Article

Bioaccumulation of Heavy Metals by Endemic Viola Species from the Soil in the Vicinity of the As-Sb-Tl Mine “Allchar”, Republic of Macedonia

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Abstract

Allchar mine is an abandoned arsenic-antimony-thallium deposit located on the north-western part of Kožuf Mt., Republic of Macedonia. Allchar is a unique deposit within the world, due to the variety of its mineral composition especially and in the high content of thallium. The aim of this work was to assess the level of contamination at this post-mining area as well as to determine the intensity of accumulation of various elements (Ag, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Rb, S, Sb, Sr, Tl, V and Zn) with focus on As, Sb and Tl, in two endemic Viola species from this locality (Viola allchariensis G. Beck, Viola arsenica G. Beck) and one Balkan endemic species (Viola macedonica Boiss. & Heldr.). Samples of different plant parts and soil were digested and then analysed by ICP-AES. It was found that the accumulation of As, Sb and Tl in these endemic species is significantly high. In this study a systematic investigation of the As-Sb-Tl contamination of soils and their bioavailability was carried out using the extraction procedure in order to explore the mobility and potential bioavailability of the As, Sb and Tl.

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... (pansies) of Viola L., rich in species tolerant to high concentrations of heavy metals in the soil (Erben 1985(Erben , 1996Prasad & de Oliveira Freitas 2003;Słomka et al. 2015). Species of the section Melanium frequently occupy calamine (Zn/Pb), serpentine (Ni/Cr/Fe/Mg), cupriferous (Cu), and arsenic (As) soils (Banásová et al. 2006;Hildebrandt et al. 2006;Stevanović et al. 2010;Bothe 2011;Bačeva et al. 2014). Similarly, V. lutea ssp. ...
... Many European metallophytes of the section Melanium are found in the mountains of the Balkan Peninsula (Bačeva et al. 2014), which is the center of the diversity of the section (Erben 1996). A cytotaxonomical conspectus of violets from this 2 A. Słomka et al. syndrome" (see Kazakou et al. 2008) visible as physiological and morpho-anatomical adaptation. ...
... These species are widely distributed through Europe, whereas V. lutea, with many mountainous stands, occurs mainly on basic rocks of Central Europe (Balme 1954;Meusel et al. 1978). Albanian violets are Balkan or Albanian endemic species (Stevanović et al. 2003;Malo & Shuka 2008;Mullaj et al. 2010;Hashani & Shuka 2013;Bačeva et al. 2014;Tomović et al. 2014aTomović et al. , 2014b. ...
Article
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The genus Viola, particularly Melanium section, rich in metallophytes, is an excellent taxon for study of microevolutionary and adaptation processes. Pollen, ovule, and microstructural floral characters were investigated by LM, SEM, and CLSM in seven endemic Albanian violets, five serpentinophytes (Viola albanica, V. dukadjinica, V. albanica × V. dukadjinica, V. raunsiensis, and V. macedonica), two from chalk soil (V. aetolica and V. schariensis), and in their closest relatives (V. lutea ssp. sudetica, V. tricolor ssp. tricolor, and V. arvensis) for their taxonomic usefulness and adaptive value. Three among analyzed characters were common in all Albanian violets however not unique. Serpentinophytes, V. aetolica and V. schariensis possessed hairs deep inside the spur, developed pollen heteromorphism, both increase the chance of pollination in unpredictable conditions and had strongly developed tannin rich layer in the outer integument of the young ovules with a protective role. They also all exhibited high pollen viability (86.9 ± 10.2%), high frequency of normally developed, enlarged (fertilized) ovules in ovary (65.0 ± 24.0%), but also high frequency of degenerations in developing ovules (40.4 ± 9.8%). Several flower characters may be adaptive in the unfavorable, high altitude environment, including serpentine soils. High pollen viability and normally developed fertilized ovules are sufficient for Albanian species maintenance.
... Several ore bodies occur within a zone of 2 km in length and around 300-500 m wide. The complex As-Sb-Tl Allchar deposit is unique in its mineral composition [6][7][8] . The most important ore minerals are Fe-sulphides, As-and Tl-minerals, cinnabarite, and As-, Pb-and Sb-sulphosalts [9][10][11] . ...
... In our previous study on the same locality, three other endemic species were found (Viola allcharensis, Viola arsenica and Thymus alsarensis Ronn.) that also have abilities to accumulate the same toxic elements 7,8 . If we compare the results for the content of As, Sb and Tl in the Centaurea leucomalla with the results for the other endemic plants, some differences could be seen (Table 3). ...
Article
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The aim of this work is to assess the accumulation of some toxic elements in relation to their mobility by plant Centaurea leucomalla Bornm. found in the areas of the abandoned As-Sb-Tl mine Allchar, Kozuf Mountain. Investigations have been initiated to determine the levels of uptake and distribution of As, Sb and Tl, as well as some other heavy metals, to the different parts of the species of Centaurea leucomalla, an endemic species from this locality. Samples of different parts of the plant and corresponding soils were processed, digested and then analysed by ICP-AES. It was found that the accumulation of As, Sb and Tl in this endemic species is significantly high. Total As content in soil ranged from 27-7750 mg/kg, and in plant from 0.25-211 mg/kg, the content of Sb in soil ranged from 0.71-8820 mg/kg and in plants from 0.25-58 mg/kg, and the content of Tl in soil ranged from 22.2-1430 mg/kg, while in plants from 0.10-239 mg/kg. Accumulation of these elements in the Centaurea leucomalla may cause these plants to be used as valuable tools for bioindication, while the accumulation of these elements in the plant can cause risk to human and animal health. @ 2018 Scibulcom Ltd. All Rights Reserved.
... Three methods were applied for the study of the plant-availability of the elements from the soil: extraction in 0.1 M HCl for 1 h and filtered with an acid-resistant filter; extraction with H2O and extraction of the soluble species of trace elements in a mixed buffered solution (pH = 7.3) of triethanolamine (0.1 mol l −1 TEA) with CaCl2 (0.01 mol l −1 ) and diethylenetriaminepentaacetic acid (DTPA, 0.005 mol l −1 ) [5]. ...
... For that issue, triple extraction methods were applied: (a) soil extraction with water which only provides information on the actual availability of elements from the soil solution (b) extraction using sequestering reagents (DTPA-CaCl2-TEA), which is often recommended for the extraction of toxic or biogenic metals and (c) extraction with acid reagents for displacing potentially available forms that are not easily extracted. In our case a solution of 0.1 M HCl was applied [5]. With the simulations of these extractions we were able to assess the level of plant-available elements and conditions that live plants. ...
Conference Paper
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Food safety and quality are a major public concern worldwide, regarding the risk associated with consumption of food stuffs contaminated with heavy metals as toxins. The levels of 8 elements contents were determined in various vegetables [garlic (Allium sativum), onion (Allium cepa) and parsley (Petroselinum crispum)], cultivated around copper mine environ. Bioaccumulation and mobility of heavy metals were determinate with three soil extraction methods: in 0.1 M HCl; in H2O and in a mixed buffered solution (pH = 7.3) of triethanolamine (0.1 mol l−1) with CaCl2 (0.01 mol l−1) and diethylenetriaminepentaacetic acid (0.005 mol l−1). Heavy metals contents were investigated for determining the bioaccumulation properties in vegetables parts in order of health risk in consuming food. Inductively coupled plasma - atomic emission spectrometry (ICP-AES) was applied to determine the contents of the analyzed metals content in the vegetables and soils.
... (3) Extraction of the soluble species of trace elements in a mixed buffered solution (pH = 7.3) of triethanolamine (TEA, 0.1 mol L −1 ) with CaCl 2 (0.01 mol L −1 ) and diethylenetriaminepentaacetic acid (DTPA, 0.005 mol L −1 ), which is often recommended for extraction of toxic or biogenic metals. The DTPA extracting solution was prepared in the following way: 0.005 mol L −1 DTPA, 0.01 mol L −1 CaCl 2 and 0.1 mol L −1 TEA was adjusted to pH to 7.30 ± 0.05 with 1:1 HCl [21]. ...
... The Teflon vessels were carefully closed and a microwave digestion method was applied. The digestion method was performed in two steps for total dissolution of the plants tissue at 180°C and pressure of 600 psi applying 100% of 1600 W power energy [16,17,21]. When the digestion was completed, the digests were quantitatively transferred into 25 mL volumetric flaks. ...
