South-central Poland Research Articles

Trace elements and stable sulfur isotopes in plants of acid mine drainage area: Implications for revegetation of degraded land

The abundances of trace elements, a low pH of water and soil in areas impacted by the acid mine drainage (AMD) may cause an excessive uptake of potentially toxic elements and nutritional imbalances in plants. Metal-tolerant, native plants are used for revegetation of degraded mining areas. We established levels of selected trace elements and stable sulfur isotopes in the above-ground plant biomass collected in a mining area in south-central Poland. In 2016, 20 samples of the most common species were collected from sites with a different influence of acid mine drainage and analyzed for trace elements by the inductively coupled plasma mass spectrometry technique. On the basis of the results obtained in 2016, the most contaminated site was selected for a more detailed study, in which sulfur contents and stable sulfur isotope ratios were determined together with trace elements in 17 samples. The results confirmed that the plants native to the AMD area efficiently accumulated trace elements, especially As and rare earth elements. Mosses showed the highest content of trace elements, but exhibited the lowest concentrations of sulfur accompanied by the highest δ34S values. It has been shown for the first time that stable sulfur isotope composition of AMD plants in south-central Poland is significantly depleted in the 34S isotope showing an average δ34S value of –10.5‰ in comparison with positive δ34S values in local vegetation growing outside the AMD area and in local precipitation.

Trace metals in surface soils under different land uses in Kielce city, south-central Poland

This work presents the influence of land use in Kielce on the spatial differentiation of heavy metals in the near-surface soil layer. The aim is to determine the amounts of ten trace elements (As, Ba, Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn) contained in soil samples of five land use categories (residential areas, roads, urban greenery, allotment gardens, agricultural areas) in the city and to evaluate the contamination using geochemical indicators. The Clarke values of Earth’s crust and the average content of the elements in Poland’s soils are exceeded only for Pb and Zn (N = 60). Soils of urban greenery and residential areas stand out in this respect. Particularly noteworthy is the fact that a high content of As has been documented in the soils of allotment gardens and confirmed by high values of the geoaccumulation index (moderate to high pollution) in relation to the Clarke values and to average contents in Poland's soils. The highest average Pb content has been found in the areas of urban greenery and residential areas. The integrated pollution index (IPI) in terms of maximum values indicates high level of metal pollution of soils in all forms of land use, except for agricultural areas (moderate). On average, IPI and potential ecological risk index are low.

Assessment of the impact of climate change on the latency period of leaf rust on triticale in Poland

ABSTRACTDisease development in plants is strongly dependent on weather conditions, with temperature playing a particularly significant role by influencing latency period duration. Using two models describing the relationship between latency period and temperature, we performed simulations aimed at predicting changes in the latency period of leaf rust (Puccina recondita f. sp. tritici) on triticale in response to expected climate change. The simulations were based on meteorological data recorded in the period 1986–2005 at locations representing 16 provinces in Poland and based on values obtained after transformation of the observed data to reflect temperature changes under four scenarios (RCP2.6, RCP4.5, RCP6.0 and RCP8.5) according to the giss_e2_r climate model. In all scenarios, the results for the two triticale cultivars studied, Witon (vulnerable to P. recondita) and Gniewko (less susceptible), showed a threat of faster development (shorter leaf rust latency period) on triticale triggered by climate change in south-east and south-central Poland than in other regions. The results also showed an increased probability of future regional diversification of leaf rust latency period duration on vulnerable triticale cultivars, opportunities for earlier start of leaf rust epidemics on triticale in Poland and an increase in final disease severity in comparison with 1986–2005.

An abrupt oceanic change and frequent climate fluctuations across the Frasnian–Famennian transition of Late Devonian: Constraints from conodont Sr isotope

