Wyniki wyszukiwania - BazTech

1

Pochodzenie i zagrożenia siarkowodorem i wysokociśnieniowym gazem ziemnym w złożu kopalń rud miedzi Polkowice-Sieroszowice i Rudna – wstępne badania izotopowe i mineralogiczne

Kotarba M. J., Bilkiewicz E., Manecki M., Pawlik W., Ciesielczyk A., Selerowicz T.

Biuletyn Państwowego Instytutu Geologicznego

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2017

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nr 469

9--33

PL

Wyniki badań składu cząsteczkowego i izotopowego (13C/12C w CH4, C2H6, C3H8, iC4H10, nC4H10 i CO2, 2H/1H w CH4 i 15N/14N w N2) dwóch próbek gazu ziemnego występującego w utworach wapienia cechsztyńskiego (Ca1) kopalni Rudna porównano z gazem ziemnym akumulowanym w utworach karbonu, czerwonego spągowca i wapienia cechsztyńskiego (Ca1) monokliny przedsudeckiej oraz gazu wytworzonego podczas pirolizy wodnej z kopalnej materii organicznej utworów dolomitu głównego (Ca2). Badany gaz ziemny charakteryzuje się normalnym składem izotopowym w układzie metan–etan–propan, co świadczy o tym, że powstał w jednej fazie generowania z tej samej skały macierzystej, zawierającej kerogen mieszanego typu II/III, prawdopodobnie w obrębie utworów karbońskich. Na podstawie badań mineralogicznych i izotopowych 13C/12C 12 próbek węglanowych i 34S/35S 14 próbek siarczanowych, pobranych w strefie głębokości eksploatacji rud miedzi od 900 do ok. 1200 m ZG Polkowice-Sieroszowice i Rudna w zakresie współczesnych temperatur od 35 do 45°C, wykazano, że w dwóch próbkach węglanów i w dwóch próbkach siarczanów pobranych z jednego rdzenia zachodzą procesy mikrobialnej redukcji anhydrytu dolnego (Ad1) cyklu PZ1 prowadzące do powstawania siarkowodoru.

EN

Composition of natural gas from the Zechstein Limestone (Ca1) strata of Rudna mine has been compared with the natural gas from Carboniferous, Rotliegend strata of the Fore-Sudetic Monocline and with gas generated from the organic matter of the Main Dolomite during hydrous pyrolysis experiments. The gas from Rudna mine is characterized by the normal methane–ethane–propane isotopic system which indicates formation in one stage from a single source rock probably of the Carboniferous age containing kerogen of mixed II/III type. Generation of the hydrogen sulphide resulted from the microbial sulphate reduction processes of the basal anhydrite has been proven by mineralogical and isotopic 13C/12C analyses of 12 carbonate and 34S/35S analyses of 14 sulphate samples. These samples were collected in the mine at the depth of about 900–1200 m at temperature range of 35–45°C and two samples of carbonates were taken from one core.

2

The effect of Ca-Pb and P-As substitutions on the solubulity of hydroxylapatites

Młynarska M., Puzio B., Kwaśniak-Kominek M., Manecki M.

Geology, Geophysics and Environment

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2016

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Vol. 42, no. 1

100--101

EN

Hydroxylapatites are important biomaterials. Substitutions of Pb for Ca and As for P in hydroxylapatites are recently intensively studied due to their significance in the environmental immobilization of Pb and As (Lee et al. 2009, Chlebowska et al. 2015, Motyka et al. 2015). The general chemical formula of minerals in the apatite group is expressed by A 5 (XO 4 ) 3 Z, where A are bivalent cations (e.g., Ca 2+ or Pb 2+ , cations are distributed on two distinct crystallographic sites), XO 4 is a trivalent oxyanion (e.g., PO 4 3, AsO 4 3 - ), and Z is a monovalent anion (OH, F, Cl, or O). Positions Z and X may be partly filled with carbonate CO 3 2−. The structure of hydroxylapatite allows for unlimited substitutions of Pb 2+ for Ca 2+ and AsO 4 3− for PO 4 3−. The ability of lead and arsenic apatites to immobilize these toxic elements result from their high durability and low solubility at the conditions on the Earth surface. Various apatites possess different thermodynamic properties including different solubility in aqueous solutions but the systematic variation of these properties in solid solution series is poorly understood. The main objective of this research is determination of systematic variation in the solubilities of hydroxylapatites resulting from cationic substitutions of Pb 2+ for Ca 2+ and anionic substitutions of AsO 4 3− for PO 4 3− in their structure. Three solid solution series were synthesized: - HPY hydroxypyromorphite Pb 5 (PO 4 ) 3 OH – HAP hydroxyapatite Ca 5 (PO 4 ) 3 OH, HMi hydroxymimetite Pb 5 (AsO 4 ) 3 OH – JBM johnbaumite Ca 5 (AsO 4 ) 3 OH, - HAP hydroxyapatite Ca 5 (PO 4 ) 3 OH – JBM johnbaumite Ca 5 (AsO 4 ) 3 OH. The phases were synthesized from aqueous solutions at high pH above 8, at ambient temperature, by dropwise mixing of chemical reagents. The products are white, fine, homogeneous crystalline powders. Chemical composition determined by SEM/EDS is close to theoretical. X-ray diffraction confirms their crystalline structure and systematic changes in unit cell parameters with ionic substitution. Dissolution experiments were run in thermostatic bath at 25°C. An aliquot of 0.5 g of apatite was dissolved in 250 mL of 0.05M NH 4 NO 3 background solution at pH in the range of 3.5–5.0. Background solution was used to keep the ionic strength constant. The dissolution was carried out for 3 months. The bottles were manually stirred at least two times a week. The solution was syringe-sampled periodically and filtered through 0.2 μm polycarbonate filter to remove the suspended solids. The concentration of Pb and Ca was determined by atomic absorption spectroscopy. The concentration of dissolved phosphates and arsenates was determined by UV-vis colorimetry using a molybdenum blue method. The plateau on concentration evolution patterns from the dissolution experiments was observed to determine equilibrium in the suspensions. Dissolution of all the phases at the conditions of these experiments is incongruent. An increase in solution pH resulting from dissolution was observed in all cases. The system was considered in equilibrium when at least three consecutive samples showed identical concentration of Ca 2+ or AsO 4 3−. The equilibrium in HPY series was assumed by analogy. All the concentrations were recalculated to activities using PHREEQC model with Llnl database. The solubility K sp determined for the endmembers at 25°C conform with the literature data and equal to: HPY-K sp = 10 −7 7. 31 , HAP-K sp = 10 −55.66 , HMi-K sp = 10 −71. 56 , and JBM K sp = 10 −37.76. This confirms that, despite the incongruence of dissolution, the experimental procedure and the calculation scheme provide reliable approximation of the solubilities. The most soluble phase is johnbaumite Ca 5 (AsO 4 ) 3 OH. The solubility of all hydroxylapatites decreases linearly with the increase of Pb and P content. These trends do not correlate with the changes in Gibbs free energy of formation of the phases in question. This indicates that structural (e.g. the size of the ions) and the chemical factors (e.g. electronegativity) play the dominant role in the solubility of substituted hydroxylapatites.

3

The Baklia Fault Zone – a regional strike-slip zone splitting Prins Karls Foreland (Svalbard

Ziemniak G., Czerny J., Manecki M., Kośmińska K.