Article
Abstract Background Bioavailability of metals occurring in soil is the basic source of its accumulation in vegetables and herbs. The impact of soil pollution (due to urban and mining areas) on the food chain presents a challenge for many investigations. Availability of metals in a potentially polluted soil and their possible transfer and bioaccumulation in sorrel (Rumex acetosa), spinach (Spinacia oleracea) and common nettle (Urtica dioica), were examined. Methods Microwave digestion was applied for total digestion of the plant tissues, while on the soil samples open wet digestion with a mixture of acids was applied. Three extraction methods were implemented for the bioavailable metals in the soil. Atomic emission spectrometry with inductively coupled plasma was used for determination of the total contents of 21 elements. Results Significant enrichments in agricultural soil for As, Pb and Zn (in urban area), Cd, Cu and Ni (in a copper mine area), compared with the respective values from European standards were detected. On the basis of three different extraction methods, higher availability was assumed for both lithogenic and anthropogenic elements. Translocation values >1 were obtained for As, Cd, Cu, Ni, Pb and Zn. Higher bioconcentrating value was obtained only for Cd, while the bioaccumulation values vary from 0.17 for Cd to 0.82 for Zn. Conclusions The potential availability of hazardous metals in urban and mining soils is examined using DTPA-TEA-CaCl2 (urban) and HCl (Cu-mines areas). Our results suggested that S. oleracea and R. acetosa have a phytostabilization potential for Cd, Cu, Ni and Pb, while U. dioica only for Cu. R. acetosa has a potential for phytoextraction of Cd in urban and copper polluted areas.
... According to Kurt et al. 2013 andÖzdeniz et al., 2017, Viola species were not recorded in the serpentine flora of Turkey. (Brooks, 1998;Jedrzejczyk et al., 2002;Liu et al., 2004;Lei et al., 2008;Stevanović et al., 2010;Bačeva et al., 2014: Tomović et al., 2021. ...
... The fact that the Zn concentration in the aboveground parts of V. kizildaghensis is markedly higher than in the soil where the plants grew indicates that V. kizildaghensis has a Zn accumulator feature. Stevanovic et al. (2010) and Bačeva et al. (2014) examined whether some Viola species in the Alchar region of Macedonia are hyperaccumulators for several heavy metals including Zn. They found that the Viola species studied had an accumulator feature for Zn. ...
... The arsenic-antimony abounded mine "Allchar" near the city of Kavadarci also affects the environment, with the main pollutants As, Sb and Tl in the soil ( Bačeva et al., 2014a), the atmosphere ( Bačeva et al., 2013), the surrounding vegetation ( Bačeva et al., 2014bBačeva et al., , 2015 or in river waters and sediments (Stafilov & Levkov, 2007;Stafilov et al., 2013;Bačeva et al., 2013;Ilić Popov et al., 2014). It was concluded that this pollution is a result of both lithological and anthropogenic sources. ...
Chapter
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The results of the systematic study of the spatial distribution of trace metals in surface soil over the Bitola Region, Republic of Macedonia, known for its coal mine and thermoelectric power plant activities are reported. The investigated region (148 km2) is covered by a sparse sampling grid of 5×5 km, but in the urban zone and around the thermal power plant the sampling grid is denser (1×1 km). In total, 149 soil samples were collected including top-soil (0-5 cm) and bottom-soil samples (20-30 cm). Inductively coupled plasma – atomic emission spectrometry (ICP-AES) was applied for the determinations of 21 elements (Al, As, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, P, Pb, Sr, V and Zn). Based on the results of factor analyses, three geogenic associations of elements have been defined: F1 (Fe, Ni, V, Co, Cr, Mn and Li), F2 (Zn, B, Cu, Cd, Na, K) and F3 (Ca, Sr, Mg, Ba and Al). Even typical trace metals such as As, Cd, Cu, Ni, P, Pb and Zn are not isolated into anthropogenic geochemical associations by multivariate statistical methods still show some trends of local anthropogenic enrichment. The distribution maps for each analysed element is showing the higher content of these elements in soil samples collected around the thermoelectric power plants than their average content for the soil samples collected from the whole Bitola Region. It was found that this enrichment is a result of the pollution by fly ash from coal burning which deposited near the plant having a high content of these elements.
... To assess the bioavailable of heavy metals in soil, three different one-step extraction methods were applied in the present study: (1) extraction with a mixture extractant (0.005 mol/L diethylene triamine pentacetate acid (DTPA), 0.100 mol/L triethanolamine (TEA) and 0.010 mol/L CaCl 2 , pH 7.3, 1:10 w/v); (2) extraction with 0.050 mol/L ethylene diamine tetraacetic acid (EDTA) (1:10 w/v); (3) extraction with 0.100 mol/L hydrochloric acid (HCl) (1:10 w/v) (Baceva et al., 2014;Rivera et al., 2016;Xiao et al., 2015). ...
... The bioaccumulation factor (BAF) is an indication of the accumulation of a substance in an organism compared to its concentration in the environment (Travis and Arms, 1988). It is a ratio between the total concentrations of the element in all parts of the plant and total concentrations of the element in the soil/sediment (Bačeva et al., 2013). BAFs of selected trace elements in V. anagallis-aquatica were calculated as a ratio between the concentration in the whole plant and the concentration in sediment. ...
Article
The present study describes the influence of extensive agriculture on the concentrations of As, Cr, Cu, Cd, Se, Pb and Zn in sediments and in the aquatic plant Veronica anagallis-aquatica. The investigation, spanning 4 years, was conducted on three watercourses in Slovenia (Pšata, Lipsenjščica and Žerovniščica) flowing through agricultural areas. The different sampling sites were chosen on the basis of the presence of different activities in these regions: dairy farming, stock raising and extensive agriculture. The concentrations of the selected elements in sediments and V. anagallis-aquatica were below the literature background values. The distribution of the selected elements among different plant parts (roots, stems and leaves) were also investigated. The majority of the studied elements, with the exception of Zn and Cu, were accumulated mainly in root tissues.
... Several heavy metal contaminants including lead (Pb), nickel, copper, cadmium, zinc and chromium (Cr) can be found in soil and sediments from bodies of water (57). Other heavy metals present in diverse contaminated sites include arsenic, strontium and titanium (58,59). Most of these heavy metals are detrimental to living organisms but bacterial community analysis has shown that microorganisms can grow in the presence of these contaminants (21,60). ...
Article
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Different aspects of bacterial and fungal siderophore biotechnological applications will be discussed. Areas of application presented include, but are not limited to agriculture, medicine, pharmacology, bioremediation, biodegradation and food industry. In agriculture-related applications, siderophores could be employed to enhance plant growth due to their uptake by rhizobia. Siderophores hindered the presence of plant pathogens in biocontrol strategies. Bioremediation studies on siderophores discuss mostly the mobilization of heavy metals and radionuclides; the emulsifying effects of siderophore-producing microorganisms in oil-contaminated environments are also presented. The different applications found in literature based in medicine and pharmacological approaches range from iron overload to drug delivery systems and, more recently, vaccines. Additional research should be done in siderophore production and their metabolic relevance to have a deeper understanding for future biotechnological advances.
... Non-essential elements, such as As and Pb, had lower concentrations in the flower buds, probably reflecting the action of a physiological barrier impeding their translocation to the seeds [73,74]. However, there are some studies showing a high accumulation of TEs in flowers and seeds [75,76]. In addition, metals and metalloids can be transferred to pollen grains and nectar, potentially affecting the composition of apiary products [31]. ...
Article
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Soil pollution by trace elements (TEs) from mining and industrial activity is widespread and presents a risk to humans and ecosystems. The use of trees to immobilize TEs (phytostabilization) is a low-cost and effective method of soil remediation. We aimed to determine the chemical composition of leaves and flower buds of Eucalyptus camaldulensis in seven sites along the Guadiamar River valley (SW Spain), an area contaminated by a mine-spill in 1998. E. camaldulensis trees in the spill-affected area and adjacent non affected areas were growing on a variety of soils with pH from 5.6 to 8.1 with low concentration of plant nutrients. The spill affected soils contained up to 1069 mg kg⁻¹ of As and 4086 mg kg⁻¹ of Pb. E. camaldulensis tolerated elevated TE concentrations in soil and, compared to other species growing in the same environment, had low TE concentrations in the aerial portions. Besides tolerance to soil contamination, E. camaldulensis had low bioaccumulation coefficients for soil contaminants. TE concentrations in the aboveground portions were below levels reported to be toxic to plants or ecosystems. Flower buds had even lower TE concentrations than leaves. Despite the relatively low concentration of TEs in leaves they were significantly correlated with the soil extractable (0.01 M CaCl2) Cd, Mn and Zn (but not Cu and Pb). The general features of this tree species: tolerance to impoverished and contaminated soils, fast growth and deep root system, and low transfer of TEs from soil to aboveground organs makes it suitable for phytostabilization of soils contaminated by TEs. In addition, eucalyptus leaves could be used for biomonitoring the soil extractability of Cd, Mn and Zn but not Cu or Pb.