The Late Devonian Frasnian–Famennian (F‐F) transition witnessed one of the “big five” mass extinction events in the Phanerozoic. We here present high‐resolution conodont Sr isotopic data from Fuhe (South China) and Kowala (South Central Poland) sections to reveal coeval climatic and environmental variations and potential causes of this biotic crisis. Fuhe and Kowala sections yield 87Sr/86Sr ratios from 0.70815 to 0.70864 and 0.70808 to 0.70836, respectively. These Sr isotopic data demonstrate three distinctive variation cycles (I, II, and III), notably at Fuhe, fluctuating from low (negative) to higher Sr isotope ratios (positive excursion). Temporally, fluctuations I and II occurred immediately before the F‐F boundary, and fluctuation III started almost from the onset of the Famennian age. These conodont 87Sr/86Sr (low‐to‐high) fluctuations temporally match well the paces of conodont δ18O (low‐to‐high) and Δ13Ccarb‐org (high‐to‐low ) fluctuations from the identical section published previously. These Sr isotopic fluctuations thus corroborate the cyclic variations in volcanic activity/flux and weathering intensity/riverine flux in parallel with climate warm‐to‐cool fluctuations. Mass balance modelling shows the first exceptionally high Sr isotope spike (I) could have been only yielded by a dramatic increase in terrestrial flux in a somewhat restricted Palaeo‐Tethys, likely due to the closure of the oceanic domain between Laurussia and Gondwana and sea‐level fall. This scenario would enhance the seawater eutrophication/anoxia in the pericontinental basins along the Palaeo‐Tethys, causing initial strikes on the low‐latitude shallow marine benthos. Subsequently, the frequent climatic fluctuations may have further caused escalating detrimental ecological pressures, leading to their massive demise.

Presence and possible origin of positive Eu anomaly in shoot samples of Juncus effusus L

BackgroundThe rare earth elements (REE) are non-essential elements for plants. They stimulate plant growth at low doses, but at high levels are phytotoxic. There are differences in concentrations of REE in various organs of the same plant species, but the normalized REE patterns can be very similar in samples of the same species collected in different locations. Here we compare normalized REE curves in above-ground samples of Juncus effusus L. (common rush, soft rush) collected from sites with different land-use types. MethodsThe concentrations of rare earth elements were measured in 55 shoot samples of J. effusus L. The samples were collected from 15 sampling sites located in the Holy Cross Mts., south-central Poland and analyzed with the use of inductively coupled plasma mass spectrometry (ICP-MS). The results were normalized to the North American Shale Composite and anomalies of different elements were calculated. ResultsTotal REE concentrations varied from 0.028 mg/kg to 2.7 mg/kg. The samples were enriched in the light REE (from La to Eu) with the highest concentrations of La and Ce. The North American Shale Composite (NASC)-normalized REE curves were roughly similar in all samples except for two samples collected in the acid mine drainageaffected areas. ConclusionAll samples showed positive europium anomalies in NASC-normalized REE concentration patterns. The most probable explanation of this is that the uptake and translocation of Eu in J. effusus (and possibly in other wetland plants) is caused by a short-term decrease of the redox potential in a rhizosphere favoring reduction of Eu3+ to Eu2+ and thus enhancing Eu mobility in the soil-plant environment.

Fungal abundance and diversity as influenced by properties of Technosols developed from mine wastes containing iron sulphides: A case study from abandoned iron sulphide and uranium mine in Rudki, south-central Poland

Reclamation of mine spoils is a process leading to initiation of soil-forming and biological processes in former mining areas. The aim of the present study was to demonstrate the change in soil fungi abundance and diversity depending on Technosols properties as an effect of reclamation in 1970s. The investigation was carried out in the area of the abandoned “Staszic” mine in Rudki village (south-central Poland). Three soil profiles developed from mine wastes were investigated. Basic physicochemical properties and fungal abundance and diversity were determined. The results showed that fungal abundance and species composition is diverse in the studied Technosols, which is closely related to soil properties, in particular with pH, total organic carbon (TOC) and total nitrogen (TN) content. Profile R1 represented a site where reclamation (i.e. neutralization of high acidity) did not succeed, therefore the pH of soil was low (3.0–3.9), plant cover was very scarce, and there was a very low concentration of TOC (up to 0.6%) and TN (up to 0.06%). Profile R1 was the most specific in terms of fungal diversity. The most frequent fungal species was acidophilous Acidiella sp. Profile R2 was located in close vicinity of R1 profile, though it represented a site where neutralization succeeded. Therefore, pH was ~7, and high contents of TOC and TN (up to 8% and 0.65% respectively) occurred in the topsoil of profile R2, whereas the subsoil was acidic (pH 3.9) and poor in TOC and TN. Profile R3 was characterized by high pH (7.2–7.6) throughout the profile, high contents of TOC and TN (up to 4.8% and 0.41% respectively) in the topsoil as well as high concentrations of trace elements (e.g. Pb, Zn, Cu). Our analysis showed that the highest fungal diversity was noted in surface horizons. The study confirmed the distinction of surface horizon of profile R2 and the whole profile R3 in terms of fungal species. High fungal abundance and diversity in R2 and R3 soil profile suggests favourable changes in the mycobiota structure as a result of improvement of soil properties due to reclamation works.