Geology, Geophysics and Environment

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2016

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Vol. 42, no. 1

142--143

EN

Prins Karls Foreland (PKF) is a westernmost island of Svalbard Archipelago belonging to the Southwestern Basement Province. The island consists of low-metamorphic facies probably Neoproterozoic metasediments, divided into two, northern and southern parts. Both parts are characterized by similar geological structures but different stratigraphy. New discoveries presented here result from joint, Norwegian Polar Institute and AGH UST Krakow expeditions in 2013 and 2014. Thorough characteristics of the location and character of a strike-slip fault splitting PKF (the Baklia Fault Zone) is presented here for the first time. To date, one succession has been distinguished in the lithostratigraphy of PKF’s basement. The northern part of the island consists of two groups: the Scotiafjellet Group and Grampianfjella Group (Dallmann et al. 2015). They comprise low-metamorphic metasediments (chlorite zone of greenschist facies), mostly slates, metapsamites and carbonates. Stratigraphic units of the southern part represent slightly higher, biotite metamorphic zone, and have been considered to be conformably underlying Scotiafjellet Group. The uppermost Peachflya Group and Geikiebreen Group (mostly phyllites with metavolcanics and carbonates) are in thrust contact with underlying Ferrierpiggen Group, comprising schistose diamictites. The Ferrierpiggen Group is a tectonic unit stratigraphically discontinuous at top and bottom. Isolated klippe of the Ferrierpiggen Group separated from Scotiafjellet Group by tectonic boundary is present in the northern part of PKF (Harland et al. 1979, 1993). These complexes have undergone the Caledonian metamorphism followed by D 1 deformation producing SE directed folding and thrusts. D 2 deformation was coaxial, but not coplanar with D 1. D 2 deformation occurred probably in Mid-Cenozoic and resulted in refolding and thrusting, followed by formation of a dextral shear zone along Scotiadalen (Morris 1989). D 3 deformation is connected with transtensional formation of the Forlandsundet Graben along NNW-SSE faults finishing the West Spitsbergen Orogeny (WSO) (Manby 1986). Distinct difference in the stratigraphy of southern and northern parts of PKF is apparent. The presence of the fault dividing the island was indicated before (Hjelle et al. 1979), but no single fault has been recognized during detailed mapping later on (Harland et al. 1979, Morris 1982, Manby 1986, Morris 1989). Mapping and structural measurements conducted by the authors in the area of Selvågen led to the discovery of the major fault zone (the Baklia Fault Zone – BFZ) dividing PKF into two terrains. The BKF have N-S trend from Haukebukta in the west coast, through the slopes of Alasdairhornet (where it trapped few hundred meters long slab of the Ferrierpiggen Group rocks), to the southern Scotiadalen. Approaching Selvågen, the fault zone bends slightly to the NNE-SSW. The zone is filled with breccias and mixture of different lithologies with slabs of rocks derived from both limbs of the fault zone. The width of the zone measures approximately 100–250 meters. To the east, it is accompanied by at least three narrow subparallel faults. The age of the BFZ is unknown. A brittle character of deformation may suggest that it is Cenozoic in age. En échelon normal faults with a drop to the north, which associate BFZ may be considered as a Riedel shears R 1 formed at the beginning of a strike-slip movement. Structural measurements on slickensides as kinematic indicators revealed that normal faulting was associated with both, dextral and sinistral shear (not simultaneous). A main movement connected with dextral shearing occurred probably earlier, during late stages of the early Cenozoic crustal shortening. The extended width of the fault zone and the presence of a mixture of rock material from both terranes suggest the significant lateral displacement that might reach tens of kilometers. The BFZ cuts through the boundary faults of the Forlandsundet Graben displacing them sinistrally by approximately one kilometer. This suggests that sinistral movement was probably associated with rejuvenation of the fault during late stages or after the Forlandsundet Graben formation. There are several regional implications of BFZ. The stratigraphic relationship of southern and northern terranes is unclear. The presence of BFZ at the boundary of the Scotiafjellet and Peachflya groups does not exclude their stratigraphic succession but makes it impossible to define. The field observations suggest that BFZ may be Cenozoic in age. It has similar tectonic style and orientation to other strike-slip zones present along western Svalbard coast. Strong tectonic deformation suggests displacement of the northern terrain of PKF by tens of kilometers. Even though southern terrain can be directly correlated with Oscar II Land, more research is needed to correlate more exotic northern terrain of PKF with the basement rocks in the southern parts of Spitsbergen. Ongoing research towards dating and detail structural characterization of this regional fault zone will allow for reconstruction of pre-Tertiary position of this part of Archipelago.

4

Characteristics of soil of “Józefka” deposit overlay, Kielce District

Pawlikowski M., Manecki M., Kozień D., Waluś E., Borecka A., Stanisz J., Pękala M., Kiecana M.

Geology, Geophysics and Environment

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2016

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Vol. 42, no. 1

116--117

EN

The aim of this article is to describe and characterize the properties of the overburden overlying rocks of “Józefka” mine, with an attempt to demonstrate a dependence of diversified mineral composition on geotechnical characteristics of the tested material. The article presents previously obtained unpublished data necessary for the evaluation of the physical characteristics of the overlying rocks. The research was conducted in the mining area of the “Józefka” mine, located in Górno – ca. 10 km eastwards from Kielce. Dolomite and calcareous rocks, estimated to be Givetian in age (Czarnocki 1938), are exploited in the mine. The obtained material is used as road aggregate. The deposit is located in the southern part of the Świętokrzyskie Mountains, in the so-called Kielce zone being a part of Małopolska Province Massif (Stupnicka 1997). Silty soils occur there as pockets and interbeds. An attempt to describe them precisely has not been undertaken as yet. Three samples with intact structure and natural moisture were collected during field work. The deposit investigations were carried out at two stages: 1) mineralogical and petrographic, and 2) geotechnical. At the first stage, the analysis included optical microscopy of thin sections, X-ray diffractometry and thermal differential analysis DTA. Clay fraction (below 2 μm) was separated by settling in water. Oriented specimens, glikoled and heated to 550°C were analyzed. The rock contains up to 70 wt% of detrital quartz. The second stage of the research programme was conducted in accordance with the engineering practice and standards (PKN-CEN ISO/TS 17892-2:20 09). Basic physical parameters were established: - natural moisture – w n [%], - bulk density – ρ [g/cm 3 ], - density – ρ s [g /cm 3 ], - granulometric composition, - plasticity – w P [%] and liquidity limits – w L [%], - swelling index – p [%]. The results of the mineralogical and petrographical tests revealed that kaolinite is the main fraction of clay minerals in all three samples. The content of clay fraction was determined with the use of two methods: - water separation – 50 g of material was prepared; the clay material in sample 1 constitutes 55% of the whole material, in sample 2–40%, and in sample 3–39%; - areometric – 35g of material was prepared; the results show that the proportions of the clay material amount to: sample 1–48%, sample 2–33%, sample 3–29%. The concurrence of results of both methods is evident. The maximum difference of clay fraction content was 10%. It indicates the difference in selecting equally representative samples. During the geotechnical determination the tested soil was classified as: sample 1 – clay (Cl), sample 2 – sandy clay (saCl), sample 3 – silty sandy clay (sasiCl) (PN-EN ISO 14688-2:2006). Moreover the following physical properties of the samples were determined: - sample 1: w n = 22.34%, w P = 22.16%, w L = 40.5%, p = 15.42%, ρ = 2.01g/cm 3, ρ s = 2.68 g/cm 3 ; - sample 2: w n = 22.97%, w P = 23.47%, w L = 52%, p = 11.97%, ρ = 2.04g/cm 3, ρ s = 2.66 g/cm 3 ; - sample 3: w n = 20.21%, w P = 21.3%, w L = 43%, p = 21.5%, ρ = 2.05 g/cm 3, ρ s = 2.68 g/cm 3. Sample 3 was classified as highly swelling, which confirms a significant content of smectite in the mineral composition. Other samples were classified as medium swelling, correspondingly sample 1: 15.42%, and sample 2: 11.97% (Niedzielski 1993). The lowest value of bulk density of sample 1 indicates increased content of clay fraction. This is confirmed by the mineralogical and petrographical tests. Soils present in “Józefka” deposit overburden may be used as an addition to vegetable fertilizers. Their use will increase sorption of cations and water in soil. This material should be mined in a selective way due to its variability.

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Weathering in a regolith on the Werenskioldbreen forefield (SW Spitsbergen) : modelling of pore water chemistry

Kwaśniak-Kominek M., Manecki M., Rzepa G., Płonka A. M., Górniak D.