... It is not rare that metal-tolerant species evolved from montane populations (for a revision, see Bothe and Słomka 2017 [13]) which could have been naturally affected by the increased amounts of heavy metals, typical for mountain soils [58]. Furthermore, the majority of European metallophytes of the Melanium section belonging to the Viola genus, e.g., V. tricolor investigated here, are commonly found in the mountains of the Balkan Peninsula [59,60]. This all suggests that a common ancestor of metal-tolerant violets could have grown in montane areas and may have been affected by the influence of the naturally enhanced concentration of heavy metals. ...
Article
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Many species of the Viola L. genus (violets) colonize areas with high concentrations of trace elements in the soil, e.g., nickel, cadmium, zinc, and lead. Although tolerance to heavy metals is a common phenomenon in violets, it is not clear whether this is the result of gradual microevolutionary processes as a part of the adaptation to the specific conditions, or whether the tolerance was inherited from the ancestor(s). We developed cell suspension cultures of five plant species: two non-metallophytes—Arabidopsis thaliana (Col-0) and Viola · wittrockiana, and three metallophytes—V. philippica, V. tricolor, and Silene vulgaris subsp. humilis for tolerance tests. The aim of the study was to measure the level of tolerance of violets in comparison with species from the other genera to verify the hypothesis of the high, innate tolerance of the former. We measured cell viability, non-enzymatic antioxidant content, and the accumulation of heavy metals after cell treatment with Zn or Pb. The results indicate they are innate and independent on the ecological status (metallophyte vs. non-metallophyte) and high in comparison with other species tolerance to Zn and Pb in violets. Viability of the cells after Zn and Pb (1000 μM) exposure for 72 h was the highest in violets. Antioxidant content, after heavy metal treatment, increased significantly, particularly in metallophyte violets, indicating their high responsivity to metals. In all species, lead was detected in the protoplasm of the cells, not in the vacuole or cell wall. All violets were characterized by the accumulation capacity of lead. Here, we clearly show that the physiological and biochemical studies conducted with the use of heavy metals on plant cells translate into the heavy metal tolerance of the species.
... Hooda [1] states that such risks are contingent on the bioavailability of trace elements, not just on their presence in the environment. Biological impacts include the health and wellbeing of flora, fauna and humans exposed to contaminated water and food resources [2][3][4]. The possible incorporation of trace metals from abandoned mining areas adjacent to population centers into biomass poses unknown hazards. ...
Article
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Larrea tridentata (creosote bush) growing in contaminated tailings of the Techatticup Mine in Nelson, Nevada were sampled and analyzed for trace metals. Samples were also collected outside the mine tailings to measure geogenic trace metal levels. These data show that some trace metals (Cu, Pb, Zn, Co, Fe, Li) enter L. tridentata through root tissues, but at significantly lower levels than in the tailings area. Trace metals that enter the root are higher in concentration in the outer than in the inner root tissue, possibly due to L. tridentata blocking their absorption at the outer root surface. Data further show the plant’s ability to block the intake of these toxic trace metals that may adversely affect the plant. Statistical analysis suggests that certain metals, while not in high abundance, may be utilized by the plant for self-defense mechanisms or to aid in plant development. Finally, differences between plant components may be the result of hyperaccumulation of useful trace metals (e.g. B, Cr, Zn) and a blockage of potentially toxic trace metals (e.g. Cd, Pb, V).
... The populations of this species from the Saint-Laurent-le-Minier area can accumulate up to 1500 μg Tl g −1 in leaves from soils containing up to 32 μg g −1 total Tl (Escarré et al. 2011). Furthermore, three species from the Violaceae family, Viola allcharensis, V. arsenica and V. macedonica, have also been reported to accumulate 2190 μg Tl g −1 , 9090 μg Tl g −1 and 4290 μg Tl g −1 in their leaves, respectively, when growing in soils with 13.7-2140 μg g −1 Tl at the former As-Sb-Tl Allchar Mine in the Republic of North Macedonia (Bačeva et al. 2014). ...
Article
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Purpose Thallium (Tl) is one of the most toxic elements known and its contamination is an emerging environmental issue associated with base metal (zinc-lead) mining wastes. This study investigated the nature of Tl tolerance and accumulation in Silene latifolia, which has so far only been reported from field-collected samples. Methods Silene latifolia was grown in hydroponics at different Tl concentrations (0, 2.5, 5, 30 and 60 μM Tl). Elemental analysis with Inductively coupled plasma atomic emission spectroscopy (ICP-AES) and laboratory-based micro-X-ray fluorescence spectroscopy (μ-XRF) were used to determine Tl accumulation and distribution in hydrated organs and tissues. Results This study revealed unusually high Tl concentrations in the shoots of S. latifolia, reaching up to 35,700 μg Tl g−1 in young leaves. The species proved to have exceptionally high levels of Tl tolerance and had a positive growth response when exposed to Tl dose rates of up to 5 μM. Laboratory-based μXRF analysis revealed that Tl is localized mainly at the base of the midrib and in the veins of leaves. This distribution differs greatly from that in other known Tl hyperaccumulators. Conclusions Our findings show that S. latifolia is among the strongest known Tl hyperaccumulators in the world. The species has ostensibly evolved mechanisms to survive excessive concentrations of Tl accumulated in its leaves, whilst maintaining lower Tl concentrations in the roots. This trait is of fundamental importance for developing future phytoextraction technologies using this species to remediate Tl-contaminated mine wastes.
... As a result, considerable amounts of metals can be accumulated in the seeds of different species (e.g., Gross et al. 1986). An extreme case is Viola species (Viola arsenica, Viola macedonica and Viola allchariensis) from a Macedonian mine, reaching more than 1000 mg kg −1 of As and Tl in their seeds (Bačeva et al. 2014). Trees in the Salicaceae family, such as Populus and Salix species, tend to accumulate Cd and Zn in leaves and even in fruits in contaminated areas (Madejón et al. 2004. ...
Article
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Seed germination is considered a critical phase in plant development and relatively sensitive to heavy metals. White poplar (Populus alba) trees tend to accumulate Cd and Zn in their tissues. We tested if soil contamination can affect P. alba progeny, reduced seed germination and explored the distribution of mineral elements in the seed. For this purpose, fruits and seeds from female P. alba trees were selected from two contaminated and one non-contaminated areas. Seeds from all the sites were germinated using only water or a nutritive solution (in vitro). Concentrations of nutrients and trace elements in the fruits and seeds were analysed. Seedling growth in vitro was also analysed. Finally, a mapping of different elements within the poplar seed was obtained by particle-induced X-ray emission (PIXE). Germination was similar between different progenies, refuting our hypothesis that seeds from a contaminated origin would have reduced germination capacity compared to those from a non-contaminated site. Seedling growth was not affected by the contaminated origin. Cadmium and Zn concentrations in fruits produced by P. alba trees in the contaminated sites were higher than by those from the non-contaminated site. However, the nutritional status of the trees was adequate in both cases. Cd in seedlings was higher in those from contaminated soils although lower than in fruits, indicating a certain exclusion from seeds. Preliminary results of the PIXE technique showed that Al and Zn were distributed uniformly in the seeds (Cd was not detected with this technique), while the nutrients P and S were concentrated in the cotyledons.
... Then the digests were quantitatively transferred into 25 ml calibrated flasks (ISO 14869-1:200). Three methods were applied for the study of the plant-availability of the elements from the soil: extraction with HCl (10 g of soil in 20 ml 0.1 M HCl) for 1 hour and filtered with an acid-resistant filter; extraction with H 2 O (10 g of soil in 20 ml deionised H 2 O) for 1 hour and filtered; extraction of the soluble species of elements with mixed buffered solution (pH = 7.3) of diethylenetriaminepentaacetic acid (DTPA, 0.005 mol L −1 ), CaCl 2 (0.01 mol L −1 ) and, triethanolamine (0.1 mol L −1 TEA), (10 g of soil in 20 ml DTPA-CaCl 2 -TEA) for 1 hour, according to Bačeva et al. (2013). ...
