Potentially toxic elements in soils and plants on a reclaimed coal-waste dump in southern Poland : preliminary study

The phase composition and concentrations of six potentially toxic elements (Zn, Pb, Mn, Cu, Ni, and Cd) in topsoil and plants were studied. The samples were taken from the waste dump in Katowice in the Upper Silesian Coal Basin. Mineral matter was identified by XRD and SEM. Mineral composition of studied topsoils depends on material composition used to forming the surface layer on the dump. There aluminosilicates (chlorite, muscovite, clays minerals), quartz, Fe and Ca sulphates and Fe oxides dominate. On plants shoots there were identified dolomites, Fe oxides, Ca sulphates, Na and K chlorides and rarely Au-Cu alloys beside quartz and aluminosilicates. By using AAS and ICP-OES contents of heavy metals in soils and plants were determined. Scanning electron microscope allowed to define the chemical composition in soils and plants and XRD to identify mineral contents. In this work measurement of pH and total organic carbon content were carried out. Results indicate that topsoil is highly enriched in heavy metals, especially in zinc, and it is positive correlated with contents of metals in plants growing on such contaminated area. In soils Zn content was in the range from 120 to 3550 mg kg-1, Pb from 31 to 905 mg kg-1, Ni from 3 to 78 mg kg-1 and Cd from1 to 11 mg kg-1. For plants it was respectively Zn to 284 mg kg-1, Pb to 59 mg kg-1, Ni to 4 mg kg-1 and Cd to 1 mg kg-1. The results indicate that application of coal wastes as reclamation material is not advised due to environmental issues