Annales Societatis Geologorum Poloniae

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2016

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Vol. 86, No. 3

249--264

EN

The mineral framework and pore waters of glacial sediments exposed in the foreland of Weren- skioldbreen in SW Spitsbergen were sampled and analyzed to model the evolution of pore water chemistry, representing the advancement of weathering in a chronosequence. Three samples were taken at distances representing snapshots of approximately 5, 45 and 70 years of exposure. Complementary mineralogical analyses of the mineral framework and chemical analyses of pore waters, coupled with thermodynamic modelling of mineral-water interactions were applied. Recently uncovered sediments of the bottom moraine underwent very little weathering underneath the glacier cover; both the sediments and pore waters in the forefield of the Werenskioldbreen represent a very immature system. Poorly sorted sediments were deposited by the glacier and not reworked by fluvioglacial waters. The ratio of ‘amorphous iron’ to ‘free iron’ Feo/Fed increases with distance from the glacier terminus from 0.30 through 0.36 to 0.49, typical for fresh glacial till. The increase in saturation with CO2 (from p(CO2) –3.8 to –2.4) and the concentration of all major ions in pore waters (from 123 to 748 mg/L total dissolved solids, TDS) was observed in this young chronosequence. The waters evolved from carbonate- dominated to sulphate-dominated, indicating that with progress in weathering the dominating processes are equilibration with carbonates, oxidation of sulphides and the influence of gypsum precipitation by seasonal freeze-thaw cycles. Mass balance calculations and inverse modelling of the composition of pore waters, verified by microscopic observations of alteration on the surfaces of mineral grains, allowed thermodynamic confirmation of the fact that the relative significance of carbonate weathering decreases and that of sulphate increases down the chronosequence. The participation of silicate minerals in weathering is low, indicating a relatively immature stage of weathering within this particular chronosequence. It is significant that the morphology of etch pits and the formation of secondary phases apparent on mineral surfaces were identical, regardless of the distance from the glacier terminus. This might indicate that the mechanisms of particular weathering processes at the mineral-water interface are the same at the initial as well as at the more mature stages and do not change at least within ca. 70 years of exposure.

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Wpływ metody syntezy na właściwości fizykochemiczne ferrihydrytu i Si-ferrihydrytu

Pieczara G., Mendsaikhan N., Manecki M., Rzepa G.

Przemysł Chemiczny

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2015

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T. 94, nr 10

1828-1831

PL

Przeprowadzono syntezę ferrihydrytów (Fe5HO8·4H2O) czystych (bez domieszki Si) i zawierających domieszki Si (stosunek molowy Si:Fe = 0,1) przez wytrącanie z roztworów wodnych. Porównano produkty otrzymane w reakcji zobojętniania roztworów siarczanu żelaza(III) (metoda siarczanowa) lub azotanu żelaza(III) (metoda azotanowa). Wykazano, że czyste ferrihydryty otrzymane metodą azotanową charakteryzują się mniejszymi rozmiarami cząstek, większą powierzchnią właściwą, mniejszym stopniem uporządkowania struktury oraz mniejszą trwałością termiczną. Sposób syntezy ma mniejszy wpływ na różnice we właściwościach ferrihydrytów z domieszką Si.

EN

Pure Fe5HO8·4H2O and Si-doped ferrihydrites (Si/Fe = 0.1 molar ratio) were pptd. from aq. solns. of Fe2 (SO4)3 and Fe(NO3)3 with NaOH optionally in presence of Na2SiO3 under stirring. Si-contg. ferrihydrites had smaller particles and showed higher thermal stability and sp. surface area than the pure ones.

7

Synthesis and mineralogical characteristics of hydroxylapatite-hydroxylpyromorphite solid solution series Ca5(PO4)3OH – Pb5(PO4)3OH

Motyka J., Oknińska J., Manecki M.

Geology, Geophysics and Environment

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2015

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Vol. 41, no. 1

112--113

EN

Lead is a widespread environmental contaminant toxic to living organisms. Soils and wastes contaminated with Pb are found in both rural and urban settings. Uptake of Pb from waste, soil or water by phosphate compounds, particularly hydroxylapatite, has been proved as effective remediation strategy (Xu & Schwartz 1994). The technology arises from the low solubility of lead apatites and from their rapid precipitation reactions. The structure of the apatite group minerals can be described by the general formula A5(BO4)3C, where positions A, B, C can be substituted by e.g. A: Ca, Pb, Sr, Ba; B: P, As, V; C: Cl, OH, F, Br, I. Apatites are very tolerant to structural distortion resulting from chemical substitution in cationic and anionic positions and consequently they are remarkably diverse in composition. Thanks to this potential for extensive solid solutions in the system, the lead apatites precipitating in the environment are not pure end members but rather Pb-Ca solid solutions. A complete solid solution between hydroxylapatite (HAP) and hydroxylpyromorphite (HPY) was determined before (Bigi et al. 1991, Hadrich et al. 2001). The results, however, are still fragmentary. The objective of the project is systematic characterization (crystal structure and infrared and Raman vibrational properties) of synthetic analogs of the minerals from HAP-HPY solid solution series. This will allow clarifying the controversies related to the change of properties towards substitution of lead for calcium. Well characterized products of the synthesis will be used in further thermodynamic study of solubility changes with substitution, which was never determined before. It is assumed t hat t he properties vary in systematic way with Pb substitution for Ca. An effective wet method of synthesis of Ca-Pb apatites was developed. A crystalline, homogeneous precipitates with stoichiometric composition were produced. Six phases of HAP-HPY solid solution series were prepared by dropwise mixing of a solution containing calcium and/or lead ions and a phosphate solution at room temperature. During the synthesis pH of 8.5 was maintained using NH4OH. Precipitates were washed, air dried and characterized by scanning electron microscopy (SEM) with the energy dispersive spectroscopy detector (EDS), powder X-ray diffraction, infrared spectroscopy (FTIR) and Raman spectroscopy. All synthetic products obtained in the experiments form hexagonal needles less than 0.1 μm long. Elemental composition of six product phases is consistent with the objectives of the experiment. X-ray diffraction patterns reveal a shift toward lower angles 2θ for phases with higher lead contents. This indicates an enlargement of the lattice constants. The variation of parameters, however, is not linear (does not follow the Vegards law). Particularly the cell parameter c changes more for phases reach in lead. These results are in agreement with those reported previously (Bigi et al. 1991, Hadrich et al. 2001). A shift of band position is also observed in both FTIR and Raman spectra. All the bands shift towards lower wave number with increasing Pb content. In most cases the shift is not linear exhibiting two trends similar to those of crystal lattice parameters. This may indicate that the vibrational properties of the phases in the series depend stronger on the bond length than on the atomic mass of substituting elements.

8

Structural and vibrational behaviour of pyromorphite-vanadinite solid solution series

Solecka U., Bajda T., Topolska J., Manecki M.