... This demands further knowledge about the pathways the elements enter the plants and especially about the relationship between macro-and microelements in ecosystems. Numerous investigations have indicated that the bioavailability and transfer of elements depend on pH, cation exchange capacity (CEC), organic matter, oxide, carbonate, or total concentrations depending on the soil type and element species (Puschenreiter and Horak 2000;Kashem and Singh 2002;He et al. 2005;IAEA TECDOC 2006;Roivainen et al. 2012;Bešter et al. 2013;Bačeva et al. 2014;Pinto et al. 2014). Usually, the number of elements is limited to either essential or some toxic elements, and naturally, the interest is directed mainly to agroecosystems where a number of additional factors (manure, irrigation, etc.) play an important role for the transfer (Kabata-Pendias and Pendias 1984; Kashem and Singh 2002;Uchida et al. 2007;Senila et al. 2012;Shtangeeva et al. 2014). ...
Article
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Purpose It is commonly assumed that the concentration of an element in a plant relates linearly to its concentration in the soil. However, the wide range of reported transfer factors shows that soil concentration of the element is not the only factor influencing its uptake. Recently, the transfer of elements from polluted soils to plants is recognized as a serious problem with a potential impact on human and animal health. The aim of the present research was to combine different factors: soil characteristics, anthropogenic influence, and fractionation of elements for evaluation of their influence on the soil-plant transfer of the elements. Materials and methods Using inductively coupled plasma mass spectrometry (ICP-MS), the concentrations of 52 elements were determined in 27 types of soils after microwave aqua regia digestion. The soil samples were collected from 12 background regions and 15 sites in Bulgaria with different anthropogenic influence. The bioavailability of the elements was established applying BRC sequential extraction scheme. Cluster and factor analyses were performed using STATISTICA 7.0 software package. The estimation of accuracy was done by the analysis of five standard reference materials: reference stream sediments STD-1, STD-3 and STD-4 (Canada Center for Mineral and Energy Technology, Geological Survey of Canada), IAEA Soil-5, and IAEA-Soil-7. Results and discussion The bioavailable part of the majority of essential elements: B, Ca, Mg, Mn, Na as well as Sr was mainly found in the carbonate and easily available fraction of Ba, Cd, Co, Ni, Rb, V, Zn—in the oxide fraction, but Cd, Co, Ni, and Zn were also found in a similar percentage in the organic/sulfide fraction. The rest of the elements were in the organic/sulfide fraction. Cluster and factor analyses revealed the interelement correlations and relations in the investigated soils, as well as the dependence of transfer factors (TFs) on the pseudo total soil concentration, concentration of the element in the soil fractions, pH, cation exchange capacity (CEC), and the organic carbon content. Conclusions The investigation of the bioavailability of 52 elements in 27 soils and the transfer in the system soil/Taraxacum officinale established that for the majority of the elements, the TF is stable irrespective of the type of soil and pollution. This confirms the linearity assumption and indicates that the plant species is a very important parameter. The fractionation analysis proved that in polluted regions, the major polluting elements are more bioavailable than in clean regions.
... Then the digests were quantitatively transferred into 25 ml calibrated flasks (ISO 14869-1:200). Three methods were applied for the study of the plant-availability of the elements from the soil: extraction with HCl (10 g of soil in 20 ml 0.1 M HCl) for 1 hour and filtered with an acid-resistant filter; extraction with H 2 O (10 g of soil in 20 ml deionised H 2 O) for 1 hour and filtered; extraction of the soluble species of elements with mixed buffered solution (pH = 7.3) of diethylenetriaminepentaacetic acid (DTPA, 0.005 mol L −1 ), CaCl 2 (0.01 mol L −1 ) and, triethanolamine (0.1 mol L −1 TEA), (10 g of soil in 20 ml DTPA-CaCl 2 -TEA) for 1 hour, according to Bačeva et al. (2013). ...
Article
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The aim of the paper is to assess the 23 elements distribution in agricultural soil and vegetables [garlic (Allium sativum), onion (Allium cepa) and parsley (Petroselinum crispum)] widely used as food in areas contaminated with toxic metals due to long-lasting copper mining activities in the Republic of Macedonia. Principal components analysis (PCA) models were computed with different variables: elements contents in vegetables and soil samples collected from contaminated and uncontaminated areas and the bioaccumulation and transferring factors for hazardously metals. Bioaccumulation and mobility of the elements were determined with three soil extraction methods: in 0.1 M HCl; in H2O and in a mixed buffered solution of diethylenetriaminepentaacetic acid, CaCl2 and triethanolamine (DTPA-CaCl2-TEA). Inductively coupled plasma - atomic emission spectrometry (ICP-AES) was applied to determine the contents of the analyzed elements content in the vegetables, soils and soil extracts. The total contents in soil were found above the European standards for As, Cd, Cu and Pb in urban and mines environ, while the vegetables were enriched with Pb and Cd in polluted areas. The PCs plant and soil models (PCA1, PCA2 and PCA3 models) were very useful in determination the relation/correlation of the elements contents in soil (total and extractable contents) and vegetable species. Significant extraction efficiency was obtained for HCl extraction agent (for Ag, Al, Ba, Ca, Cr, K, Li, Mg, Mn, Mo, Na, Ni, P, V and Zn) and for DTPA-CaCl2-TEA (for Cd, Cu, partially Ni, and Pb). Parsley, onion and garlic showed higher translocation efficiency for As, Cd, Cu and Pb in urban area and mines polluted areas (TF>1).
... This demands further knowledge about the pathways the elements enter the plants and especially about the relationship between macro-and microelements in ecosystems. Numerous investigations have indicated that the bioavailability and transfer of elements depend on pH, cation exchange capacity (CEC), organic matter, oxide, carbonate, or total concentrations depending on the soil type and element species (Puschenreiter and Horak 2000;Kashem and Singh 2002;He et al. 2005;IAEA TECDOC 2006;Roivainen et al. 2012;Bešter et al. 2013;Bačeva et al. 2014;Pinto et al. 2014). Usually, the number of elements is limited to either essential or some toxic elements, and naturally, the interest is directed mainly to agroecosystems where a number of additional factors (manure, irrigation, etc.) play an important role for the transfer (Kabata-Pendias and Pendias 1984; Kashem and Singh 2002;Uchida et al. 2007;Senila et al. 2012;Shtangeeva et al. 2014). ...
... Some of the moss samples which were collected in the vicinity of the mine have a significantly higher content for Tl; more precisely, the sample A-35 had a significantly higher content of Tl at 290 mg kg −1 The spatial distribution of Tl is also strongly dependent on lithology and very similar to arsenic spatial distribution (Fig. 7c). Very high content of thallium was also found in the other endemic species from the Crven Dol area from this locality (Bačeva et al. 2013). Antimony has considerably low deposition compared with As and Tl, and it has no significant variation between the Allchar areas and the moss survey in the Republic of Macedonia from 2002, 2005, and 2010 (Barandovski et al. 2008Barandovski et al. , 2012Barandovski et al. , 2013). ...
Article
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A systematic study was carried out to investigate air deposition and to explore the natural distribution and enrichment (contamination) with trace elements in the small area (cca. 13 km(2)) of an antimony-arsenic-thallium mineralization outcrop at an abandoned mine "Allchar." The mine is located on the northwestern part of Kožuf Mount, Republic of Macedonia. The locality of Allchar is unique in its mineral composition; besides a very intriguing mineral, lorandite, there are 45 other minerals, some of which are rare. The distribution of 53 elements (with special attention to As, Sb, and Tl) were detected in 69 moss samples from eight various species collected from this area. Moss samples were analyzed following microwave digestion by inductively coupled plasma-mass spectrometry and inductively coupled plasma-atomic emission spectrometry. It was found that the atmospheric deposition for As in the moss samples on or around the Allchar mine is >6.5 times higher and for Tl is 19 times higher compared to values for the samples from the rest of the Allchar area. By the application of multivariate cluster and R-mode factor analyses (FA), five geochemical associations were determined. Cluster and R-mode FA were used to identify and characterize element associations, and five associations of elements were determined by the method of multivariate statistics. F1 (Co, Cr, Fe, Sc, Li, V, Ga, Y, Ni, Mn, Al, La-Lu, Cu, Ge, Be, Bi, and Hf); F2 (As, Tl, Sb, and Mg); F3 (Rb, Cs, and Mo); F4 (Sr, Ba, Hf, Zr, La-Lu, and Bi), and F5 (Cd, Zn, Ag, and Cu).