Metale ciężkie w środowisku glebowym olkuskiego rejonu eksploatacji rud Zn-Pb

The Upper Silesian-Cracovian ore deposits are MVT (Mississippi Valley type) deposits and the ores are characterized by simple mineral compositions. In the Zn-Pb-Fe sulphidic ores, the following heavy metals are present: Zn, Pb, Fe, Mn, Cd, Tl, Ag associated with metalloid elements such as As and Sb. In the Olkusz area, though near-surface exploitation of the Pb-Ag ores was conducted ever since the 12th century, the exploitation of Zn-Pb ores began only in the 19th century. The ores were, at that time, enriched by the washing of oxidized Zn-Pb bearing deposits. In the second half of the 20th century, rapid development of Zn-Pb mining occurred with yearly outputs of ore exceeding two million tons of Zn-Pb sulphide. In parallel, oxidized ores were processed by roasting in rolldown furnances that were used until the 1980s. Since the 1970s, new techniques of hydrometallurgical ore enrichment have been developed which have enabled the recovery of high purity, electrolytic zinc. In areas of Zn-Pb ore exploitation, enrichment and metallurgical processing, heavy metals are concentrated in the superficial zone of the ground soil; these contaminate ground- and surface waters and penetrate into trophic chains. Investigations on minerals in the soil environment are of great importance in revealing the chemical transformation processes involved in the bio-concentration of particular metals in plants as well as in micro- and mezzo-fauna organisms. The source of heavy metal ions such as Zn2+, Pb2+, Fe3+, Mn2+, Cd2+ and Tl+ are metal-bearing mineral grains deriving from secondary, post-flotation waste deposits and from post-mining and post-metallurgical wastes. Further sources of these metals are high- and low-level emissions of air-borne dust from metallurgical plants and other industrial activities in the area. A significant influence on the increased concentrations of metals in the near-surface rock layer and in the in-situ created soil is the geological setting of the area and of the shallow occurrence of ore-bearing dolomites in particular (Figs 1, 2, 3). The subject of this research was the near-surface layer of the soil (depth: 0—0.05 m) in the area. This was industrially transformed by historical mining activity as well as by ore enrichment and metallurgical processing of Zn-Pb ores. The research area extends for a distance of 7 km to the north and north-east from post-flotation waste dumps (Fig. 10), which were sited several kilometers to the west of the town of Olkusz. In this research, the author of the thesis used a range of analytical techniques, including: X-ray diffraction (XRD), ASA — atomic absorption spectroscopy (for chemical composition detection) and scanning microscopy, which enabled the investigation of submicroscopic features of the mineral grains (BSE images) and their elemental composition (EDS analysis). Representative submicroscopic forms of minerals containing Zn, Pb, Fe, Mn, Cd, AS, Sb, Cu, Cu, Sn and other elements are presented on 11 illustrations comprising 101 BSE images (Photos 2—13). Elemental compositions of the mineral grains are presented on several tens of EDS spectra. Of particular interest in the research were the roots of plants which had settled on highly polluted ground. The investigation focused on the forms, elemental compositions and the manner of occurrence of both primary- and secondary minerals present in the epidermal layer of the roots of such plants as Dianthus carthusianorum, Festuca ovina, Viola tricolour, Cardaminopsis arenosa, Armeria maritime and others. Submicroscopic analysis of plant-root epiderm and of fine-grained soil indicates that metal-bearing minerals are abundant in the compositions of both. In the investigated rhizospheres, the research identified mineral grains with forms and chemical compositions different from those of the minerals occurring in both primary- and oxidized Zn-Pb ores. Roots of plants and shreds of fungi are covered by a secondary glaze, and coatings and superficial concentrations of metal-bearing minerals, all formed as a result of the biochemical activity of biotic soil components which were rich in solutions and metals. The formation of such surface forms on the roots may reflect the defensive reaction of the plants to high concentrations of heavy metals. The research focused on the origin and on the forms of Ca sulphate found on the plant roots and on other organic constituents in the soil, e.g., on needles of Pinus silvestris. The results of the research point to the major importance of submicroscopic analysis in the recognition of acid waste drainage (AWD) processes occurring in soils rich in Zn-Pb and Fe sulphides. Metal-bearing minerals are represented in the area by Zn- and Pb carbonates, Fe-Zn-Pb sulphides, Fe oxides and by unstable sulphates of Fe, Zn and Pb. Commonly, the minerals are of submicroscopic size < 20 μm) and in the form of irregular grains and aggregates with morphologies that indicate that the minerals had been subject to weathering processes during the stage of their hypergenesis. The parageneses of ore minerals recognized in the soils of the Olkusz region are identical to those found in the primary Zn-Pb ores. The simple, metal bearing sulphides present, such as sphalerite, galena, marcasite and pyrite, are typical of Zn-Pb ores of MVT type. In the near-surface layer of the soil, the chemical transformations of the sulphides are similar to those seen in the primary Zn-Pb ores. Among Zn-Pb-Fe minerals recognised in the soils, smithsonite, cerussite, and Fe oxides and hydroxides, are the most common. In the areas of both historicand contemporary post-industrial waste heaps, the processes of sulphide oxidation are very distinctly marked by the secondary crystallization of Ca and Fe sulphates on the roots of plants. A significant volume of metals occurs in polymineral aggregates characterized by complex structures and chemical compositions. In those areas close to the metallurgical plant, characteristic spherical aggregates were recognized (Photos 9—10) which, apart from Si and Al, also contain Fe, Zn, Pb, Mn, Cd and As. The presence of these elements is evidence for the major involvement of metallurgical-process emissions in the pollution of the soil. The superficial layer of soil which covers land reclaimed during the last several years does not contain spherical mineral phases. During his research, the author established that since the end of the last century, metal- bearing post-metallurgical aggregates had been no longer emitted into the atmosphere. The near-surface layer of the soil (depth; 0—0.05 m) formed on the post-mining waste deposits, in the vicinity of post-flotation tailing dumps and in places where the processing of Zn-Pb ores had taken place in the past, is very commonly characterized by exceptionally high metal contents. In areas neighboring post-flotation tailings, i.e., at distances of 0—1.2 km, analysis of numerous soil samples revealed very high concentrations of Zn (5 000—10 000 mg kg–1), Pb (1 000—5 000 mg kg–1), Fe (10 000—40 000 mg kg–1), Cd (10—100 mg kg–1) and Tl (5—50 mg kg–1). Total contents of metals in the superficial soil layer as well as the size of mineral grains containing Zn, Pb, Cd, Fe and Mn, show significant correlations with distance from the sources of the polluting emissions (Fig. 21). The distribution of metals, i.e., Zn, Pb, Fe, Mn, Cd, and Tl, in soil samples divided into specific grain size groups is also presented. The techniques of scanning electron microscopy (SEM) enable quick and easy recognition of particular groups of metal-bearing minerals occurring in the soil. Particularly good results were obtained for the mineral grains present on the epiderm of plant roots as well as on other organic material such as shreds of fungi or algae. SEM analysis, conducted in the low-vacuum working mode (0.3 Torr), makes it possible to distinguish components which are rich in Zn, Pb, Cd, Fe and Mn. The identification of Tl-bearing material is not possible with the use of EDS spectral analysis. The soils containing the significant concentrations of the metal-bearing minerals constitute a sort of reservoir for heavy metals. These metals are a potential threat to the natural environment. Commonly, however, the heavy metals are bound in stable- and difficult-to-dissolve mineral phases. Thus, the possibility for migration of the metal ions into underground waters, soil-originated solutions and trophic chains of organisms is limited and continues very slowly