Geology, Geophysics and Environment

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2015

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Vol. 41, no. 1

135--136

EN

Pyromorphite Pb5(PO4)3Cl and vanadinite Pb5(VO4)3Cl belong to the apatite supergroup. They are secondary minerals formed in the oxidation zones of lead ore deposits. Both crystallize in hexagonal symmetry with the space group P63/m (Dong et al. 2002). The crystal structure of these two minerals allows to accommodate both metal cations and anionic complexes. It is the reason, why pyromorphite and vanadinite forms solid solution series. Isovalent replacement of P with V is one of the most common anionic substitution. Lead apatites are one of the least soluble along apatites group minerals and characterized by high thermal stability (Dong et al. 2002, Flis et al. 2011). Characteristic properties of apatite structure cause that these minerals are successfully used in many fields, especially for the immobilization of toxic waste and lead-contaminated soil (Ma et al. 1993, Chen et al. 1997, Dong et al. 2002, Kim et al. 2005). So far, pyromorphite and mimetite are the most known and used for the immobilization of lead. Pyromorphite and mimetite are isostructural with vanadinite, therefore it has been predicted that this mineral is also important for the environment. Accordingly, the aim of this study was to characterize of the pyromorphite-vanadinite solid solution series. This research presents systematic changes in the structure of these minerals. Pure pyromorphite and vanadinite and minerals with intermediate compositions Pb5(TO4)3Cl, where T = P + V, of various P/V ratios were synthesized from aqueous solutions at 298 K and pH = 3.5. Synthetic solids were analyzed by X-Ray diffraction (XRD), infrared absorption spectroscopy (FTIR) and Raman spectroscopy. Based on the X-Ray analysis, it was found that synthetic precipitates represent homogeneous phases of pyromorphite and vanadinite, which have intermediate chemical composition. Diffraction peaks of pyromorphite-vanadinite solid solution series were shifted due to replacement of PO4 by VO4. Replacement of PO4 by VO4 anions is causing changes in the structure of apatite and hence these shifts. Unit cell parameters of studied solid solutions show a linear variation. In the FTIR and Raman spectra of pyromorphite-vanadinite solid solutions series, the bands which are characteristic for vibrations of P-O bonds of the PO4 tetrahedra as well as vibrations of V-O bonds of the VO4 tetrahedra appeared. Analysis of Mid-IR spectra and Raman spectra also allowed observing correlation between the band positions and the extent of the anionic substitution among the studied series. The structure of pyromorphite and vanadinite is generally similar, although the two minerals vary in chemical composition. This variability results probably from the properties of individual ions.

9

Enviromental assesment of Skawina area based on selected parameters

Majer A., Kozień D., Michalec J., Manecki M.

Geology, Geophysics and Environment

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2015

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Vol. 41, no. 1

104--105

EN

The main aim of this study is to evaluate the assessment of the environmental effect of the city and industry in Skawina. Skawina is a town with a population of 25,000 situated about 15 km to the south-west of Kraków (S Poland). The main industrial facilities, located in the western part of the city, include: a coal-fired electric power plant, Lajkonik Snacks S.A. (food industry), the Vesuvius refractory ceramics factory and about 50 smaller industrial entities. Until 1980s of last century, one of the largest Polish aluminum smelters was operating in the western part of town. In 1981 the electrolysis department was closed due to huge emission of lethal fluorine, which was the major source of air, soil and water pollution in the area. It is hypothesized here that current environmental problems in the area result from contemporary and local urban or industrial activities rather than from historical pollution. Skawina is located at the junction of transit routes. The prevailing winds are SW and W bringing the air pollution from nearby Silesia. The town lies on the Skawinka River, a tributary to the Vistula River. Since the prevailing winds are SW and W, parallel to the river valley, temperature inversions and fogs are frequent. The Skawinka River is the source of city water for Skawina. In the lower part it receives a large volume of cooling water from the power plant. This is the Vistula River processed in the plant. It accepts municipal wastewater discharge too. Studies conducted in the 1970s showed extremely high levels of SO2 and particular matter in the atmosphere of Skawina. However, since the 1980s, there has been a significant improvement in air quality following decreases of industrial emissions. According to the data from the air monitoring network in the Małopolska region (Małopolska Sieć Monitoringu Powietrza 2007) and reports by the Voivoidship Inspectorate for Environmental Protection in Kraków (Wojewódzki Inspektorat Ochrony Środowiska w Krakowie 1994–2005), the improvement is observed for the whole Małopolska region.This study involved 10 soil samples from selected locations in the city of Skawina and 10 samples of water from the Skawinka River. The pH, loss of ignition and total elemental composition (using X-ray fluorescence XRF) was determined in soils. Bioavailability of selected elements was estimated based on extraction with HCl 1M. The temperature, pH, electric conductivity, colour and turbidity, as well as concentration of major ions (using atomic absorption spectrometry AAS) were determined in waters. The results were compared with current standards and legal regulations regarding water and soil pollution in urban areas. In spring 2015, a soil sampling campaign is planned for determination of current fluorine content in soils around the former aluminum processing plant. The soils are typical for urban areas: rich in clay and silt and lacking horizontal stratification. The pH exhibits bimodal distribution with maximums around 5 and around 8. Alkaline pH correlates with higher lost of ignition (ca. 8 wt. %) indicating the presence of carbonate fraction. Total concentration of selected elements in soils (particularly Ba up to 850 ppm, Zn up to 390 ppm, Pb up to 157 ppm, Cr up to 300 ppm) exceeds 105the limits of soil pollution in Poland. Therefore, the soils are classified as class pollution C typical for industrial zones according to Rozporządzenie Ministra Środowiska...(2002). The bioavailability determined using HCl 1M varies broadly and does not correlate with other parameters. This may indicate that bioavailable forms of metals are already complexed with organic components of the soil. The waters of the Skawinka River are strongly affected by the industry. All the physical and chemical parameters are strongly altered below the outlet of cooling water from the power plant. The plant uses water from the Wisła River. The discharge pollutes the waters of the Skawinka River mostly increasing the temperature (from 12 to 16°C) and mineralization (conductivity increases from 560 to 1230 mS/cm). Increased mineralization results mostly from increase in NaCl salinity. This results in drastic increase in turbidity (from 7 to 27 NTU) due to eutrophization. The waters are classified as IInd class according to Rozporządzenie Ministra Środowiska... (2011).Comparison of the results with previous studies indicates that the improvement of the state of the environment is small. This area was under heavy influence of various industry for many years resulting in strong deterioration of the soils. The waters of the Skawinka River are still under constant anthropogenic pressure. The results indicate that contamination of soils represents regional, long-range air pollution with historical component. The Skawinka River in turn, is under contemporary local environmental stress which should be improved particularly since recreational and sport facilities are developed on the river banks.

10

Arsenate substitution in synthetic hydroxylapatite – structural characterization of the Ca5(PO4)x(AsO4)3-xOH solid solution

Chlebowska P., Manecki M., Młynarska M., Puzio B.

Geology, Geophysics and Environment

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2015

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Vol. 41, no. 1

66--67

EN

Occurences of dissolved As in surface and ground waters and observed adverse health effects have emphasized the need for better understanding of reactions that govern As mobility. Precipitation of Ca apatites is quite often used for immobilization of toxic forms P and As in the environment. Hydroxylapatite – Ca5(PO4)3OH (HAP) and johnbaumite – Ca5(AsO4)3OH (AsHAP) are isostructural apatite minerals naturally occurring in the oxidation zones.The main objective of this research is identification of systematic relation between structural and spectral properties and As content in the Ca5(PO4)3OH, Ca5(PO4)2(AsO4)OH, Ca5(PO4)1,5(AsO4)1,5OH, Ca5(PO4)(AsO4)2OH, Ca5(AsO4)3OH. Recent studies of this isomorphic series provide inconsistent results (Lee et al. 2009, Zhu et al. 2009) indicating controversies and the need for further studies. Awet method of synthesis from aqueous solutions was used to precipitate precisely defined phases from the series: HAP, AsHAP and three intermediate compositions. For the synthesis of pure HAP solution of Na2HPO4 was mixeddrop wise using a syringe pump with aCa(NO3)2 solution.The pH was set at 11 with 1M NH4OH. Precipitated powders were washed five times in redistilled water and air dried. The other phases were precipitated in the presence of KH2AsO4 at various proportions. Johnbaumite was synthesized at 75°C. Ca5(PO4)3OH, Ca5(PO4)2(AsO4)OH, Ca5(PO4)1,5(AsO4)1,5OH, Ca5(PO4)(AsO4)2OH, Ca5(AsO4)3OH synthesized phases were characterized using scanning electron microscopy with energy dispersive spectroscopy (SEM/EDS), powder X-Ray diffraction (XRD), Infrared absorption spectroscopy (FTIR) and Raman spectroscopy. SEM-EDS analysis confirms that the products of the synthesis are homogeneous. The crystals size varies between 0.1–1.0 μm and increases with the increase of Ascontent. Semi-quantitative elemental analysis by EDS indicates that Ca, O, P and Asare the only elements detected and that the molar proportions correspond to theoretical composition of HAP, Ca5(PO4)2(AsO4)OH, Ca5(PO4)1,5(AsO4)1,5OH, Ca5(PO4)(AsO4)2OH and finally AsHAP. Systematic shift of peaks is apparent on the diffraction patterns. Hexagonal system and P63/m group of symmetry were used for unite cell parameters calculation. The results show systematic increase in the unit cell parameters with substitution of As for P in the series: parameter a from 9.41 to 9.43 and parameter c from 6.85 to 6.87. Crystal volumes also increase with increasing amount of As in synthesized phases. Calculated values are within the error similar to these reported by Zhu et al. (2009). In contrary to their results, a linear increase of unit cell parameters w it h As content is observed. This is in accordance with Lee et al. (2009). The intensity and the position of PO4 and AsO4 absorption bands varies systematically in the FTIR spectra being shifted towards higher wavenumber with increasing As content. The bands originating from CaO and OH (3400 cm–1) are practically not affected in all five spectra. The Raman spectra have shown systematic variation in stretching and bending vibrations in the series. Observed shifts in positions of Raman effects correlate linearly with As increase. This can be explained by the fact that atomic mass of As is higher than of P and that As-O bonds are longer than P-O bonds. Bands originating from P-O vibration modes shift in less regular manner. In the range of 610–550 cm−1 we observe shift of bands originating from CaO bond. The results correlate well with and expand upon the observations by Lee et al. (2009).Taken together, in this research we have explored possibility of HAP-AsHAP isomorphic series synthesis and we found it structural properties. Obtained results suggest that further insights may be obtained from more research on these minerals. It may find potential applications inremoval of toxic arsenic from the environment and this is a goal of future research.