The origin of pyrite mineralization: Implications for Late Cambrian geology of the Holy Cross Mountains (south-central Poland)

This paper presents results of a petrographic, mineralogical and geochemical study of ore, gangue and rock-forming minerals that occur within the Upper Cambrian (Furongian)-age siliciclastic rocks of the Wiśniówka massif (western part of the Main Range, Holy Cross Mountains, south-central Poland). This area is characterized by the presence of ubiquitous pyrite that makes up two stratiform mineralization zones assigned to the early and middle Late Cambrian, giving rise to acid mine drainage. The oldest zone comprises additionally sedimentary breccias with intraclast-supported pyrite cement. The predominant microscopic (colloform) and partly framboidal pyrite typically shows high concentrations of As (up to 8.23 wt%) and a distinct enrichment in the light sulfur isotope (δ34S from −41.4 to −23.6‰). The occurrences of large amounts of As-rich pyrite showing strongly negative δ34S values are rather uncommon in Paleozoic sedimentary formations worldwide that exhibit distinctly smaller amounts of As and mostly enrichments in heavier sulfur isotope (δ34S up to 63‰). Another specific feature of the Wiśniówka rock series is the presence of REE-bearing aluminophosphate and phosphate minerals that occur primarily in clayey-silty shales and bentonites. Based on the results obtained, a sequence of hydrothermal index minerals was discriminated, including pyrite (whose grains are usually made of alternating arsenic-rich and arsenic-poor bands), as well as paragenetic assemblages of dickite, nacrite, xenotime and the crandallite series of aluminum-phosphate-sulfate minerals. Both mineral composition and specific microtextures are indicative of multistage hydrothermal activity that took place in the Wiśniówka depositional basin during the Late Cambrian time. This is in distinct contrast to the remaining part of the Main Range, which is devoid of the hydrothermal pyrite imprint. Moreover, the results of this study give insight into the complex sedimentary and early diagenetic history of the southwestern passive margin of the Baltica craton. This currently makes up a part of the Łysogóry Block (Terrane) that borders on the Trans-European Suture Zone separating the Precambrian East-European Craton from the Paleozoic Platform of Central Europe. This study is important because we still lack the full knowledge about the hydrothermal processes that took place in Early Paleozoic depositional basins.

The use of a geostatistical model supported by multivariate analysis to assess the spatial distribution of mercury in soils from historical mining areas: Karcz\xf3wka Mt., Miedzianka Mt., and Rudki (south-central Poland)

For the purpose of this study, 181 soil samples were collected from three post-mining areas (Miedzianka Mt. (62), Karczówka Mt. (61), and Rudki (58)) in the Holy Cross Mountains, south-central Poland. Collected samples were dried, disaggregated, and digested in a closed microwave system. All solutions were analyzed for Hg concentrations with cold vapor-atomic absorption spectroscopy (CV-AAS) technique using a continuous flow vapor accessory. The average Hg concentrations and the upper limits of geochemical background (UBG) were as follows: Miedzianka Mt. Hg 0.501 mg kg−1, UBG 0.312 mg kg−1; Karczówka Mt. Hg 0.150 mg kg−1, UBG 0.180 mg kg−1; Rudki area Hg 0.216 mg kg−1, UBG 0.193 mg kg−1. The use of a spatial distribution map of mercury concentrations integrated with computed geochemical factors and results of cluster analysis showed a direct relationship between mercury contents and mining activity conducted in these areas. Only in the case of Miedzianka Mt., this relationship was visible and probably resulted from the presence of tennantite (Cu,Fe)12As4S13 in soil samples, which was also confirmed with the factor analysis. Higher Hg concentrations in soil samples from Karczówka Mt. and Rudki resulted from the presence of clay and other secondary minerals that increase the mercury adsorption from atmospheric deposition. Fossil fuel and biomass combustion was classified as the main anthropogenic source of the metal, but the neighborhood of a cement factory may be taken under consideration. Our results showed that the use of integrated geostatistical models allows for better data visualization and interpretation.