Forms of heavy metals (Zn, Pb, Cd) occuring in rhizospheres from the areas of former and contemporary Zn-Pb ore mining

The research areas were selected in the regions heavily polluted by wastes from the former washing plant, flotation waste dump and by non-sulphide Zn-Pb ores from open pit mining in the Olkusz region. The submicroscopic phases occurring in the surface of plant roots and in the rhizospheres were investigated by XRD and SEM/EDS methods. Morphology of submicroscopic metalliferous phases and their manner of occurrence were the subject of study. The analysis of EDS spectra enabled to identify phases and mineral aggregates including Zn, Pb, Fe, Mn, Cd in their structure. The soils from the washing plant and areas of open pit exploitation are contaminated by diverse complexes of minerals. The occurrence of unstable Fe, Pb, Ca sulphates indicate that these wastes are still intensively geochemically active

Wpływ minerałów metalonośnych na biotyczne składniki wierzchnich warstw składowisk odpadów z flotacji rud cynku i ołowiu

The mineral components of topsoil in the zinc and lead flotation tailings ponds were analyzed. To examine such mineral components the authors used methods such as scanning electron microscopy (SEM), energy dispersive spectrometry (EDS) and atomic absorption spectroscopy (AAS). The goal of this study was to pay particular attention to the secondary metalliferous mineral phases formed in rhizosphere zones mainly on plant roots and the influence of autochthonous sulphur bacteria and ferric bacteria on the chemical mechanism of waste components. This study aims both to recognize the (bio)chemical change of flotation tailings which is of great significance for the vegetation of plants, fungi and microorganisms and to properly plan the treatment connected with reclamation and phytoremediation of the area affected by waste disposal

Vegetation and Environmental Changes on Contaminated Soil Formed on Waste from an Historic Zn-Pb Ore-Washing Plant

Post-mining waste from Zn-Pb ore exploitation undergoes processes of spontaneous succession and changes in soil chemical composition. The Zakawie area was industrially transformed by historical mining activity, ore enrichment, and the metallurgical processing of Zn-Pb ore. The subject of the study was to analyse the rate of vegetation succession (from 1999 to 2019), soil chemistry, and the relationships between them in an anthropogenic habitat with high concentrations of potentially toxic metals. Ecological and geochemical studies were carried out in an area contaminated with waste from a disused Zn-Pb ore-washing plant. Between 1999 and 2019, the transformation of grassland and meadow vegetation into scrub and forest–grassland communities was observed. This transformation led to a decrease in the area of Molinietum caeruleae meadow (from 25.8% in 1999 to 10.7% in 2019), whose place was taken by Prunus spinosa and Rhamnus cathartica. The community of xerothermic limestone grasslands completely disappeared, being replaced in favour of the Diantho-Armerietum and Prunus spinosa community. In this period, the share of lifeforms of plants and species composition (46 and 60, respectively) also changed. The Shannon and Simpson biodiversity index reached high values in the second investigation period, and it was 0.893 and 0.86, respectively. The anthrosols had a high content of Zn—85,360 mg kg−1, Pb—28,300 mg kg−1, Cd—340 mg kg−1, and As—1200 mg kg−1. Carbonates, clay minerals, and fe-oxides are predominant in the mineral composition of the rhizosphere; the metal-bearing phases are stable; and hardly soluble minerals include smithsonite, cerussite, monheimite, hemimorphite, and oxides of Fe and Fe-Mn. Mineralisation/crust processes formed on the epidermis, and their influences on root development were found. Scanning electron microscopy and energy-dispersive X-ray spectroscopy studies on rhizosphere soil components provide information on the type of minerals and their susceptibility to heavy metals release. The identification of some biotic and mineral structures in rhizospheres can be an interesting source of information on pedogenic processes identified in back-scattered electron images

Rola glonów glebowych w inicjalnych etapach rozwoju gleby na zanieczyszczonych obszarach piaszczystych