11

Welcome in Herlandia 2014 XVth International Conference of Young Geologists Her'lany 2014 Międzybrodzie Żywieckie, Poland, May, 8th-10th 2014

Dwornik M., Manecki M., Zahradnikova B., Kovacova M., Zahradnik L., Greganova M., Kondela J., Strba L., Vizi L., Bazarnik J., Majka J., Kwaśniak-Kominek M., Kośmińska K.

Geology, Geophysics and Environment

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2014

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Vol. 40, no. 1

77

EN

The 15th International Conference of Young Geologists was held in the Polish Outer Carpathians, in Międzybrodzie Żywieckie, located in the Beskid Mały Mts. All participants were hosted in Niagara resort. The conference was organized by the AGH University of Sciences and Technology (AGH), Krakow (PL), Faculty of Natural Sciences of Comenius University (CU), Bratislava (SK) and the Faculty BERG of Technical University (TUKE), Kosice (SK). For several years the members of the scientific committee have been Prof. Dusan Plasienka (CU), Julian Kondela (TUKE) and Prof. Maciej Manecki (AGH). The conference was organized by Ph.D. students from AGH and the members of the Geological Club from Bratislava. This year 70 young scientists from Poland, Slovakia, Czech Republic and Russia participated in the conference. They presented over 50 talks covering a very wide spectrum of Earth science disciplines such as: tectonics, sedimentology, mineralogy, petrology, paleontology, geophysics, geoengineering and geoinformatics. The best student presentation in English was awarded with the Rudolf Mock Award. This year, the award went to Karolina Kośmińska, Ph.D. student from AGH, for excellent presentation in petrology on blueschists from Svalbard. The award was presented during closing ceremony by Professor Maciej Manecki. An important part of the meeting was "evening dinner discussion", where Professor Jan Golonka (AGH) presented his lecture on evolution of the Outer Carpathians. Topic of the lecture was also an introduction to the geological excursion. On Saturday, the participants visited pumped-storage hydroelectric power plant in Porąbka and unique outcrops of cieszynity in Cieszyn area. A guided tour in Brewery Museum in Żywiec ended the excursion. The next conference will return to the original location, Her'lany, Slovakia.

12

Weathering of siderite in the polar conditions

Figura P., Manecki M., Rzepa G.

Geology, Geophysics and Environment

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2014

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Vol. 40, no. 1

84--85

EN

Rapid retreat and thinning of glaciers perturb balance of polar ecosystems. These processes influence global climate (Anderson et al. 2000, Płonka 2009). For better understanding of changes and their consequences for global climate, it is necessary to extend our knowledge about processes occurring contemporary in the forelands of retreating glaciers. Numerous researches were carried out on this subject (Anderson et al. 1997, Bukowska-Jania et al. 2003, Pulina et al. 2003). For example, upliftdriven climate change hypothesis assumes that decrease of temperature results from regression of glaciers and is connected with chemical denudation of silicate sediments, which acts as a sink of CO2 from the atmosphere (Płonka 2009). Despite of this, many processes and dependences in polar environment are poorly known. Retreating glaciers and high chemical denudation observed in Polar Regions play significant role in weathering of regolith. Fast retreat of many glaciers exposures great amounts of fresh and fine sediment. Weathering of rock-forming minerals is a source of ions in waters as well as secondary minerals and nutrients in initial soils. These issues are object of interest recently because intensified weathering in Polar Regions may affect global cycle of many elements, particularly Fe (Anderson et al. 1997, 2000, Brenasconi 2008). This study is a part of large research, concerning mechanisms, budget and transport of iron from the foreland of fast retreating arctic glacier. The objective of this research is to determine processes and products of siderite weathering in the polar condition. The area of this study is located on the SW part of the Spitsbergen, in the foreland of Werenskioldbreen. It is hypothesized that in Arctic these processes differ significantly from their equivalents in Alpine regions. Field experiment on Spitsbergen lasted eight years. Samples of the siderite were buried in the surface layer of bottom moraine (in the initial polar soils) 100 m, 250 m and 2000 m from glacier front. This represents a chronosequence of sediment uncovered from underneath the glacier ca. 5-, 10-, and 90-years ago. Samples were recovered after 1 year and after 8 years of burial. Optical microscopy in transmitted and reflected light, scanning electron microscopy SEM/EDS and powder X-ray diffractometry were applied to characterize both, control sample and experimental samples. Siderite with manganese substitutions sampled from the outcrops of metamorphic carbonate in the vicinity of Werenskiold glacier was used for the experiment. This resembles mineral fragments eroded and transported by the glacier. Characterization of control sample (siderite before the experiment) indicates that it already exhibits advanced stages of transformation into secondary phases. Secondary minerals include oxides and hydroxides of iron, such as: goethite, hematite and lepidocrocite. The same mineral phases were identified in experimental recovered after burial. Additionally, 8-year sample shows traces of dissolution. Weathering of siderite in polar initial soils in the foreland of retreating glacier leads to formation of secondary goethite, hematite and lepidocrocite. These phases appear to be the most stable products of siderite weathering in this environment. There is no difference between the samples buried in very young and in older, more evolved initial soil. Additionally, transformations of siderite are identical in initial polar soils and in the outcrops of siderite rock. Traces of dissolution noticed on the surface of older samples indicate that part of iron is permanently removed from the system by solutions. This process, probably mediated by microorganisms, requires further investigation.

13

Structural and Raman spectroscopy studies of schultenite - phosphoschultenite isomorphic series

Młynarska M., Manecki M., Bajda T.