... Certain regions in the Republic of Macedonia are rich in arsenic, among which is the Kožuf Mountain. Arsenic has a significant impact on the environment, especially in the region around the abandoned mine of arsenic, antimony and thallium "Allchar" [21][22][23][24]. As it can be seen from data presented in Tables 1, 2 and 5, and Figures 5 and 6, the concentration of arsenic is bellow the detection limit (< 10 mg/l) in all of the samples except for the samples from the Majdanska and Blašnica rivers after Allchar locality, where its concentration ranges from 0.010 to 0.199 mg/l, with a mean concentration of 0.082 mg/l and median of 0.052 mg/l, which is higher than the maximum permissible concentration (Table 4) for the second (0.03 mg/l) and the third class (0.05 mg/l). ...
Article
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An investigation of the distribution of 23 chemical elements (Ag, Al, As, B, Ba, Ca, Cd, Co, Cr, Cu, Fe, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Sr, V and Zn) in surface water samples from the entire basin of the Crna River, Republic of Macedonia, was carried out. In total 31 water samples were collected, from which 8 samples from the Crna River and 4 samples from four main tributaries of Crna River in the Pelagonia Valley (Blato, Prilepska Reka, Dragor and Jelaška Reka). Also, surface water samples were collected from 3 locations in the Tikveš Lake, 8 locations from the Majdanska River and river of Blašnica before its inflow into the Tikveš Lake and from 7 locations of the lower course of the Crna River after the dam of Tikveš Lake until its inflow into the river of Vardar. Determination of the concen-tration of the investigated elements was performed by using atomic emission spectrometry with inductively coupled plasma (ICP-AES). All data obtained for the analyzed samples were statistically processed using software Stat Soft 11.0 where the descriptive statistical analysis of the value for the concentration of the elements was performed. The maps of spatial distribution of the concentration for each element and a histograms for the representation of elements with mean values of the concentrations by regions, were also prepared. The obtained results show that the concentration of investigated element are mainly followed the lithology of the region. However, higher concentrations of arsenic were found in the water samples from the river of Blašnica which is a result of anthropogenic influence from the abounded Allchar mine on the Kožuf Mountain. Also, the increased concentrations of nickel were found in the samples from the lower couse of the Crna River after the dam of Tikveš Lake due to the anthropogenic influence from the ferronickel smelter plant Feni Industry, which can influence the quality parameters of surface waters.
... Such as bacteria that we isolated in the Crven Dol mine or plants (Bačeva et al., 2014) with capacity to accumulate heavy metals found in the surrounding environment of Allchar area. Microbial-based remediation is generally considered as a promising technology for the treatment of metal contaminated soils but requires optimal conditions favouring sorption mechanisms while limiting desorption (Jin et al., 2018). ...
Article
Novel hyper-resistant bacteria were isolated from the Crven Dol mine (Allchar, North Macedonia), arsenic-rich extreme environment. Bacteria were recovered from a secondary mineral mixture, an alteration of hydrothermal realgar rich in arsenates (pharmacolite, hornesite, and talmessite). The sample was recovered from the dark part of the mine at 28 m depth. Three bacterial strains and a bacterial consortium were isolated for their capacity to survive exposure to 32 g/L (209 mM) of arsenite, and 176 g/L (564 mM) of arsenate. The 16S rRNA gene analysis identified bacterial isolates as Stenotrophomonas sp. and two Microbacterium spp. This analysis also revealed that bacterial consortium comprise two Bacteriodetes exhibiting similarity to Olivibacter ginsengisoli and to uncultured bacterium, and one γ-proteobacteria with similarity to Luteimonas sp. Among all isolates Stenotrophomonas sp. exhibited the highest tolerance to As compound as well as the capacity to accumulate As inside the cells. Analysis of genes involved in As-resistance showed that recovered isolates possess the genes encoding the ArsB, Acr3(1) and Acr3(2) proteins, indicating that at least a part of their resistance could be ascribed to As-efflux systems described in isolates obtained from human-polluted environments.
... Thallium influences the indices of plant seed germination, chlorophyll content, and enzymatic activity of soils (Pavlickova et al. 2005(Pavlickova et al. , 2006Ferronato et al. 2016;Guo et al. 2018;Kolesnikov et al., 2021;Luo et al. 2020). Thallium has a toxic effect on the soil and has a high accumulation rate in plants (Baceva et al., 2014;Sabermahani et al., 2016;Sizmur et al., 2016). Selenium concentration in soil varies within 0.01-2.0 ...
Article
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The content of various chemical elements such as metals, metalloids, and nonmetals in the environment is associated with natural and anthropogenic sources. It is necessary to normalize the content of metals, metalloids, and nonmetals as potentially toxic elements (PTE) in the Haplic Chernozem. The soils of the Southern Russia are of high quality and fertility. However, this type of soil, like Haplic Chernozem, is subject to contamination with a wide range of PTE. The aim of the work was to rank metals, metalloids, and nonmetals by ecotoxicity in Haplic Chernozem. To assess the ecotoxicity of chernozem, data for 15 years (2005–2020) were used. Biological indicators used to assess the ecotoxicity of Haplic Chernozem: catalase activity, cellulolytic activity, number of bacteria, Azotobacter spp. abundance, to change of length of radish’s roots. Based on these biological indicators, an integral indicator of the state of Haplic Chernozem was calculated. The ecotoxicity of 23 metals (Cd, Hg, Pb, Cr, Cu, Zn, Ni, Co, Mo, Mn, Ba, Sr, Sn, V, W, Ag, Bi, Ga, Nb, Sc, Tl, Y, Yb), 5 metalloids (B, As, Ge, Sb, Te) and 2 nonmetals (F, Se) as priority pollutants. It is proposed to distinguish three hazard classes of metals, metalloids, and nonmetals to Haplic Chernozem: I class — Te, Ag, Se, Cr, Bi, Ge, Sn, Tl, Hg, Yb, W, Cd; II class — As, Co, Sc, Sb, Cu, Ni, B, Nb, Pb, Ga; III class — Sr, Y, Mo, Zn, V, Ba, Mn, F. It is advisable to use the results of the study for predictive assessment of the impact of metals, metalloids, and nonmetals on the ecological state of the soil during pollution.
... Besides its unique mineral composition and high thallium grades of the ore, the Allchar deposit probably reflects one of the highest documented Tl-concentration in technosols worldwide, with up to 20 000 mg/kg (median 660 mg/kg) (Bačeva et al., 2014a), which by far exceeds the typical Tl content in soil of <1 mg/kg (Karbowska, 2016). The highest Tl contents have been measured in the soils at the Crven Dol locality in the northern, Tl-and As-rich part of the Allchar deposit. ...
Article
Secondary minerals could be effective scavengers of toxic arsenic (As) and thallium (Tl). In environments polluted by mining, these elements are abundant both in acid rock/mine drainage scenarios, as well as in carbonate-buffered environments. In this study we have investigated the behavior of As and Tl during weathering in mine waste dumps and an associated technosol sample from the Crven Dol locality (Allchar Tl-As-Sb-Au deposit, North Macedonia) contaminated with up to 142 g∙kg–1 of As and 18 g∙kg–1 of Tl, making it an As- and Tl-extreme environment. We identified As and Tl reservoirs and discuss their difference from those observed in other naturally As- and Tl-rich environments. The pore waters show high concentrations of As (up to 196 mg·L⁻¹) and Tl (up to 660 μg·L⁻¹). Mild extractions mobilized up to 46% of the total Tl and 11% of the total As, indicating that a large amount of these toxic elements is weakly bound and can be easily mobilized into the environment. Apart from the recognition of Tl storage in several secondary phases (mainly as Tl(I) in members of the pharmacosiderite and jarosite groups, as well as Mn oxides, but also as very minor Tl(III) in other secondary phases), this study also provides the first evidence of Tl uptake by previously unknown thallium arsenate phases (with Tl:As ratios ∼ 2 and 4), detected in carbonate-buffered (near-neutral pH) As- and Tl-rich technosols and waste dumps. These results indicate the need for further studies on Tl speciation in extremely As- and Tl-rich environments.
