals occurrences are related to the successive episodes of the geological history of the Karkonosze–Izera Massif:

• -formation of the Saxothuringian Basin and its passive continental margin (about 500–490 Ma)
• -Variscan thermal events:
  • -regional metamorphism (360–340 Ma)
  • -Karkonosze Granite intrusion (328–304 Ma)
• -Late Cretaceous and Neogene-to-Recent hypergenic processes.

The oldest ore deposits and ore minerals occurrences of the Karkonosze–Izera Massif are represented by pyrite and magnetite deposits hosted in the Leszczyniec Unit as well as by magnetite deposit and, presumably, by a small part of tin mineralization hosted in the Izera–Kowary Unit. All these deposits and occurrences were subjected to the pre-Variscan regional metamorphism.Most of the Karkonosze–Izera Massif ore deposits and occurrences are related to the Karkonosze Granite intrusion. This group includes a spatially diversified assemblage of small ore deposits and ore mineral occurrences of: Fe, Cu, Sn, As, U, Co, Au, Ag, Pb, Ni, Bi, Zn, Sb, Se, S, Th, REE, Mo, W and Hg located within the granite and in granite-related pegmatites, in the close contact aureole of the granite and within the metamorphic envelope, at various distances from the granite. Assuming world standards, all these deposits are now uneconomic. Various age determinations indicated that ore formation connected with the Karkonosze Granite might have taken place mostly between about 326 and 270 Ma.The last ore-forming episode in the Karkonosze–Izera Massif is related to hypergenic processes, particularly important in the northern part of the massif, in the Izera–Kowary Unit where some uranium deposits and occurrences resulted from the infiltration of ore solutions that originated from the weathering of pre-existing accumulations of uranium minerals. A separate problem is the presence of oxidation zones of ore deposits and occurrences, both the fossil and the recent.A full list of ore minerals identified in described deposits and occurrences of the Karkonosze–Izera Massif together with relevant, key references is presented in the form of an appendix.     

Chemical and isotopic variations in the Wiśniówka Mała mine pit water,Holy Cross Mountains (south-central Poland)

In 2005 and 2006, hydrogeochemical study was carried out in the bipartite Wiśniówka Mała pit lake of the Holy Cross Mountains (south-central Poland). This is the largest acidic water body in Poland. This report presents the element concentrations in the water and sediment, stable sulfur and oxygen isotope ratios in the soluble sulfates, and stable oxygen isotope ratio in the water. The scope of the investigation also encompassed mineralogical examinations (scanning electron microscope, X-ray diffraction) of the sediment. The results of this study show that there is a spatial and temporal variability in concentrations of most elements and sulfur isotope ratios in the examined pit lake. The water of the western pond displayed a lower pH with a mean of 3.73 and higher conductivity (390 μS cm⁻¹) as well as higher concentrations of sulfates (156 mg L⁻¹) and most of the cations and anions. The concentrations of Fe²⁺ and Fe³⁺ averaged 0.8 and 0.4 mg·L⁻¹. In contrast, the eastern pond water revealed a higher pH (mean of 4.36), lower conductivity (293 μS cm⁻¹) and lower sulfate (90 mg L⁻¹) and trace metal levels. Similar variations were recorded in the stable sulfur isotope ratios. The δ³⁴S_V-CDT(SO₄ ²⁻) values in the water of the western pit pond were in the range of −6.7 to −4.6‰ (mean of −5.6‰), whereas that in the eastern pit pond ranged from −2.2 to −0.9‰ (−1.6‰). The alkalinity of the entire lake water was below 0.1 mg·L⁻¹ CaCO₃. No distinct difference in the δ¹⁸O_V-SMOW(SO₄ ²⁻) was noted between the western and eastern pit ponds. Compared to the Purple Pond in the Sudetes (Poland) and similar sites throughout the world, the examined pit lake is highlighted by distinctly low concentrations of sulfates, iron and other trace metals. Based on this and other studies performed in the Holy Cross Mountains, a conclusion can be drawn that the SO₄ ²⁻ in the Wiśniówka Mała pit lake water is a mixture of SO₄ ²⁻ derived from the following sources: (1) pyrite oxidation (especially in the western pond water), (2) leaching of soluble sulfates from soils and waste material, as well as (3) subordinate deposition of airborne sulfate precipitation.     