Research to evaluate the role of the soil algae in the initiation of pedogenesis in sandy areas and to establish the mineral, chemical and organic composition of soil-algal crusts was done. The investigations area is located in southern Poland in a landscape of drift sand (Bledowska Desert) formed as a result of medieval deforestation related to Ag, Pb and Fe mining activities. Fifteen species of algae (Cyanophyta, Chlorophyta and Heterokontophyta) were identified. In the soil-algal crusts, Corg contents ranged from 0.35-2.23%, Pavail from 9-34 mg · kg–1 and Nt was variable. In investigated area the ground on which soil algae developed was acidic (pH 4.4-5.7 in KCl). Among mineral components in the crust, phases rich in Fe and K dominated (776.5(±2.3) - 2803(±31) mg · kg–1 and 230.5(±3.7) - 696(±22) mg · kg–1, respectively) and elevated concentrations of Zn, Mn and Pb occurred. Soil-crust organic matter includes aliphatic and aromatic compounds, carbohydrate derivatives, phenols, furan and pyrene structures. N compounds have significant contribution in composition of soil-algal crusts - the algae are main source of organic matter in this stage of soil formation. It could accelerate the regeneration of disturbed ecological systems

Ołów w środowisku

W publikacji zostały opisane zagadnienia związane z naturalnym występowaniem ołowiu w środowisku oraz jego wtórnymi, antropogenicznymi koncentracjami w glebach, wodach i pyłach atmosferycznych. Przedstawiono zmieniające się kierunki wykorzystania ołowiu w okresie ostatnich kilku tysięcy lat. Zwrócono uwagę, że stosunkowo niskie temperatury hutniczej produkcji oraz korzystne właściwości sprzyjały masowemu wykorzystaniu ołowiu, jednego z siedmiu najwcześniej poznanych metali. Wskazano, że jedną z przyczyn szybko rosnącego wydobycia ołowiu było pozyskiwanie srebra ze złóż galeny. Omówiono geochemię i mineralogię ołowiu w kontekście koncentracji oraz form występowania tego pierwiastka w różnych środowiskach litosfery. Silna skłonność ołowiu do wiązania się z siarką powoduje, że najczęściej występuje w siarczku Pb, galenie. W etapie utlenienia powstaje węglan Pb, cerusyt, znacznie rzadziej, w obecności jonów innych pierwiastków, np.: P, As, Mo, V, Cr tworzy fosforany, arseniany, molibdeniany, wanadyniany i chromiany ołowiu. Scharakteryzowano geologię oraz zespół minerałów występujących w śląsko-krakowskich złożach rud Zn-Pb. Stosunkowa niska aktywność geochemiczna jonów ołowiu Pb2+ powoduje, że w warunkach naturalnych transfer ołowiu do organizmów żywych jest ograniczony, jednak znacząco rośnie dla syntetycznych minerałów lub związków ołowiu. Opisano metody przeróbki rud Zn-Pb oraz hutniczej produkcji ołowiu, która od XIX wieku była związana z szybko rosnącą produkcją cynku, dlatego jednym ze znaczących źródeł emisji ołowiu są huty cynku. Wskazano na znaczącą rolę regionu śląsko-krakowskiego dla globalnej produkcji ołowiu, cynku i kadmu w okresie XIX i na początku XX wieku. Przedstawiono wielkość produkcji ołowiu na świecie i w Polsce. W kontekście rożnych zastosowań ołowiu (akumulatory, stopy, farby, dodatek czteroetylku Pb do benzyn itp.) wskazano na najważniejsze źródła emisji ołowiu i jego związków do gleb, wód i atmosfery. Zestawiono źródła i wielkość emisji Pb w Europie w latach 1955–2010. Bardziej szczegółowe informacje dotyczące emisji ołowiu do środowiska odnoszą się do regionu śląsko-krakowskiego, gdzie od ponad 200 lat liczne huty produkowały ołów, cynk oraz stopy metali nieżelaznych, co wiązało się z lokalnym i regionalnym zanieczyszczeniem środowiska metalami ciężkimi. Szczególnie silne, toksyczne oddziaływania na organizmy żywe wywiera ołów, szczególnie jego syntetyczne formy emitowane przez huty oraz zakłady wykorzystujące ten metal. Okresy największej prosperity śląskiego hutnictwa ołowiu, cynku i kadmu wiązały się ze wzrostem zatrudnienia, z rozwojem gospodarczym i ogromnymi zyskami dla właścicieli. Z drugiej strony przyczyniły się do katastrofalnego zanieczyszczenia środowiska oraz trudnej do oszacowania skali zachorowań dzieci i dorosłych w wyniku zatrucia ołowiem