... Although Tl concentrations in surface soils range from 0.1 to 2 mg kg −1 , with most reported concentrations being b1 mg kg −1 (Fergusson, 1990;Tremel et al., 1997), it occurs at higher concentrations in environments associated with epithermal metallogeneses (b200°C) of sulfide minerals (Sobott, 1995). Natural mineralization or mining of Tl-rich sulfide minerals can produce Tl pollution in the environment, raising environmental concerns in China and other parts of the world Baceva et al., 2014). Anthropogenic Tl contamination mainly results from mining of Tl-rich sulfide minerals (Vanek et al., 2013;Romero et al., 2015), acid mine drainage (Casiot et al., 2011) and tailings spills such as the dam failure accident of Aznalcóllar mine (Spain) in 1998 (Martin et al., 2004). ...
... albanica, V. dukadjinica for Ni, V. allchariensis and V. arsenica for As) or even hyperaccumulators (V. vourinensis for Ni, V. allchariensis and V. arsenica for Tl) of PTE (Psaras and Constantinidis 2009;Słomka et al. 2011Słomka et al. , 2015Bačeva et al. 2014). This phenomenon was particularly evident in species from the ultram a f i c s , w h e r e t h e l a r g e s t n u m b e r o f hyperaccumulator (mainly of Ni) species was found (van der Ent et al. 2013b). ...
Article
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The aim of the present study was to assess the metal concentrations in five species of the genus Viola L. (section Melanium) from 12 ultramafic outcrops and two non-ultramafic (prolluvium and dolomite) soils from Serbia and Bosnia and Herzegovina. The concentrations of P2O5, K2O, Ca, Mg, Fe, Mn, Zn, Cu, Cr, Co, Cd and Pb in soils and plant samples, as well as their shoot-to-root ratio, biological concentration and accumulation factors were determined. Five investigated Viola species growing on 14 different localities displayed considerable differences in concentration of potentially toxic elements in their roots and its accumulation in their shoots. Viola kopaonikensis and V. beckiana from ultramafic soils could be classified as strong Ni accumulators, since moderately high level of Ni was measured in their shoots (up to 266 mg kg−1 and 337 mg kg−1, respectively), while in V. tricolor high amount of the same element was accumulated in the roots (up to 395 mg kg−1). Population of V. beckiana from dolomitic site in Bosnia and Herzegovina accumulated high concentrations of Pb in the shoots (67.1 mg kg−1), as well as of Cd in both roots and shoots (81.1 mg kg−1 and 60.5 mg kg−1). The results also suggest that V. kopaonikensis populations from the ultramafic soils of Serbia emerge as Cr accumulators, which is quite rare trait within the genus Viola. It seems that species from Melanium section apply quite different strategies against toxic elements. Future studies should strive to explain what adaptive mechanisms are hidden behind it.
... It exhibits higher accumulation in plants compared to other pollutants, which makes it a significant concern (Sizmur et al. 2016). It can be easily accumulated by plants when it is available in soil because it commonly exists as a thermodynamically fixed element (Baceva et al. 2014). Many technologies for Tl removal have been reported (Huangfu et al. 2017;Li et al. 2018b) and reviewed Twidwell and William Beam 2002). ...
Article
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Thallium (Tl) is an extremely harmful metal that is substantially distributed in the environment. It can threaten human health via consumption of food potentially derived from Tl-contaminated agricultural production. Little information is available on how to utilize biochar to remediate Tl contamination in agricultural soils. More efforts are urgently needed to be devoted to developing effective techniques to empower biochar with high selectivity of Tl in agricultural soils. In this review, we provided comprehensive information on Tl contamination in agricultural soils. We also discussed recent developments and assessed the current status of biochar applications. We briefly reviewed the bridge between biochar preparation technology and utilization wherein further developments can exhibit potential in terms of Tl remediation. Hence, biochar is expected to exhibit excellent Tl remediation performance in contaminated agricultural soils with promising application prospects. The obtained knowledge provides further insights into the remediation of Tl contamination in agricultural soils.
... Bioremediation of heavy metal enriched soils and groundwater illustrates an immense perspective for upcoming improvement because of its environmental compatibility and probable expenditure efficiency (Baceva et al., 2014). It relies on microbial actions to diminish, mobilize, or immobilize noxious heavy metals through biosorption, biovolatilization, precipitation, surface complexation, and oxidationereduction processes (Paul et al., 2014;Teixeira et al., 2014). ...
... Therefore, it is imperative to use an integrated bioremediation approach by using the consortium of microbes for degradation of petrochemicals containing hydrocarbons. Bioremediation of heavy metal enriched soils and groundwater illustrates an immense perspective for upcoming improvement because of its environmental compatibility and probable expenditure efficiency (Baceva et al., 2014). It relies on microbial actions to To protect the rights of the author(s) and publisher we inform you that this PDF is an uncorrected proof for internal business use only by the author(s), editor(s), reviewer(s), Elsevier and typesetter TNQ Books and Journals Pvt Ltd. ...
Chapter
The release of various inorganic and organic chemicals from various industries like petrochemicals, textiles, pharmaceuticals, agro-based industries, and tanneries are highly toxic to the environment and human health. There are various Several processes and technologies such as physical, chemical and advanced oxidation processes are available for the treatment of these pollutants such as physical, chemical and advanced oxidation processes. However, these processes and technologies have their own limitations and the end- products are also of toxic nature. Therefore, there is a need for identifying and exploring sustainable and eco-friendly methods which require a lesser amount of chemicals, economically feasible and produce non-toxic end- products. The bioremediation approaches to clean- up environmental pollutants are considered as emerging and sustainable methods recently. Bioremediation process is based on an integrated approach employing microbial communities such as actinomycetes, bacteria, fungi and earthworms. It is considered as a sustainable process for management of organic pollutants-rich solid wastes and wastewater. Many microorganisms metabolize toxic chemicals to produce CO2 or CH4, water, and biomass. These pollutants may be enzymatically altered to metabolites that are less noxious or innocuous. Moreover, the solid residue generated in this process has been found to have a potential influence on soil macro- and micro-nutrients, indicating its application as organic manure. However, bioremediation technique required more research for its establishment at a larger scale with an emphasis on the environmental consequences of the end products. In this chapter, we have performed a literature survey based on biological methods for the management of organic pollutants. Microbes responsible for degradation processes have also been presented in the later part of the chapter. In this chapter, a thorough understanding of the bioremediation processes and methods applied for abatement and remediation of organic pollutants have been described in detail.
... In 1990, Percival reported a large Au anomaly in the central and southern portions of the deposit. Allchar is estimated to contain approximately 500 t of Tl, making it one of the largest Tl anomalies in the world (Janković and Jelenković, 1994;Percival and Radtke, 1994;Bačeva et al., 2014). ...