Influence of contaminated Vistula River water on the groundwater entering the Zakrzówek limestone quarry, Cracow region, Poland

 Chemical composition of water inflows in the Zakrzówek quarry, developed in fractured and karstified Upper Jurassic limestones, is controlled by infiltration of polluted water from the Vistula River and by infiltrating meteoric water. The river water TDS value is 2.5 g/dm³. The quarry waters have 0.6–2.0 g/dm³ TDS. Highly mineralised waters belong to Cl-Na type. With decreasing TDS the percentage of sulphates, calcium, magnesium and hydrocarbonates increases. This seems to result from various processes including dilution of polluted river water, leaching of aquifer rocks, and ion exchange. The transfer time of river water to the quarry is about 100–120 days. Concentration of contaminants contained in the river water declines during the migration through limestones to the quarry. Received: 7 March 1997 · Accepted: 7 December 1998     

Groundwater vulnerability map of the Chrzanów karst-fissured Triassic aquifer (Poland)

A map shows intrinsic vulnerability to pollution of the Chrzanów karst-fissured aquifer (273 km²) in the southern part of Poland. This aquifer is intensively drained by numerous intakes and Zn-Pb ore mines. A DRASTIC-type parametric system was applied for groundwater vulnerability evaluation. Vulnerability assessment is based on six factors (depth to groundwater table, lithology of the unsaturated zone, net recharge, hydraulic conductivity of the aquifer, groundwater flow velocity, aquifer thickness). For the final vulnerability map construction at the scale of 1:50,000, a combination of the aquifer simulation model (using MODFLOW) and a geographical information system was applied. Maps of the net recharge, hydraulic conductivity of the aquifer and groundwater flow velocity were derived by aquifer modelling. Based on the vulnerability index (21-182), six relative vulnerability classes were selected. Reliability of the map has been verified.     

Fluid influence on mineral reactions in ultrahigh-pressure granulites: a case study in the Śnieżnik Mts. (West Sudetes, Poland)

Small tectonic slices of undeformed eclogites and ultrahigh-pressure granulites occur in three tectonic units of the Śnieżnik Mts. (SW Poland). Ultrahigh-pressure granulite/eclogite transitions with peak metamorphic conditions between 21 and 28 kbar at 800 to 1000 °C occur only in the Złote unit. Conventional U-Pb multigrain analyses of zircons from a mafic granulite provided ²⁰⁷Pb/²⁰⁶Pb ages between 360 to 369 Ma which are interpreted to approximate timing of original crystallisation from a melt. Diffusion kinetics and the restricted availability of a fluid phase mainly controlled the conversion from granulite to eclogite, although some bulk-chemical differences were also recognised. The ultrahigh-pressure granulites from the Złote unit exclusively contain H₂O-rich inclusions with variable salinities which distinguishes them from high-temperature (HT)-granulites world-wide. This is also in contrast to the fluid regime (H₂O-N₂-CO₂) recognised in the lower-temperature eclogites (600–800 °C) from the closely associated Międzygórze and Śnieżnik units. The variation in fluid composition between the lower-temperature eclogites and ultrahigh-pressure granulites on the one hand and ultrahigh-pressure granulites and HT-granulites on the other hand probably indicates contrasting P-T-t paths as a result of different tectonic environments. Received: 15 June 1998 / Accepted: 2 March 1999     

Geology,stratigraphy and palaeoenvironmental evolution of the Stephanorhinus kirchbergensis-bearing Quaternary palaeolake(s) of Gorzów Wielkopolski (NW Poland,Central Europe)