Self-heating coal waste fire monitoring and related environmental problems : case studies from Poland and Ukraine

The self-heating of coal waste dumps is considered as a serious environmental issue, wherever active or inactive coal mining has been present. This issue is introduced from two active coal mining regions from Poland (Upper Silesian Coal Basin) and Ukraine (Donetsk Coal Basin) based on mineralogy, organic petrography and geochemistry, and remote sensing techniques. Thermally affected coal wastes reveal changes recorded by organic and mineral matter. Irregular cracks and fissures appear within and at the edges of organic matter particles, which are oxidised, devolatilised and plasticised. Mineral phases underwent oxidation, dehydration, structure rebuilding and recrystallisation. Highest temperatures generated during the fire cause melting and paralava formation. During selfheating, some chalcophile elements like Hg (mostly present as HgS), Pb, Zn can be enriched and released, or different organic pollutants like phenols (originated from vitrinite particles), different PAHs with alkyl substitutes, chlorinated PAHs, or sulphur heterocycles are formed. The introduced remote sensing techniques helped to localise and monitor hot spots with different temperature ranges. Applying SWIR bands of Landsat hot spots from extremely burning dumps in Ukraine were successfully localised, however, only night-time scenes with SWIR can be used. The sun’s disturbing effects should be considered as an influential factor for both thermal imaging camera or satellite images. Thermal cameras can reveal the most detailed signs of low to high temperature anomalies with different cracks and line shapes

Self-Heating Coal Waste Fire Monitoring and Related Environmental Problems: Case Studies from Poland and Ukraine

The self-heating of coal waste dumps is considered as a serious environmental issue, wherever active or inactive coal mining has been present. This issue is introduced from two active coal mining regions from Poland (Upper Silesian Coal Basin) and Ukraine (Donetsk Coal Basin) based on mineralogy, organic petrography and geochemistry, and remote sensing techniques. Thermally affected coal wastes reveal changes recorded by organic and mineral matter. Irregular cracks and fissures appear within and at the edges of organic matter particles, which are oxidised, devolatilised and plasticised. Mineral phases underwent oxidation, dehydration, structure rebuilding and recrystallisation. Highest temperatures generated during the fire cause melting and paralava formation. During self-heating, some chalcophile elements like Hg (mostly present as HgS), Pb, Zn can be enriched and released, or different organic pollutants like phenols (originated from vitrinite particles), different PAHs with alkyl substitutes, chlorinated PAHs, or sulphur heterocycles are formed. The introduced remote sensing techniques helped to localise and monitor hot spots with different temperature ranges. Applying SWIR bands of Landsat hot spots from extremely burning dumps in Ukraine were successfully localised, however, only night-time scenes with SWIR can be used. The sun’s disturbing effects should be considered as an influential factor for both thermal imaging camera or satellite images. Thermal cameras can reveal the most detailed signs of low to high temperature anomalies with different cracks and line shapes

Colheita e Análise de Águas de Consumo, Piscinas e Residuais

Com o objectivo de evidenciar a importância da avaliação da qualidade da água para a saúde humana, a saúde pública e o meio ambiente em si, o presente trabalho apresenta três casos de estudo, abordando as fases essenciais à monitorização de três tipos de água, nomeadamente, água de consumo, água de piscina e água residual. O relatório descreve as técnicas de colheita mais adequadas para cada tipo de água e parâmetro a analisar, fazendo referência aos recipientes de recolha/armazenamento e ao modo de conservação das amostras até ao momento da realização da análise. Apresenta também os métodos analíticos utilizados para determinação dos parâmetros organoléticos, físico-químicos e microbiológicos estudados; e as consequências que cada parâmetro tem, direta ou indiretamente, na saúde humana e no meio ambiente. Os resultados obtidos permitiram concluir que a água residual analisada se encontra em conformidade com a legislação aplicada. No caso da água de piscina, verifica-se conformidade em todos os parâmetros analisados, excepto a condutividade eléctrica, os Germes a 37 °C e os Estafilococos totais. Quanto à água de consumo, verifica-se a conformidade em todos os parâmetros analisados, excepto o cloro residual livre. As análises efectuadas foram objecto de verificação por aplicação de métodos de controlo previamente definidos, podendo concluir-se que todos os ensaios realizados estiveram de acordo com o critério de aceitaçã