Seasonal changes in concentrations of trace elements and rare earth elements in shoot samples of Juncus effusus L. collected from natural habitats in the Holy Cross Mountains, south-central Poland

Selected trace elements (Ag, As, Ba, Bi, Cd, Co, Cr, Mn, Cu, Fe, Ni, Pb, Tl, U, Zn) and rare earth elements were determined in 13 samples of Juncus effusus collected from three investigation sites in the Holy Cross Mts., south-central Poland. Sampling was carried out four times during a vegetative season of 2014. Almost all the elements examined showed different seasonal trends in their concentrations, except for Ag, Co and Ni. Maximum concentrations of Ag in samples of three investigation sites were found in May (0.068, 0.062, 0.047 mg/kg) whereas Co (0.124, 0.070, 0.079 mg/kg) and Ni (1.8, 0.998, 2.8 mg/kg) in July, respectively. Mean concentrations of Mn and Cd were higher in shoots (558 and 2.35 mg/kg) than in roots (435 and 1.7 mg/kg). Both these elements revealed much higher concentrations in J. effusus than their typical contents in plant samples. Principal component method allowed us to allocate Ni, Ba, Cd and Cu to one group with the highest positive loadings. The most probable explanation for this correlation is that bioavailability of these metals is increased by J. effusus through a release of oxygen to the rhizosphere. Light rare earth elements concentrations predominate over heavy rare earth elements in the samples examined. A fractionation of lanthanides occurs during their transport from roots to shoots, although this transport is rather limited. All shoot samples have a strong positive Eu anomaly.

Extreme enrichment of arsenic and rare earth elements in acid mine drainage: Case study of Wiśniówka mining area (south-central Poland)

The Wiśniówka rock strip mining area (south-central Poland) with quartzite quarries, acid water bodies and tailings piles is one of the most unique acid mine drainage (AMD) sites throughout the world. This is due to the occurrence of enormous amounts of pyrite unknown in sedimentary formations worldwide. Of the two mineralization zones, one that is the most abundant in arsenical pyrite occurs in the lowermost Upper Cambrian formation of the Podwiśniówka quarry. The As-rich pyritiferous clastic rocks are exposed as a result of deep quartzite extraction during 2013–2014. In addition, the clayey-silty shale interbeds are enriched in rare earth element (REE) minerals. The mining operation left an acidic lake with a pH of about 2.4–2.6 and increased contents of sulfates, metal(loid)s and REE. The Podwiśniówka pyrite-rich waste material was stacked up in many places of the mining area giving rise to strongly acidic spills that jeopardized the neighboring environment. One of these unexplored tailings piles was a source of extremely sulfate- and metal(loid)-rich pools with unusual enrichments in As (up to 1548 mg L−1) and REE (up to 24.84 mg L−1). These distinctly exceeded those previously reported in the Wiśniówka area. A broad scope of geochemical, mineralogical and petrographic methods was used to document these specific textural and mineralogical properties of pyrite facilitating its rapid oxidation. The pyrite oxidation products reacted with REE-bearing minerals releasing these elements into acid water bodies. Statistical methods were employed to connect the obtained tailings pool hydrogeochemical data with those derived from this and the previous studies of the Podwiśniówka and Wiśniówka Duża acid pit lakes. In contrast to metal(loid) profiles, the characteristic shale-normalized REE concentration patterns turned out to be more suitable for solving different AMD issues including provenance of mine waste material in the tailings pile examined.

Arsenic in the Wiśniówka acid mine drainage area (south-central Poland) – Mineralogy, hydrogeochemistry, remediation