Geology, Geophysics and Environment

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2014

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Vol. 40, no. 1

110--111

EN

In many countries, there is a problem of lead and arsenic soils contamination. Lead can be immobilized using phosphate amendments (Cao et al. 2003). This technique, however, results sometimes in arsenic migration. Mineral phases, which can precipitate in this conditions include schultenite PbHAsO4 and phosphoschultenite PbHPO4. Only recently it has been experimentally shown that these minerals can form a continuous solid solution series in Earth surface environments (Zembal 2012). Therefore, it is important to extend our knowledge on the properties of schultenitephos-phoschultenite solid solution series in order to solve certain environmental problems. For the first time, Raman spectroscopy was used to characterize schultenite, phosphoschultenite and their solid solutions. The main objective of this research is the identification and interpretation of systematic changes in the results of X-ray diffractometry and Raman spectroscopy applied to synthetic schultenites with various P to As ratio. Six samples were synthesized from aqueous solutions at ambient conditions. The ratio of P/(P + As) varied from 0 to 1 by 0.2 (Zembal 2012). Schultenite PbHAsO4 and phosphoschultenite PbHPO4 belong to monoclinic crystallographic system. The standard model of the P2/c symmetric group was used in the calculation of unit cell parameters. The results show systematic increase in unit cell parameters with substitution of P for As in the series: parameter a from 4,6737 to 4,8588, parameter b from 6,6381 to 6,7528 and parameter c from 5,7617 to 5,8495. The Raman spectra have also shown systematic variation in stretching and bending vibrations in the series. The ν1 stretching As-O band shifts from 463 cm-1 in schultenite PbHAsO4 to 469 cm-1 in P-substituted schultenite while ν 4 bending As-O band shifts form 824 cm-1 to 841 cm-1. Similar is observed in phosphoschultenite: the v1 stretching P-O band shifts from 555 cm-1 to 569 cm-1 and v bending P-O band shifts form 905 cm-1 to 940 cm-1 with increasing P content Observed shifts in position of Raman effects correlate linearly with As-P substitution: the bands originating from vibration modes shift to higher wave numbers with the substitution of P for As from schultenite PbHAsO4 towards phosphoschultenite PbHPO4. This can be explained by the fact that atomic mass of As is higher than that of P and that As-O bonds are longer than P-O bonds. The results extend our knowledge about schultenite-phosphoschultenite isomorphic series. Systematic shifts of Raman effects correlate strongly with chemical composition of analyzed phases. This is associated with systematic linear variation in the height (between 4,403 and 411 units for As-0 ν 4 bending band and between 825 and 70 units for P-0 v4 bending band) and area under certain peaks on Raman spectra (between 71,423 and 30,805 units for As-O ν 4 bending band and between 28,982 and 2,095 units for P-O ν 4 bending band). Current findings suggest that it is possible to estimate the overall P/(P+As) ratio in mineral samples by precise determination of the position and area under the respective Raman spectra and comparison with standard measurements.

14

Pressure-temperature estimates on blueschists from the Vestgötabreen complex (Western Svalbard)

Kośmińska K., Majka J., Manecki M., Kozub G. A.

Geology, Geophysics and Environment

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2014

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Vol. 40, no. 1

94--95

EN

In Oscar II Land (Motalafjella area, western Svalbard), an exotic high-pressure (HP) metamorphic unit, namely the Vestgötabreen Complex (Kanat & Morris 1988) occurs. It is thrust over low-grade metasediments (e.g. Labrousse et al. 2008) of inferred Neoproterozoic age. This complex is subdivided into the Lower (LU) and Upper Unit (UU) differing from each other in terms of lithologies and pressure-temperature (P-T) conditions. The LU is composed of high pressure-low temperature (HP-LT) metasediments with minor intercalations of blueschists, whereas the UU comprises metasediments, more voluminous blueschists and scattered lenses of eclogites. Radiometrie dating yield the age of c. 470 Ma for the HP metamorphism in the Motalafjella region (Horsfield 1972, Dallmeyer et al. 1990, Bernard-Griffiths et al. 1993). The P-T conditions for carpholite-bearing schists from the LU yield the pressures up to c. 16 kbar and temperatures in the range of 330-450°C (Agard et al. 2005), whereas eclogites from the UU were subjected to 18-24 kbar pressure and temperatures of 580-640°C (Hirajima et al. 1988). The aim of this study is to decipher meta-morphic evolution of blueschists using thermodynamic phase equilibrium modeling. Samples have been collected from the UU, cropping out at the Skipperryggen ridge. They contain mostly garnet, glaucophane, phengite, rutile and chlorite. Additionally lawsonite, ilmenite and epidote can be found in minor amounts. Garnet typically forms euhedral to subhedral porphyroblasts. It contains voluminous inclusions of white mica, epidote, rutile and amphibole. Garnet shows chemical compositional variation from Alm63Prp19Grs22Sps2 in the cores to Alm60Prp19Grs20Sps1 in the rims. The pyrope zoning is bowl-shaped, whereas grossular and spessartine profiles show bell-shaped trends. The almandine content is generally constant through the grain. The P-T conditions were estimated using the phase equilibrium modeling in the NCKFMASHTO system using the Perple_X software (Connolly 2005). Modeling was based on bulk-rock chemistry as well as garnet and phengite compositional isopleths. P-T estimates indicate peak conditions of ca. 20 kbar and 520°C. These estimates for studied blueschists from Skipperryggen are in agreement with previous studies on the Vestgötabreen Complex. Also, recent studies in Nordenskiöld Land (south of Oscar II Land) revealed the occurrence of blueschist facies rocks. These blueschists yielded similar P-T conditions to blueschists from the Vestgötabreen Complex (18 kbar, 470°C; Kośmińska et al., in press). More regionally, all aforementioned HP-LT lithologies may be correlated with the ophiolitic sequence occurring within the Pearya Terrane of northern Ellesmere Island (e.g. Labrousse et al. 2008, Kośmińska et al., in press). Detailed tectonic, petrological and geochronological studies are in progress.

15

Optimization of synthesis conditions of pyromorphite-vanadinite and mimetite-vanadinite solid solution series

Janicka U., Bajda T., Topolska J., Manecki M.

Geology, Geophysics and Environment

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2014

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Vol. 40, no. 1

88

EN

Minerals: pyromorphite Pb5(PO4)3Cl, mimetite Pb5(As04)3Cl and vanadinite Pb5(VO4)3Cl belong to the apatite supergroup. Commonly they form in hypergenic conditions. They are best known from the oxidation zones of lead ore deposits. Natural pyromorphite usually contains admixture of arse-nates or vanadates, whereas mimetite or vanadinite contain admixtures of phosphates. Solid solutions of the pyromorphite-mimetite series are well known, while the knowledge about anionie substitutions in vanadinite is incomplete. Therefore, the aim of this study was to find optimal conditions for the synthesis of pyromorphite-vanadinte and mimetite-vanadinite solid solution series. This research will allow to check the range of possible anionie substitutions, formation conditions such as pH, temperature and in, turn, to obtain better knowledge about the properties of these minerals. Pyromorphite, mimetite, vanadinite and pyromorphite-vanadinite and mimetite-vanadinite solid solutions series were synthesized from aqueous solutions. Solutions containing Pb2+, PO43-, AsO43-, VO3- , VO43- and Cl- ions in stoichiometric molar proportions were dropwise mixing. This method of synthesis allows controlling the stoichiometry of the chemical composition of synthetic precipitates. Synthesis reactions were carried out at various pH and at different temperatures (range from 25°C to 85°C). After the synthesis, suspensions were left for two weeks for aging. Then the suspensions were filtered using a Biichner funnel. The precipitates were washed with double-distilled water and acetone, and then dried. Synthetic precipitates were analyzed using various analytical techniques including X-Ray diffraction (XRD), Scanning electron microscopy coupled with Energy Dispersive Spectroscopy (SEM/EDS), Infrared absorption spectroscopy (FTIR) and Raman spectroscopy. Results of XRD, SEM/EDS, FTIR and Raman spectroscopy analyzes of studied samples showed that temperature 25°C and pH = 3.5 are optimal conditions to synthesize pyromorphite-vanadinite and mimetite-vanadinite solid solution series. Chervetite Pb2V2O7 was formed together with studied phases at lower pH values (1.7, 2.2), or higher temperatures (75°C, 85°C). At pH = 11.5, minerals with hydroxyl groups were formed. It has been observed that the formation of pyromorphite-vanadinite and mimetite-vanadinite solid solution series mainly depends on the pH values. The temperature is less important.

16

HP metamorphism recorded by kyanite-garnet gneisses in the Kafjord Nappe, Northern Norway -preliminary results

Ziemniak G., Majka J., Kośmińska K., Manecki M., Czerny J.