The sedimentary succession exposed in the Gorzów Wielkopolski area includes Eemian Interglacial (MIS 5e) or Early Weichselian (MIS 5d–e) deposits. The sedimentary sequence has been the object of intense interdisciplinary study, which has resulted in the identification of at least two palaeolake horizons. Both yielded fossil remains of large mammals, alongside pollen and plant macrofossils. All these proxies have been used to reconstruct the environmental conditions prevailing at the time of deposition, as well as to define the geological context and the biochronological position of the fauna. Optically stimulated luminescence dating of the glaciofluvial layers of the GS3 succession to 123.6 ± 10.1 (below the lower palaeolake) and 72.0 ± 5.2 ka (above the upper palaeolake) indicate that the site formed during the Middle–Late Pleistocene (MIS 6 – MIS 5). Radiocarbon-dating of the lacustrine organic matter revealed a tight cluster of Middle Pleniglacial Period (MIS 3) ages in the range of ~41–32 ka cal bp (Hengelo – Denekamp Interstadials). Holocene organic layers have also been found, with ¹⁴C ages within a range of 4330–4280 cal bp (Neolithic). Pollen and plant macrofossil records, together with sedimentological and geochemical data, confirm the dating to the Eemian Interglacial.     

From back-arc to rifted margin: Geochemical and Nd isotopic records in Neoproterozoic?-Cambrian metabasites of the Bystrzyckie and Orlickie Mountains (Sudetes,SW Poland)

Metamorphosed during the Variscan orogeny, sediments of the ca. 560 Ma M?ynowiec Formation and ca. 530 Ma Stronie Formation in the Bystrzyckie and Orlickie Mountains (Central Sudetes, Poland) contain metabasites with a range of basaltic compositions. Immobile trace element and Nd isotope features allow distinction of dominant, either E-MORB-like (Group 1: Zr/Nb 9–20, εNd₅₃₀ +2.6 to +6.7) or mildly enriched N-MORB-like tholeiites (Group 2: Zr/Nb 21–27, εNd₅₃₀ +0.2 to +6.7), and scarce but genetically important OIB-like alkaline (Group 3: Zr/Nb 5, εNd₅₃₀ +2.2) or depleted tholeiitic rocks (Group 4: Zr/Nb 67, εNd₅₃₀ +7.9). Neither the radiogenic age nor age relationships between these four groups are known. However, field evidence suggests that the metabasites are younger than the M?ynowiec Formation and that their emplacement must have been coeval with the accumulation of the Stronie Formation sediments. The OIB affinity of Group 3 is interpreted to reflect an enriched mantle (EM)-type asthenopheric source whilst the groups of tholeiitic rocks indicate involvement of depleted (locally slightly residual) MORB-type mantle (DMM). Several geochemical signatures, the decoupling between Nd isotope and trace element characteristics, and melting models indicate variable enrichment of the DMM-like source, here ascribed to asthenosphere-derived OIB-like melts (Group 1 and 2) and a contribution from a supra-subduction zone (Group 2 and 4). Based on contrasting back-arc basin (BAB)- and within-plate-like affinities of the metabasites, and on petrogenetic constraints from the spatially related infill of the Stronie Formation rift basin, the studied magmatic episode is suggested be related to cessation of the supra-subduction zone activity, presumably induced by ridge-trench collision. This event might have led to slab break-off, the development of a transform plate boundary, opening of a slab window and upward migration of sub-slab enriched asthenosphere. Decompression melting of the upwelling asthenosphere could then have produced OIB-like melts which segregated and infiltrated into the mantle of the former subduction zone, with randomly distributed slab-derived components. In an extensional regime, magmas generated at shallow levels from heterogeneous mantle regions were emplaced within sedimentary rocks of the overlying rift basin. The vestiges of subduction-related processes and within-plate style of mantle enrichment suggest that the metabasites could be related to final stages of the Cadomian orogeny and incipient Early Palaeozoic rifting of Gondwana that heralded the opening of the Rheic Ocean.     