Article
The Allchar Au-As-Sb-Tl deposit is situated in the western part of the Vardar zone, the main suture zone along the contact between the Adriatic and the Eurasian tectonic plates. It is spatially and temporally associated with a Pliocene (~5 Ma) postcollisional high-K calc-alkaline to shoshonitic volcano-plutonic center. The Allchar deposit shares many distinctive features with Carlin-type gold deposits in Nevada, including its location near a terrain-bounding fault in an area of low-magnitude extension and intense magmatism. The mineralization is mostly hosted in calcareous sedimentary rocks at intersections of high-angle faults in perme-able stratigraphy. The alteration types (carbonate dissolution, silicification, and argillization), ore mineralogy (auriferous arsenian pyrite and marcasite, stibnite, realgar, orpiment, and lorandite), high Au/Ag ratios, and low base metal contents are also typical of Carlin-type gold deposits in Nevada. However, the Allchar deposit differs from Nevada Carlin-type gold deposits as follows: it is an isolated Au prospect with a close spatial and temporal relationship to a shoshonitic volcano-plutonic center in a mineral belt dominated by intrusion-related Cu-Au porphyry, skarn, and hydrothermal polymetallic deposits. The deposit is clearly zoned (proximal Au-Sb to distal As-Tl), it has a significantly higher Tl content, trace elements in pyrite and marcasite are homogeneously distributed, and synore dolomitization is a widespread alteration type.Gold mineralization is most abundant in the southern part of the deposit. It occurs mostly as invisible Au in disseminated pyrite or marcasite and as rare native Au grains. Gold mineralization is accompanied by intense decarbonatization and silicification. Fluid inclusions and the hydrothermal alteration mineral assemblage indi-cate that Au was deposited from hot (>200°C), saline (up to ~21 wt % NaCl equiv), moderately acidic (pH <5) fluids that carried traces of magmatic H2S and CO2. In the calcareous host rocks, mixing of such fluids with cool, dilute, near-neutral groundwater triggered deposition of Au and Fe sulfides. In Tertiary tuff, isocon analysis shows that sulfidation of preexisting Fe minerals was a critical factor for deposition of Au and Fe sulfides. Antimony mineralization prevails in the central part of the deposit, and it is mostly associated with dark-gray to black jasperoid. Stibnite, the most common Sb mineral in the Allchar deposit, occurs as fine-grained dissemi-nations in jasperoid and as fine- to coarsely crystalline masses that fill vugs and fracture zones lined with drusy quartz. Fluid inclusions entrapped by stibnite-bearing jasperoid, quartz, and calcite crystals suggest that stibnite was deposited from more dilute and cooled fluids (aqueous-carbonic fluid inclusions: 6.0–3.5 wt % NaCl equiv, TH = 102°–125°C; aqueous fluid inclusions: 14.5 and 17.1 wt % NaCl equiv, TH = 120°–165°C). In contrast to stibnite, As sulfides (orpiment and realgar) and Tl mineralization are associated with argillic alteration. Fluid inclusions hosted by realgar, orpiment, dolomite, and lorandite record deposition from more dilute (2.6–6.9 wt % NaCl equiv) and relatively cold fluids (TH = 120°–152°C) enriched in K. Isocon diagrams show a tight link between Tl and the low-temperature argillic alteration as well as a significant correlation between Tl and K. The spatial relationship of Tl mineralization with dolomite suggests that Tl deposition was also promoted by neutralization of acidic fluids. The dD and d18O data obtained from gangue minerals and fluid inclusions indicate that magmatic fluid mixed with exchanged meteoric water at deep levels and with unexchanged meteoric water at shallow levels in the system. The d13C and d18O values of carbonate minerals and extracted fluid inclusions suggest mixing of carbonate rock buffered fluids with magmatic and atmospheric CO2. The sulfur isotope values of early dis-seminated pyrite and marcasite show that H2S was initially derived from diagenetic pyrite in sedimentary rocks. In contrast, Sb and As mineralization indicate a strong input of magmatic H2S during the main mineralization stage. Late-stage botryoidal pyrite and marcasite are depleted in 34S, which indicates a diminishing magmatic influence and predominance of sulfur from sedimentary sources during the late-mineralization stage. Frac-tionation of isotopically light sulfide species from isotopically heavy sulfates due to oxidation under increased oxygen fugacity cannot be excluded.
Chapter
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Application of several moss species and attic dust for monitoring of anthropogenic impact on heavy metals air pollution in Bregalnica River Basin, Republic of Macedonia, was studied. Moss samples were reviewed for their potential to reflect heavy metals air pollution. The attention was focused on their quantification ability, underlying the metal accumulation within moss plant tissue and attic dust “historical archiving.” Potential “hot spots” were selected in areas of copper mine (Bučim mine) and lead and zinc mines (Zletovo mine and Sasa mine) as main metal pollution sources in the Eastern part of the Republic of Macedonia. Continuously, dust distribution from ore and flotation tailings occurs. This results with air-introduction and deposition of higher contents of certain metals. Several moss species (Hypnum cupressiforme, Homalothecium lutescens and Scleropodium purum) were used as plant sampling media. Determination of chemical elements was conducted by using both instrumental techniques: atomic emission spectrometry with inductively coupled plasma (ICP-AES) and mass spectrometry with inductively coupled plasma (ICP-MS). Combination of multivariate techniques (PCA, FA and CA) was applied for data processing and identification of elements association with lithogenic or anthropogenic origin. Spatial distribution maps were constructed for determination and localizing of narrower areas with higher contents of certain anthropogenic elements. In this way influences of selected human activities in local (small scale) air pollution can be determined. Summarized data reveal real quantification of the elements distribution not only in order determination of hazardously elements distribution, but also present complete characterization for elements deposition in mines environs.
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Moss biomonitoring technique was used for a heavy-metal pollution study in Macedonia in the framework of the International Cooperative Program on Effects of Air Pollution on Natural Vegetation and Crops (UNECE IPC Vegetation). Moss samples (n = 72) were collected during the summers of 2002, 2005, and 2010. The contents of 41 elements were determined by neutron activation analysis, atomic absorption spectrometry, and inductively coupled plasma atomic emission spectrometry. Using factor and cluster analyses, three geogenic factors were determined (Factor 1, including Al, As, Co, Cs, Fe, Hf, Na, Rb, Sc, Ta, Th, Ti, U, V, Zr, and rare-earth elements–RE; Factor 4 with Ba, K, and Sr; and Factor 5 with Br and I), one anthropogenic factor (Factor 2, including Cd, Pb, Sb, and Zn), and one geogenic-anthropogenic factor (Factor 3, including Cr and Ni). The highest anthropogenic impact of heavy metal to the air pollution in the country was from the ferronickel smelter near Kavadraci (Ni and Cr), the lead and zinc mines in the vicinity of Makedonska Kamenica, Probištip, and Kriva Palanka in the eastern part of the country (Cd, Pb, and Zn), and the former lead and zinc smelter plant in Veles. Beside the anthropogenic influences, the lithology and the composition of the soil also play an important role in the distribution of the elements.
Chapter
By the statistical processing of data and spatial distribution maps of the element contents in the moss in North Macedonia in 2015 two associations of elements were established, Cd, Pb and Zn and Co, Cr, Ni and Mo. It was found that the first group of elements have higher content in mosses from the region of the capital city of Skopje as a result of urban and industrial activities; then in the area of the town of Veles due to the soil pollution and slag landfill from the former work of the Pb and Zn smelter in the town and in the eastern part of the country, the area with higher contents of Cd, Pb and Zn in the moss samples, which is due to the emission of particles from the flotation tailings the landfills from the mine and flotation processes from the Pb-Zn mines "Zletovo" near the town of Probištip, "Sasa" near Makedonska Kamenica and "Toranica" near Kriva Palanka. The association of Ni, Cr, Co and Mo is a geogenic and anthropogenic association. Higher content of these elements are found in the central part of the country due to the increased content of these elements in the Neogene clastitic sediments and due to the pollution from the ferronickel smelter plant located near the town of Kavadarci processing ore reach with elements. If we compare the distribution maps of Ni, Cr and Co, it can be concluded that their distribution is similar, especially in the Kavadarci region where high contents of these elements occur as a result of the work of the ferronickel smelter located in the surroundings of Kavadarci.
Chapter
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The distribution of certain elements, which in higher content represents hazard to the environment, causes certain unwanted consequences on human health. Therefore, the environmental monitoring not only for the lithogenic but also for the anthropogenic distribution leads to determination of the main hot spots in environment. The anthropogenic activities for exploitation of natural resources and their processing represent a global problem of pollution of the environment. Bregalnica River Basin in the Republic of Macedonia was selected as a study area with the presence of three potential emission sources: lead and zinc mines (“Zletovo” and “Sasa” mines) and copper mine (Bučim mine). Lithogenic and anthropogenic distribution of 69 elements (Ag, As, Al, Au, B, Ba, Be, Bi, Br, Ca, Cd, Ce, Co, Cr, Cs, Cu, Dy, Er, Eu, Fe, Ga, Gd, Ge, Hf, Hg, Ho, I, In, Ir, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, Os, P, Pb, Pd, Pr, Pt, Rb, Re, Rh, Ru, Sb, Sc, Se, Sm, Sn, Sr, Ta, Tb, Te, Ti, Th, Tl, Tm, V, W, Y, Yb, Zn and Zr) was evaluated in river water, sediment and alluvial and automorphic soil from Bregalnica River Basin in the Eastern part of the Republic of Macedonia. The monitoring was conducted in the period of 2012-2013. Determination of the total elements contents was performed using mass spectrometry with inductively coupled plasma (ICP-MS) and atomic emission spectrometry with inductively coupled plasma (ICP-AES). The obtained values for the contents of certain potentially toxic elements show significantly higher values in all types of samples taken from the vicinity of the mines. The geochemical associations F1 (Ca, K, Mg, Na, Ba, Li, Mn, Sr, V); F2 (Al, Fe) and F3 (Sb), were the basic lithogenic markers for the elements distribution in river`s water, with insignificant variations. Distribution of the anthropogenic chemical association (As, W, Ba, Ag, Cu, Tl, Zn, Sb, Mo, In, Cd, Te, Bi, Pb) in the sediments, dominate in the Pb-Zn deposits (“Sasa” and “Zletovo” mines), characterized with anthropogenic impacts. Soil analysis indicates that the lithogenic distribution is represented by the following factors: F1 (Ti, Eu-Lu, Y, Fe, Sc, V, Nb, Co, La-Gd, Ga, Ge, Cu), F3 (Rb, K, W, Ba, Ta, Tl), F4 (Zr, Hf, Br, Pd, Sr, As), F5 (Ni, Cr, Mg) and F6 (B, Na). The anthropogenic distribution represents the factor F2 (Cu, Pb, Sb, Cd, Sn, Zn, Te), where the regions of mines cover 90 percentile of the contents of these elements.