This paper summarizes different aspects of arsenic mineralogy and geochemistry in the Wiśniówka acid mine drainage (AMD) area, south-central Poland. The basic source of this metalloid in AMD water bodies is micro-grained pyrite that forms two different mineralized zones within the Upper Cambrian rock formation. Due to specific textural and geochemical characteristics, this mineral undergoes rapid oxidation on exposed quarry walls and unvegetated tailings piles, thus contributing to elevated arsenic concentrations in acid pit lakes and ponds, and locally intermittent pools. The latter were highlighted by the highest As levels reaching even 370 mg/L. Of the three AMD large reservoirs, the Podwiśniówka (eastern) lake revealed distinctly raised As concentrations varying from 7.02 to 22.2 mg/L. Another interesting water body is the Marczakowe Doły acid pond showing diverse seasonal As concentration patterns in colloids and a water column. Results of geochemical modeling showed that the saturation indices (SI) of hematite and goethite exhibited the highest values (range of 6.96 to 12.84 and 2.47 to 5.39, respectively) tending to precipitate in all the water bodies examined. In addition, the positive SI values of nanosized ε-Fe2O3 (1.64 to 4.13) and schwertmannite (0.90 to 2.10) were found only in the Wiśniówka Duża and Marczakowe Doły acid waters. Laboratory experiments revealed that the best chemical and cost-effective method (out of the limited number of options) of arsenic removal from the AMD waters examined was the use of high-grade powdered limestone (fraction 0.0–0.09 mm) or more effective although more expensive limewater (calcium hydroxide). The positive SI values of hematite, goethite, ε-Fe2O3 and schwertmannite of neutralized solutions suggest that these minerals should precipitate. Due to diverse concentrations in the examined rock series, arsenic has been used for fingerprinting “hot” places within the mining and neighboring areas, as well as for predicting the directions and effects of strip mining for quartzites. The As signature can also be applied to monitor a detrimental AMD impact on local surface and underground waters.

Geochemical anomalies of trace elements in unremediated soils of Mt. Karczówka, a historic lead mining area in the city of Kielce, Poland

Concentrations of selected trace elements (Ag, As, Ba, Cd, Co, Cr, Cu, Mn, Ni, Pb, Zn) and rare earth elements were determined in 61 samples of surface soils collected from Mt. Karczówka, a historic Pb ore mining area located in the city of Kielce, south-central Poland. Some of these samples were subjected to XRD analyses and Pb stable isotope measurements. The mineral and chemical composition of rock samples were also examined. Mining activity in the study area was conducted mostly during 15th–17th centuries using technologically primitive methods, and was finally ceased in the first half of the 19th century. More than three thousand old shafts, pits and adits occur in the study area and its vicinity. The soils of the study area have not been remediated since the end of the mining operations. The trace elements of the examined surface soils are heterogeneously distributed with lead concentrations in the range of 41–9114 mg/kg and Pb isotopic signatures similar to those of local galena. The results of trace element measurements allowed us to discriminate geochemical anomalies from background levels and to link mineralogy of the host rocks to the origin of anomalous element concentrations. This study shows that elevated levels of elements of geogenic origin have remained in surface soil for two centuries after cessation of mining operations.

Stable isotope geochemistry of acid mine drainage from the Wiśniówka area (south-central Poland)

This paper presents the results of a current isotopic study of pyrite mineralization, acid mine drainage (AMD), and nearby rivers and farmer's wells located in the western part of the Main Range, Holy Cross Mountains (south-central Poland). The principal source of dissolved sulfates in acid lakes, ponds and intermittent pools is the predominant microscopic-grained and locally framboidal pyrite (FeS2) that tends to oxidize rapidly on exposed quarry walls and unvegetated historic and current tailings piles. This process is expedited by the occurrence of arsenic in the pyrite crystal structure, which greatly decreases its resistance to weathering. The δ34S signature of pyrite from the Podwiśniówka quarry (mean of −24.0 ± 3.1‰) was different from that of the Wiśniówka Duża quarry (mean of −17.4 ± 7.2‰). These values fingerprinted two basic pyrite mineralization zones assigned to lowermost and middle Upper Cambrian rock series, respectively. The δ34S-FeS2 differences also were reflected in dissolved sulfates that displayed distinctly different δ34S values: −15.3 ± 1.0‰ (Podwiśniówka) and −10.0 ± 1.7‰ (Wiśniówka Duża). These negative δ34S values stand in contrast to their positive equivalents of the Cambrian Main Range, as well as in the examined rivers and farmer's wells unaffected by AMD processes. The acid water bodies also displayed diverse seasonal variations of δ34S-SO42–, δ18O-SO42– and δ18O-H2O that were linked to surface area, site topography, exposition to radiation, changing weather patterns, especially temperature and a periodical influx of rainwater or meltwater. The isotope data also suggest that evaporation occurred after pyrite oxidation without a direct contact with lake/pond waters, which is also evidenced by the occurrence of sulfate efflorescences on Podwiśniówka and Wiśniówka quarry faces. The stable S, O and H isotopes have been employed for fingerprinting different geochemical processes and for assessing a potential impact of AMD waters on nearby rivers and local perched aquifers, particularly in case of no visual indications. The S isotope signatures of ponds and pools have also been used for determining the provenance of historic and recent mine waste material.