Neoproterozoic and Cambro-Ordovician magmatism in the Variscan Kłodzko Metamorphic Complex (West Sudetes,Poland): new insights from U/Pb zircon dating

The Kodzko Metamorphic Complex (KMC) in the Central Sudetes consists of meta-sedimentary and meta-igneous rocks metamorphosed under greenschist to amphibolite facies conditions. They are comprised in a number of separate tectonic units interpreted as thrust sheets. In contrast to other Lower Palaeozoic volcano-sedimentary successions in the Sudetes, the two uppermost units (the Orla-Googowy unit and the Kodzko Fortress unit) of the KMC contain meta-igneous rocks with supra-subduction zone affinities. The age of the KMC was previously assumed to be Early Palaeozoic–Devonian, based on biostratigraphic findings in the lowermost tectonic unit. Our geochronological study focused on the magmatic rocks from the two uppermost tectonic units, exposed in the SW part of the KMC. Two orthogneiss samples from the Orla-Googowy unit yielded ages of 500.4±3.1 and 500.2±4.9 Ma, interpreted to indicate the crystallization age of the granitic precursors. A plagioclase gneiss from the same tectonic unit, intimately interlayered with metagabbro, provided an upper intercept age of 590.1±7.2 Ma, which is interpreted as the time of igneous crystallization. From the topmost Kodzko Fortress unit, a metatuffite was studied, which contains a mixture of genetically different zircon grains. The youngest ²⁰⁷Pb/²⁰⁶Pb ages, which cluster at ca. 590-600 Ma, are interpreted to indicate the maximum depositional age for this metasediment. The results of this study are in accord with a model that suggests a nappe structure for the KMC, with a Middle Devonian succession at the base and Upper Proterozoic units at structurally higher levels. It is suggested here that the KMC represents a composite tectonic suture that juxtaposes elements of pre-Variscan basement, intruded by the Lower Ordovician granite, against a Middle Palaeozoic passive margin succession. The new ages, combined with the overall geochemical variation in the KMC, indicate the existence of rock assemblages representing a Gondwana active margin. The recognition of Neoproterozoic subduction-related magmatism provides additional arguments for the hypothesis that equivalents of the Teplá-Barrandian domain are exposed in the Central Sudetes.     

Sorption of uranium(VI) at the clay mineral–water interface

Batch experiments were conducted to study the sorption of uranium on selected clay minerals (KGa-1b and KGa-2 reference kaolinite, SWy-2 and STx-1b reference montmorillonite, and IBECO natural bentonite) as a function of pH (4–9) and 0.001, 0.01, and 0.025 M NaCl in equilibrium with the CO₂ partial pressure of the atmosphere. Uranium concentrations were kept below 100 μg L⁻¹ to avoid precipitation of amorphous Uranium-hydroxides. Solely PTFE containers and materials were used, because experiments showed significant sorption at higher pH on glass ware. All batch experiments were performed over a period of 24 h, since kinetic experiments proved that the common 10 or 15 min are in many cases by far not sufficient to reach equilibrium. Kaolinite showed much greater uranium sorption than the other clay minerals due to the more aluminol sites available. Sorption on the poorly crystallized KGa-2 was higher than on the well-crystallized KGa-1b. Uranium sorption on STx-1b and IBECO exhibited parabolic behavior with a sorption maximum around pH 6.5. Sorption of uranium on montmorillonites showed a distinct dependency on sodium concentrations because of the effective competition between uranyl and sodium ions, whereas less significant differences in sorption were found for kaolinite. The presence of anatase as impurity in kaolinite enhanced the binding of uranyl-carbonate complexes with surface sites. The kinetic of uranium sorption behavior was primarily dependent on the clay minerals and pH. A multisite surface complexation model without assuming exchange is based on the binding of the most dominant uranium species to aluminol and silanol edge sites of montmorillonite, respectively to aluminol and titanol surface sites of kaolinite. For eight surface species, the log_k was determined from the experimental data using the parameter estimation code PEST together with PHREEQC.     