Geology, Geophysics and Environment

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2014

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Vol. 40, no. 1

152--153

EN

Scandinavian Caledonides are Himalaya-type mountain belt consisting of allochthons that are a result of the Ordovician-Silurian collision of Baltica and Laurentia (Gee et al. 2008). The Skibotn Nappe Complex, traditionally ascribed to the Upper Allochthon (but possibly being a part of the Middle Allochthon) is situated in northern Norway. It consists of the Normandsvik, Kafjord and Vaddas nappes (Anderson et al. 1992). The Kafjord Nappe has not been fully examined, so the information about the age and metamorphic conditions are lacking. The main goal of this project is to provide a new data about peak metamorphic conditions to which the Kafjord Nappe has been exposed and to compare them with possible equivalents within the Scandinavian Caledonides. Three samples of kyanite-garnet gneisses from different parts of the Kafjord Nappe have been studied. All of them contain similar mineral assemblage. Progressive paragenesis occurs in lenses and contains garnet, kyanite, quartz, white mica, biotite, plagioclase, rutile and opaque minerals. Retrogressive paragenesis contains similar minerals with additional presence of chlorite. Two generations of garnet, white mica and biotite are present. Garnet I occurs as large poikiloblasts up to 6 mm in diameter with abundant variably sized inclusions, whereas garnet II is smaller (up to 1 mm) with less numerous inclusions. Biotite and white mica appear as flakes conformable with the main foliation and as transversal blasts. Kyanite occurs as transversal blasts up to 5 mm in size, with moderate number of inclusions. All the observations mentioned above suggest that these rocks were probably subjected to at least two metamorphic events, one of which could have happened under high pressure conditions. On the basis of chemical composition of minerals and rocks bulk chemistry, thermodynamical modeling will be performed and peak temperature and pressure as well as the retrogressive paths will be determined. Similarities in lithologies and the inferred grade of metamorphism suggest that, in contrast to the previous correlations, the studied gneisses from the Kafjord Nappe may be an equivalent of the Seve Nappe Complex described by Hacker & Gans (2005).

17

Halogen substitution in synthetic lead apatite compounds Raman spectroscopy study

Witkowska M., Motyka J., Kwaśniak-Kominek M., Manecki M.

Geology, Geophysics and Environment

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2014

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Vol. 40, no. 1

141--142

EN

Mimetite Pb10(AsO4)6Cl2, vanadinite Pb10(VO4)6Cl2 and pyromorphite Pb10(PO4)6Cl2 are minerals isostructural with apatite occurring in the oxidation zones of Pb deposits. They exhibit hexagonal structure and rod-shape morphology. To date, most published research on crystal chemistry of lead apatites concentrated on cationic substitutions in crystalline structure (Ca, Pb, Sr etc.). Little is known, however, on anionic solid solutions, particularly on systematic changes in the structure and properties due to halogen substitutions in lead apatites. Precipitation of lead apatites is often used for immobilization of toxic forms of Pb and As in the environment. More recently, immobilization of radioactive isotope 129I in the form of lead apatites was proposed. This isotope is released as a result of accidents at nuclear power plants (Zhang et al. 2007, Stennet et al. 2011, Redfern et al. 2012). Halogen varieties of lead apatites are also used in chemical engineering as environmentally friendly catalysts (Masaoka & Kyono 2006). The objective of this project was synthesis of halogen-substituted lead apatites in pyromorphite series Pb10(PO4)6(F, Cl, Br, I)2, mimetite series Pb10(AsO4)6(F, Cl, Br, I)2, and vanadinite series Pb10(VO4)6(F, Cl, Br, I)2, followed by characteristics of X-ray diffraction patterns and Raman spectra. This will contribute to our knowledge on mechanisms and effects of anionie substitutions in this group of mineral phases. Based on the literature and pilot experiments we developed an efficient method of synthesis of Pb apatite solid solutions which allows for full control on stoichiometry, and results in crystalline, homogeneous precipitate. Lead apatites were synthesized at room temperatures from aqueous solutions of Pbq , phosphates/arsenates/vanadates, and Faq, Claq, Braq, or Iaq solutions mixed in stoichiometric proportions. Solutions are mixed dropwise in large (2 dm3) reactor with distilled water. Suspension is left for 48 hours for aging, filtered and air-dried. X-ray powder diffraction is used for identification of solid phases. Qualitative analysis allows also for identification of systematic shifts in diffraction patterns resulting from halogen substitutions. Calculation of lattice parameters is used to quantify the systematic effects of substitutions on unit cell dimensions. For the first time Raman spectroscopy was applied to most of crystalline phases in question. Analysis of systematic spectral shifts with anionic substitutions was performed which allowed for explanation of molecular structural reasons for spectral shifts as well as for development of identification procedures with the use of Raman spectroscopy. All phases preserve their hexagonal crystalline structure. Both diffraction patterns and Raman spectra corresponding to each synthesized phases exhibit systematic shifts in the series. The most pronounced features on Raman spectrum are shifts of double bands resulting from phosphate stretching mode from 968/932 through 945/918 to 941/910 cm-1 for F, Cl and Br substituted pyromorphites, respectively. Similar trends are observed for mimetite and vanadinite series. These shifts progress towards lower angles 2Θ in XRD patterns and lower Raman shifts on the spectra which is consistent with the increasing ionic radius and atomic mass of the elements resulting in larger unit cell and more rigid chemical bonds. These results confirm that solid-solutions between these phases are possible and result in systematic changes in the structure and spectroscopic properties.

18

Assesment of contamination of water and sediments in the Wilga River, Poland

Puławska A., Puzio B., Polewka M., Manecki M.

Geology, Geophysics and Environment

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2014

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Vol. 40, no. 1

120--121

EN

The Wilga River, one of the dextral tributaries of the Wisła, is one of the most polluted rivers in Kraków region. In the middle section it drains the Swoszowice region which is known for the natural mineral spring waters that are rich in sulphides, bicarbonates, calcium and magnesium. In the lower section of the Wilga valley an extensive, old dumps of soda factory are located. The waste consists in 70% of CaCO3 and remaining 30% are CaCl2, SiO2, Ca-phosphates, Ca, Mg and Ba-sulphates and NaCl (Wójcik & Morawski 2009). The aim of this study is the geochemical contribution to the assessment of the state of the environment of the Wilga River based on characteristics of water and bottom sediments. In contrast to the previous studies which concentrated on the polluted parts of the Wilga, this project aims at a systematic analysis of natural background in the upper parts as well as anthropogenic effects in the lower parts of the river. Sediments and water samples were collected from six locations from springs to the mouth of the river. Temperature, pH and specific conductivity were measured on site. Chemical composition of water (major and selected trace elements) was determined by atomic absorption spectroscopy AAS (Na, K, Cu, Zn, Pb, Cd, Mn, Fe), by titration (Ca2+, Mg2+, HCO3-, Cl-) and by spectrotometry UV-VIS (SO42-, PO43-). X-ray fluorescence spectrometry (XRF) was applied for determination of major and trace elements in the sediments. This was accompanied with qualitative mineralogical characteristics using powder X-ray diffraction (XRD). The results were compared with the previous studies (Wójcik & Morawski 2009). From springs to just below Swoszowice the chemical composition of water and sediments as well as concentrations of trace elements are at the level of regional geochemical background. No influence of natural (sulphide) mineral springs was detected in Swoszowice. This is probably a result of small volumes of spring water compared to the volume of the Wilga River there. Elevated ion concentrations are apparent, however, in the river waters near the Kraków Soda waste dumps. This was also determined before by Wójcik & Morawski (2009). With respect to geochemical background in the upper parts of the river, chloride concentration increases from 80 mg/L to 466 mg/L, sodium increases from 40 mg/L to 230 mg/L, and calcium from 84 mg/L to 146 mg/L. This is associated with increase in Zn content in sediments. The water type changes from HCO3-Ca-Cl-Na above to Cl-HCO3-Na-Ca type below the dumps area. Discharges and leakage of industrial waste dumps and agricultural waste (possibly resulting from extensive reclamation of post-industrial area) appear as major reasons of water quality deterioration in this area. All the parameters indicating pollution, however, are lower than measured 5 years ago indicating improvement and positive effects of remediation procedures applied in contaminated area.