Geochemistry and mineralogy of technogenic soils developed on old mine heaps of abandoned iron ore mines in the Ławęczna area (Holy Cross Mountains, south-central Poland)

Abstract The article presents the results of preliminary geochemical and mineralogical studies of technogenic soils (Technosols) of abandoned iron ore mines on the Ławęczna Hill near Miedziana Góra in the Holy Cross (Świętokrzyskie) Mountains, southcentral Poland. The results of chemical analyses (XRF) were used to calculate the soil enrichment factors of arsenic, copper, iron, lead and zinc, and compare the element concentrations to their levels in uncontaminated soils across Poland and in the city of Kielce. The highest values of soil enrichment factors of metals (As 27.699, Ni 26.455, Cu 9.353, Zn 3.344, Pb 0.62) were recorded for the sand fraction composed of iron oxyhydroxides and hematite, whereas the lowest (Ni 0.22, Cu 0.069, Zn 0.007, Pb 0.028) for the clay–silt and sand fractions, which were primarily composed of calcite and quartz as well as for gravel fraction. The clay-silt fraction shows the highest enrichment in arsenic (27.69). The examined metals and arsenic show positive geochemical anomalies.

Springs in South-Central Poland – changes and threats

Springs in South-Central Poland – changes and threats

Rare earth and trace element signatures for assessing an impact of rock mining and processing on the environment: Wiśniówka case study, south-central Poland.

A detailed hydrogeochemical study was performed in the Wiśniówka mining area (south-central Poland). This covered three acid pit bodies, historic tailings acid ponds, acid pools, and additionally two neighboring rivers. All these acid mine drainage (AMD) waters are characterized by the pH in the range of 1.7 (pools) to 3.5 (tailings ponds). The most interesting is the Podwiśniówka acid pit lake that shows a very low pH (2.2–2.5) and very high concentrations of SO4 2− (2720–5460 mg/L), Fe (545–1140 mg/L), Al (86.2 mg/L), As (9603–24,883 μg/L), Co (1317–3458 μg/L), Cr (753–2047 μg/L), Cu (6307–18,879 μg/L), Ni (1168–3127 μg/L), and rare earth element (REE) (589–1341 μg/L). In addition, seeps that drain the Podwiśniówka mine tailings and partly aggregate piles form strong acid pools in the mining area. Along with these pools, in which As and REE contents reach 369,726 and 6288 μg/L, respectively, these waters are among the most distinctive As- and REE-rich AMD surface waters across the world. It is noteworthy that the Podwiśniówka acid pit lake and Wiśniówka Duża acid pit sump exhibit different element signatures and REE concentration patterns normalized to North American Composite Shale (NASC): the Podwiśniówka acid pit lake always shows a characteristic roof-shaped medium REE (MREE) profile with distinct enrichments in Gd, Eu, and Tb whereas the other one displays a step-shaped heavy REE (HREE) profile with positive Tb and Gd anomalies. The REE undergo fractionation during weathering and the subsequent leaching of dissolved and suspended fractions from rocks to acid water bodies where these and other elements are further fractionated by geochemical processes. This study shows that the individual REE have greater affinities for Mn, HREE for Fe and SO4 2−, and only La and Ce for Al. This specific water geochemistry has enabled us to (i) pinpoint the location of AMD “hot spots” originated from quartzite mining and processing operations conducted by current and previous mining companies, (ii) predict the directions and effects of future strip mining for quartzites in the Wiśniówka Duża and Podwiśniówka open pits, and (iii) evaluate the potential impact of mining and processing effluents on the quality of rivers.