Mafic rocks in a deep-crustal segment of the Variscides (the Góry Sowie, SW Poland): evidence for crustal contamination in an extensional setting

Coronitic metagabbronorites (so-called hyperites) and metabasites occur within gneisses, migmatites and minor granulites in the high-grade metamorphic Góry Sowie Block in the Sudetes (SW Poland). Incompatible trace-element and )Nd data, combined with field and petrographic evidence, suggest that three groups may be distinguished: (1) "enriched" amphibolites (Zr/Nb ca. 8, )Nd₅₀₀ +1 - +2.5), (2) "depleted" amphibolites (Zr/Nb >30, )Nd₅₀₀ +5 - +6), and (3) metagabbronorites (Zr/Nb 13-19, )Nd₅₀₀ scattered between +5.3 and -1). These characteristics favour an extensional within-plate setting, consistent with their field occurrence as small bodies scattered within metasedimentary and felsic metaigneous gneisses. In that setting, enriched mantle sources were partially melted to produce a range of basic magmas, showing affinities with continental tholeiites (within plate-type basalts). Presumably, in a more advanced stage of rifting, more depleted varieties, transitional to N-MORB, were emplaced. These mafic magmas were variably contaminated during their ascent in the crust. The metagabbronorites, with their well-preserved igneous textures, were previously interpreted as having been intruded after the main deformation and after the peak of amphibolite facies metamorphism (some authors suggesting a relation to the "circum Góry Sowie ophiolites"). However, the geochemical characteristics and P-T estimates suggest that the metagabbronorites are unrelated to the ophiolitic gabbros found in the neighbourhood of the Góry Sowie Block and, in contrast to them, have experienced a complex, polybaric P-T path.     

Progressive failure leading to the 3 December 2013 rockfall at Puigcercós scarp (Catalonia,Spain)

A detailed analysis of the pre-failure behavior of the 3 December 2013 rockfall (1,012 m³) occurred on Puigcercós pilot study area (Catalonia, Spain) is presented. The exact date of failure was obtained based on a photographic monitoring performed every 4 h. The long-term monitoring (2,217 days) of the rock slope carried out by a Terrestrial LiDAR allowed the early detection of both pre-failure deformation and precursory rockfalls preceding the final failure. By means of the analysis of the pre-failure deformation, four different deformed areas were detected and the tertiary creep phase was observed in three of them. An attempt to predict the time to failure was performed using the Fukuzono’s (1985) method. Furthermore, the temporal evolution of the precursory rockfalls occurred in those four areas during the progressive failure showed a close resemblance with the exponential pattern of the cumulated displacements at tertiary creep stage. Finally, the study of the meteorological conditions did not show any single triggering factor associated with the final failure. Reversely, the increase in the occurrence of precursory rockfalls on several areas of the slope together with the observed acceleration on the deformation pattern reinforce the role of a progressive degradation of the stability conditions, which ultimately leaded to the 3 December rockfall event.     

A new Cenomanian vertebrate tracksite at Tamajón (Guadalajara,Spain): Palaeoichnology and palaeoenvironmental implications