19

A Raman spectroscopic study of hydroxyl analogues of pyromorphite-mimetite solid solutions

Giera A., Manecki M., Kwaśniak-Kominek M., Marchlewski T., Borkiewicz O., Rakovan J.

Geology, Geophysics and Environment

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2014

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Vol. 40, no. 1

86--87

EN

Pyromorphite Pb10(PO4)6Cl2 and mimetite Pb10(AsO4)6Cl2, minerals belonging to apatite group, receive increased attention recently. Induced precipitation of pyromorphite and mimetite in soil pore solutions or waste solutions belongs to the best remediation and reclamation methods (Ma et al. 1995, Maniecki et al. 2009). These phases are the most stable forms of Pb2+ and As5+ in the environment. Deficiency of Cl in the environment can cause formation of their hydroxyl forms: Pb10(PO4)6(OH)2 and Pb10(AsO4)6(OH)2 or their solid solutions. Apatite structure allows for extensive and varied ionic substitutions in all positions. The isomorphic substitutions affect unitcell parameters and chemical properties of these minerals (Botto et al. 1997). Solid solutions of hydroxyl analogues of pyromorphite and mimetite have not been sufficiently characterized to this day. A detailed description of phases from this series is, however, necessary for optimization of the remediation methods. A Raman spectroscopic study of mimetite-pyromorphite series demonstrated a strong correlation between the positions of the vibrational modes and the As/(As+P) ratio (Bajda et al. 2011). Such a correlation may be used to determine the composition of the examined samples of minerals from the series. The current research is based on the assumption that in the case of solid solutions of their hydroxyl analogues similar correlations occur. Therefore, the aim of this study is structural (X-ray diffraction) and spectroscopic (Raman) investigation of the effect of PO4-AsO4 isomorphic substitution on the structure and vibrational spectra. Seven phases were synthesized in computer-controlled chemistate at pH = 11 and 80°C by dropwise mixing of solutions containing Pb2+, PO4 3- and AsO4 3- in stoichiometric proportions. The composition of the final products was Pb10[(PO4)6-x(AsO4)x(OH)2, where x = 0, 1, 2, 3, 4, 5, 6. High-resolution powder X-ray diffraction data was obtained using the diffractometer at beamline 11-BM at the Advanced Photon Source (Argonne National Laboratory, Chicago). A detailed Raman spectroscopy was performed with the use of confocal Raman microscope and OMNIC software (AGH Kraków). The morphology and elemental composition of the samples were characterized by means of Fei Quanta variable pressure SEM/EDS (AGH UST Kraków). Moreover, the chemical composition of synthetic phases was determined by wet chemical analysis. Unit cell parameters increase with substitution of AsO4 for PO4 . Parameter a increases from 449.879 Å to 10.189 Å, while parameter c - from 7.427 Å to 7.516 Å. This is consistent with other solid solution series of lead apatites (Flis et al. 2009). The area under selected Raman effects is also strongly correlated with P and As content. Additionally, systematic shift of the position of Raman effects is observed. The band attributed to the (AsO4)3- ν1 symmetric stretching mode shifts from 808 cm-1 in Pb10(AsO4)6(OH)2 to 814 cm-1 in Pb10[(PO4)5(AsO4)](OH)2. The range of the peak positions for the (PO4)3- ν1 symmetric stretching mode is even wider: from 918 cm-1 in Pb10[(PO4)(AsO4)5](OH)2 to 926 cm-1 in Pb10(PO4)6(OH)2. The observed correlations may be used for semi-quantitative estimation of As and P content using non-destructive Raman spectroscopy.

20

Petrographic-mineralogical and textural changes in reservoir and sealing rocks (Zaosie anticline) as a result of a long-term experiment in CO2-brine-rock interactions

Wdowin M., Tarkowski R., Manecki M.

Gospodarka Surowcami Mineralnymi

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2013

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T. 29, z. 4

137--153

PL

Artykuł przedstawia wyniki badań mineralogiczno-petrograficznych oraz teksturalnych na próbkach skalnych ze skał zbiornikowych i uszczelniających (piaskowce, iłowce, mułowce) z utworów dolnej jury z antykliny Zaosia (środkowa Polska), z otworów wiertniczych Zaosie 2 i Buków 2. Próbki poddano eksperymentowi oddziaływania CO2-solanka-skała celem określenia ich przydatności pod kątem geologicznej sekwestracji CO2. Eksperyment polegał na zamknięciu próbek skalnych na 20 miesięcy w zbudowanym reaktorze, gdzie były one poddane oddziaływaniu solanki i dwutlenku węgla w temperaturze pokojowej (20–25°C), przy ciśnieniu otrzymanym z butli z CO2 (ok. 6MPa). Analizy mineralogiczno petrograficzne obejmowały obserwacje w świetle przechodzącym (planimetria), SEM-EDS, XRD próbek skalnych. Dodatkowo dla skał uszczelniających wykonano XRD z frakcji ilastej. Badania te pozwoliły określić skład mineralny oraz morfologię ziaren jak również strukturę i teksturę skały. W przypadku analiz teksturalnych określona została powierzchnia właściwa BET oraz rozkład i wielkość porów. Miały na celu określenie zmian w matrycy skalnej i spoiwie badanych skał w wyniku eksperymentu oddziaływania pomiędzy solanką-skałą-CO2. Eksperyment nie wpłynął znacząco na badane parametry. W przypadku każdej z analizowanych skał obserwuje się nieznaczne zmiany w porowatości przed i po eksperymencie, co związane jest z rozpuszczaniem się matrycy skalnej i spoiwa oraz wytrącaniem niektórych faz mineralnych. Zmiany zaobserwowane w piaskowcach (skały zbiornikowe) są zmianami, które nie wpływają negatywnie na proces składowania CO2. W przypadku mułowców i iłowców (skał uszczelniających) wyniki badań pokazały, że eksperyment nieznacznie wpłynął na analizowane skały. Wskazywać to może na dobre właściwości uszczelniające tych skał. Niemniej jednak wyniki powinny zostać zweryfikowane i potwierdzone w uzupełnieniu o dalsze badania petrofizyczne (porowatość, przepuszczalność), analizy solanek przed i po eksperymencie, jak również modelowanie geochemiczne oddziaływania CO2 na skały w obecności solanki.

EN

This article presents the petrographic-mineralogical and textural test results from rock samples from the reservoir and sealing rocks (sandstones, claystone, mudstone) of the Lower Jurassic formation of the Zaosie anticline (central Poland), from boreholes Zaosie 2 and Buków 2. Samples were subjected to an experiment involving CO2-brine-rock interactions in order to determine their suitability for the geological sequestration of CO2. The experiment consisted of closing the rock samples for 20 months in constructed autoclaves where they were subjected to the influences of brine and carbon dioxide at room temperature (20–25°C) and under pressure (about 6 MPa). Mineralogical and petrographic analyses included observations under transmitted light (planimetric analysis), and SEM-EDS and XRD of rock samples were carried out. Additionally, XRD analysis of the clay fraction was conducted to examine the sealing characteristics of the rock. These studies allowed for the determination of the mineral composition and morphology of the grains as well as the structure and texture of the rocks. For the textural analysis, the BET specific surface area and pore size distribution were identified. The study aimed to determine the changes in the rock matrix and cement of the rocks caused by the brine-rock-CO2 interactions experiment. The experimentation did not significantly affect the analyzed parameters. For each of the examined rocks, little change in the porosity before and after the experiment was observed, which was associated with the dissolution of the rock matrix and cement as well as the precipitation of some mineral phases. The changes observed in the sandstones (reservoir rocks) are differences that do not affect the process of CO2 storage. In the case of mudstone and claystone (sealing rocks), the experiment had some slight effect on the analyzed rocks. This study nevertheless indicates good sealing properties of these rocks, though the results should be verified and proven by petrophysical (porosity, permeability) examination, the analysis of brines before and after the experiment, as well as geochemical modeling of the impact of CO2 on a rock in the presence of brine.