Geochemical background of potentially toxic trace elements in reclaimed soils of the abandoned pyrite–uranium mine (south-central Poland)

Spatial distribution patterns of As, Ba, Cd, Cr, Cu, Mn, Ni, Pb, U and Zn were determined in topsoil samples collected after 40 years of chemical remediation conducted in the inoperative “Staszic” pyrite–uranium mine in the Holy Cross Mountains, south-central Poland. Soil samples were taken from 58 sites using a systematic random sampling design. Selected samples were subjected to an X-ray diffractometry analysis on bulk soils and separated clay fractions. Hematite, goethite and gypsum are common mineral phases in soil samples. Technogenic soils developed on reclaimed mine spoils show uniform spatial element distribution patterns and additionally a distinct enrichment in As, Pb, Mn, U and Zn. Mineral and chemical composition of soils vs. rocks points to the lithogenic source of the determined elements. The results of chemical analysis have been used for evaluation of geochemical background of trace elements in the study area with the iterative 2σ-technique. This investigation shows that using mean crustal element concentrations (Clarke values) as proxies of threshold values in soils are not useful for determination of strongly positive geochemical anomalies. A modified enrichment factor, i.e. a local enrichment factor, is proposed for identification of sites where soils are contaminated.

Estimation of plant sampling uncertainty: an example based on chemical analysis of moss samples.

In order to estimate the level of uncertainty arising from sampling, 54 samples (primary and duplicate) of the moss species Pleurozium schreberi (Brid.) Mitt. were collected within three forested areas (Wierna Rzeka, Piaski, Posłowice Range) in the Holy Cross Mountains (south-central Poland). During the fieldwork, each primary sample composed of 8 to 10 increments (subsamples) was taken over an area of 10 m2 whereas duplicate samples were collected in the same way at a distance of 1–2 m. Subsequently, all samples were triple rinsed with deionized water, dried, milled, and digested (8 mL HNO3 (1:1) + 1 mL 30 % H2O2) in a closed microwave system Multiwave 3000. The prepared solutions were analyzed twice for Cu, Fe, Mn, and Zn using FAAS and GFAAS techniques. All datasets were checked for normality and for normally distributed elements (Cu from Piaski, Zn from Posłowice, Fe, Zn from Wierna Rzeka). The sampling uncertainty was computed with (i) classical ANOVA, (ii) classical RANOVA, (iii) modified RANOVA, and (iv) range statistics. For the remaining elements, the sampling uncertainty was calculated with traditional and/or modified RANOVA (if the amount of outliers did not exceed 10 %) or classical ANOVA after Box-Cox transformation (if the amount of outliers exceeded 10 %). The highest concentrations of all elements were found in moss samples from Piaski, whereas the sampling uncertainty calculated with different statistical methods ranged from 4.1 to 22 %.

The Application of the Multi-Layered Chert Sourcing Approach (MLA) for the Characterisation and Differentiation of ‘Chocolate Silicites’ from the Holy Cross Mountains, South-Central Poland

Chocolate silicites from the Świetokrzyskie (Holy Cross) Mountains in south-central Poland were widely used for stone tool production from Middle Palaeolithic times to the Early Iron Age. Their presence extends beyond Poland into lithic assemblages from the Czech Republic, Slovakia, Hungary and eastern Austria. Outcrops of this material are situated within a narrow strip of Mesozoic (Upper Jurassic) sediments at the northeastern footslopes of the Holy Cross Mountains. Attempts of a raw material characterisation were repeatedly undertaken, however, a clear differentiation of the visually defined subvarieties was never achieved. For the present study, we applied the Multi-Layered Chert Sourcing Approach (MLA) by combining macroscopic, microscopic and geochemical analyses using Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) to samples from five chocolate silicite deposits in order to characterise the materials and to assess the potential of a source differentiation. Secondly, we included chert samples from Sąspow near Krakow for differentiation on a larger scale. Our results illustrate that a source separation of Holy Cross Mountains chocolate silicites is possible to a certain extent – there are limitations due to their geographic proximity and the resulting similar geologic genesis environments. However, our study showed clear possibilities to differentiate chocolate silicites from Jurassic-Krakow silicites based on characteristic microfossil inclusions and trace element contents.

A long-term influence of anthropogenic alkalization on molluscs biodiversity in an area affected by cement industry, Świętokrzyskie Mountains, South-Central Poland

AbstractThe presented paper reports data from malacological and pedological studies carried out at sites representing diverse biotopes (beech wood, coniferous forest, and meadow) located 2 km away from the Dyckerhoff Cement Plant in Sitkówka-Nowiny in 1992 and in 2008–2009. The studies aimed to determine physicochemical properties of soils exposed to cement and limestone dust emission and to identify composition of snail communities inhabiting three different biotopes in relation to physicochemical properties of soils, and to grasp the dynamics of the alkalization-dependent changes in physicochemical properties of soils and their impact on the composition and ecological structure of malacofauna.