A new Upper Cretaceous vertebrate tracksite has been discovered at Tamajón (Iberian Ranges, Guadalajara, Spain). The track level is a relatively smooth and slightly undulating sandy ferruginous crust, corresponding to an erosive surface at the base of a small meandering channel. It is incised into the underlying planar cross-bedded sandstones of coastal bars located at the middle-upper part of the Utrillas Formation (middle-upper Cenomanian). The site shows an extraordinary concentration of vertebrate tracks, among which numerous sets of two to five isolated digit impressions (“swim tracks”) and, at least, two trackways referred to crocodyliforms, and a single tridactyl footprint probably produced by a theropod dinosaur can be recognized. There are also several long traces (epichnial grooves) revealing sharp direction changes (up to 90°) which seem to be fish fin traces (Undichna unisulca), although crocodyliforms (tail marks) and/or fish invertebrates cannot be rejected as possible tracemakers. Some crocodyliform tracks reveal a thin raised rim, due to the displacement of the sediment by the pressure produced by the feet. Several impressions are moderately deformed by small sediment slides, only preserving their deepest part (claw marks). This is clearly indicative of a soft substrate with a high degree of plasticity and water content at the time of the track registration. Nevertheless, the sediment was hard enough to preserve manus and pes print morphologies and also possible crocodyliform tail and/or fish fin traces. Small rhizoliths can also be recognized and may belong to herbaceous wetland vegetation. The morphology of the palaeochannel, the sedimentary context and the track preservation seem to indicate that the tracks were impressed in a shallow channel located near the coast, under wet conditions and in different moments of time. This discovery represents the first occurrence of vertebrate ichnites in the Utrillas Formation, a stratigraphic unit where osteological and ichnological remains are relatively scarce, and it confirms that some crocodyliforms lived in near coast channels during the deposition of this unit.     

Prehistoric soil and water detention structures (gabarbands) at Phang,Sindh Kohistan,Pakistan: An adaptation to environmental change?

Five gabarbands (dams), components of integrated soil and water conservation systems, were investigated in the arid region of Sindh Kohistan. The dams are associated with two prehistoric Kot Dijian settlements, Phang and Kohtrash (3200–2800 B. C.). The dams were constructed with relatively permeable materials. Three of the dams, South, East, and North, close off water gaps and a strike valley, respectively, to form a detention basin. The West Dam, located on Phang Nai, upstream of the detention basin removed the coarser sediment fraction from the flows. Spring Dam, located in a water gap to the north of the detention basin, acted as a low-head weir to distribute flow from a perennial spring onto the floodplain of Baran Nai, where double-cropping was probably practiced. Faulting eliminated the spring, which had probably supported the Kohtrash site, and led to construction of the detection basin for the purposes of subsurface storage of detained flows. Association of both modern and prehistoric sites with springs suggests that there has not been appreciable climate change in Sindh Kohistan in the last 5000 years. © 1993 John Wiley & Sons, Inc.     

Early Carboniferous (Viséan) emplacement of the collisional Kłodzko–Złoty Stok granitoids (Sudetes, SW Poland): constraints from geochemical data and zircon U–Pb ages

Sensitive high-resolution ion microprobe zircon U–Pb dating and geochemical data of igneous rocks from the composite K?odzko–Z?oty Stok (KZS) Granite Pluton, Sudetic Block, indicate that the granitoids represent an Early Carboniferous Viséan phase of Variscan metaluminous, high-K, I-type, syn-collisional granite magmatism within the Saxothuringian Zone of the Central European Variscides. Igneous zircon records hypabyssal magmatism that produced various granitoids and lamprophyre (spessartite) emplaced from ca. 340 to 331 Ma. The KZS granitoids have compositions ranging from granodiorite to monzonite, low A/CNK ratios (<1), and are associated with abundant mafic members. Most of them are alkaline, highly potassic, and moderately evolved. The major and trace element contents of the KZS granitoids suggest geochemical heterogeneity, and the hybrid nature of magmas derived from a range of sources in the middle crust, with a strong input of material from the upper mantle. Mixing of magmas of mantle origin with high-K material from partly melted continental crust was probably a more important factor than fractional crystallization, in controlling the evolution of the magmas. The mean Pb–U ages of the main population of igneous zircon from a quartz monzodiorite (?elazno) and hornblende monzonite (Droszków) are 340.2 ± 2.5 Ma and 339.5 ± 3.1 Ma, respectively. A slightly younger biotite-hornblende granodiorite from Chwalis?aw, 336.7 ± 2.5 Ma, was cut by a spessartite dyke at 333.1 ± 3.1 Ma. This indicates that mafic magmas were immediately intruded into fractured, probably incompletely solidified, granodiorites. The lamprophyric dyke also contains igneous zircon of Neoproterozoic age, 566.3 ± 6.4 Ma, typical of the crust in the Saxothuringian Zone. Tonalite from Ptasznik Hill near Droszków is of similar age to the spessartite, 331.5 ± 2.6 Ma. High REE contents in the tonalite and its igneous zircon indicate advanced differentiation of granitic magma, producing a more leucocratic melt associated with post-magmatic activity including abundant late crosscutting pegmatites and quartz veins, and contact metasomatic mineralization. The KZS granitoids have rather similar petrographic and geochemical characteristics to granitoids from other parts of the Central European Variscides, where a thickened orogenic root caused a substantial rise in crustal temperatures, producing granitoid magmas closely correlated with regional tectonic activity between the Saxothuringian and Brunovistulia Terranes at the NE margin of the Bohemian Massif.     

Late Maastrichtian cephalopods,dinoflagellate cysts and foraminifera from the Cretaceous–Paleogene succession at Lechówka,southeast Poland: Stratigraphic and environmental implications

The Lechówka section comprises the most complete Cretaceous–Paleogene (K-Pg) boundary succession in Poland and is among 29 sites worldwide with the youngest ammonite record. Here, cephalopods (ammonites and nautilids), organic-walled dinoflagellates (dinocysts) and foraminifera from the uppermost Maastrichtian interval are studied. In terms of ammonite biostratigraphy, the upper Maastrichtian Hoploscaphites constrictus crassus Zone is documented up to a level 120 cm below the K-Pg boundary. There is no direct, ammonite-based evidence of the highest Maastrichtian H. constrictus johnjagti Zone. However, the predominance of the dinocyst marker taxon Palynodinium grallator suggests the presence of the equivalent of the uppermost Maastrichtian Thalassiphora pelagica Subzone, which is correlatable with the H. c. johnjagti ammonite Zone. The planktonic foraminiferal assemblage is coeval with that from the H. c. johnjagti Zone as well. These data indicate that the top of the Maastrichtian at Lechówka is complete within the limits of biostratigraphic resolution, albeit slightly condensed. The dinocyst and foraminiferal assemblages are dominated by taxa that are characteristic of high-energy, marginal marine environments. A reduction in test size among the calcareous epifaunal benthic foraminifera is observed at a level 50 cm below the K-Pg boundary, which is possibly related to environmental stress associated with Deccan volcanism.     

X-ray absorption spectroscopy investigation of aqueous Co(II) and Sr(II) sorption at clay–water interfaces

Sorption processes typically control trace metal concentrations in aquatic systems. To illustrate the impact of various types of surface sites on metal ion sorption behavior, Co(II) and Sr(II) sorption by several clay minerals under a range pH and background electrolyte conditions was studied. X-ray absorption spectroscopy (XAS) was used to characterize the surface complexes formed to explain the basis for the sorption trends. At low pH, Co(II) could be displaced from the surface by increasing the Na ion concentration. XAS analysis of these samples showed that sorbed Co(II) retained the coordination structure of aqueous phase Co(II), suggesting the formation of weakly associated, outer-sphere, mononuclear Co complexes at permanent charge sites. At high pH, sorbed Co could not be displaced by increasing the Na ion concentration. The XAS analyses of these samples indicated the formation of Co coprecipitates. The results of the Sr(II) sorption experiments suggested weaker bonding between sorbed Sr and the solid surfaces, regardless of solution conditions and adsorbent. XAS analysis of Sr sorption samples revealed the formation of mononuclear, outer-sphere complexes of Sr at clay–water interfaces, similar to the outer-sphere Co sorption samples observed only at low pH.     

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