Chapter
The Allchar mine, located in the southern part of the Republic of Northern Macedonia, has а unique mineral composition. This mine locality is world-famous for its thallium minerals but also known for the large amounts of minerals of arsenic and antimony. Because of the specifcity and enriched contents of these potentially toxic lements in the soil, at this site grow seven local endemic plant species: Viola allchariensis G. Beck, Viola arsenica G. Beck, Thymus alsarensis Ronn., Centaurea leucomalla Bornm., Onobrychis degenii Dörfer, Knautia caroli-rechingeri Micev., and Centaurea kavadarensis Micev. The main goal of this investigation was to establish the accumulation of some toxic elements (As, Sb, Tl) in relation to its mobility in the endemic plant species. Investigations have been initiated to deter�mine the levels of uptake and distribution of As, Sb, and Tl, as well as some other toxic elements, to the different parts of plant tissues (root, stems, leaves, fower, and seeds) of these endemic species. The plant samples were digested and then ana�lyzed, applying atomic emission spectrometry with inductively coupled plasma (ICP-AES). It was found that the accumulation of As, Sb, and Tl in these endemic species is signifcantly high. Such behavior of As, Sb, and Tl was confrmed by the extraction tests of soil samples applying various solvents.
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The aim of this study was to determine the concentrations of potentially toxic elements in soil samples and plant tissues of Minuartia recurva and M. bulgarica, predominantly or exclusively calcifuge species. Biological concentration (BCs) and translocation factors (TFs) were used to evaluate their accumulation potential. Considerable differences were observed between M. recurva and M. bulgarica assessions in terms of accumulation strategies of potentially toxic elements (PTEs). In M. recurva, most of the elements analyzed (Mn, Cu, Zn, Cd, and Co) were transported to the shoot, whereas in M. bulgarica, these elements remained predominantly in the roots. The Cu concentrations in the shoot samples of M. recurva from an abandoned iron-copper mine at Mt. Kopaonik were clearly above the notional hyperaccumulation threshold, characterizing this species as a possible Cu hyperaccumulator. Additionally, strong accumulation potential for Cr, Ni, Zn, Pb, and Cd was observed in M. recurva assessions, but without significant accumulation due to the low concentrations of these elements in the soils. The strong accumulation capacity and the different strategies in tolerance to PTEs indicate a potential of the two species for an application in phytoremediation: M. recurva for phytoextraction and M. bulgarica for phytostabilization.
Chapter
Thallium (Tl) is a typical heavy metal-bearing, extremely toxic soil pollutant. Excessive Tl can be enriched in human bodies by consuming agricultural products grown on Tl-contaminated farmland soils, leading to potentially harmful effects on human health. It is well-known that the chief anthropogenic sources of Tl are the emissions from various mining and high-temperature smelting activities of Tl-bearing minerals. In spite of the great potential threat posed by Tl from soil to food-chain migration and accumulation, limited studies have been performed on how to mitigate Tl contamination in the farmland soils. Therefore the present paper addresses the recent research progress on Tl pollution in farmland soils, focusing on its origin, modes of occurrence, and its behavior in the soil-crop system contaminated by different representative mining and smelting activities. The mechanisms of potential amendment of Tl-polluted farmland soils by using biochar-based materials have also been proposed.
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Allchar mine, located in the southern part of the Republic of Macedonia, is a unique deposit within the world, due to the variety of its mineral composition especially in the high content of arsenic and thallium. The goal of this investigation was to establish the intensity of accumulation of various elements (Ag, Al, As, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, K, Li, Mg, Mn, Mo, Na, Ni, P, Pb, Rb, S, Sb, Sr, Tl, V and Zn) with focus on As, Sb and Tl, in three endemic plant species from Allchar locality, Onobrychis degenii Dörfler, Knautia caroli-rechingeri Micev. and Centaurea kavadarensis Micev. Samples of different parts of these plants and corresponding soils were collected, prepared, digested and then analyzed by inductively coupled plasma – atomic emission spectrometry (ICP-AES). From this investigation it was found that the content of As in soil samples that were taken from the locations where the plants grow was high ranged from 102 mg/kg to 5288 mg/kg, while the content of Tl in the soil samples was also high, from 4.45 mg/kg to 409 mg/kg. In comparison to the content of As and Tl in soil samples, the content of Sb was low ranged from 8.4 mg/kg to 80.7 mg/kg. The results showed that the accumulation of As, Sb and Tl in the investigated endemic species is significant, indicating that they are able to hyperaccumulate toxic elements in their roots and shoots. Accumulation of these elements in the studied endemic species may be used as a valuable tools for bioindication, while, from the other hand, the accumulation of these toxic elements in the plants can cause high risk to the human and animal health.
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Establishing a vertical interval of mineralization is a complex geological task based on the knowledge of many parameters and quantities that describe the genesis of an ore deposit. It is particularly important to know the time and the primary depth of the formation of an ore-body and its recent position. The establishment of the vertical mineralization interval is considered in this work on the example of the Alšar Sb-As-Tl mineral deposit. The research methods used were geomorphological analysis (the principal exploration method), measurement of cosmogenic radioactive (10Be, 26Al) and stable (3He, 21Ne) nuclides to determine the erosion velocity (control method) and comparison of the obtained results with the geological exploration data from operative mine workings. A detailed geological study of the formation of the Alšar deposit preceded the research. The research data are the following: depth interval of the ore-body is 10-50 m below the present ground surface; average level of erosion in the Alšar deposit area is 20-80 m over a period of 106 years (Ma), or about 100-400 m from the beginning of the volcanic activity to the present day (≈5 Ma); thickness of the eroded rock complex over the ore bodies from the beginning of the hydrothermal alteration and the formation of ore bodies (4.31 Ma) to the present is ≥150 m (Crven dol), or ≥230 m (central deposit); the palaeointerval of the formation of the ore-body is 230 m (200-430 m); and, finally, the potentially mineralized interval is deep, from 10 m to 280 m below the surface.
Article
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Referee: Professor Alan J.M. Baker, School of Botany, The University of Melbourne, VIC 3010, Australia A relatively small yet diverse group of plants are capable of sequestering metals in their shoot tissues at remarkably high concentrations that would be toxic to most organisms. This process, known as metal hyperaccumulation, is of interest for several reasons, including its relevance to the phytoremediation of metalpolluted soils. Most research on hyperaccumulators has focused on the physiological mechanisms of metal uptake, transport, and sequestration, but relatively little is known regarding the genetic basis of hyperaccumulation. There are no known cases of major genetic polymorphisms in which some members of a species are capable of hyperaccumulation and others are not. This is in contrast to the related phenomenon of metal tolerance, in which most species that possess any metal tolerance are polymorphic, evolving tolerance only in local populations on metalliferous soil. However, although some degree of hyperaccumulation occurs in all members of the species that can hyperaccumulate, there is evidence of quantitative genetic variation in ability to hyperaccumulate, both between and within populations. Such variation does not appear to correlate positively with either the metal concentration in the soil or the degree of metal tolerance in the plant. Studies using controlled crosses, interspecific hybrids, and molecular markers are beginning to shed light on the genetic control of this variation. As molecular physiology provides greater insights into the specific genes that control metal accumulation, we may learn more about the genetic and regulatory factors that influence variable expression of the hyperaccumulation phenotype.
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Viola calaminaria (Gingins) Lej. is a rare and threatened species, endemic to metalliferous soils in E Belgium, S Netherlands and W Germany. In order to provide basic information for a conservation strategy, we performed an ecogeographic survey of almost all V. calaminaria populations currently existing in Belgium. Twenty-four populations were found, distributed in three geographic groups all in the Province of Liège. The area covered by V. calaminaria ranged from < 1 m2 to 3.2 ha. The largest populations were found in sites contaminated by atmospheric deposits from metal smelters. Soils were extremely variable in heavy metal and nutrient concentrations, but concentrations of Zn, Pb and Cd were consistently higher than reference values for normal soils. V. calaminaria was most often found in association with other metallophyte and pseudometallophyte taxa typical of metalliferous sites. Plant communities identified by TWINSPAN analysis generally fitted the heavy metal associations previously described but two unusual heavy metal plant communities were identified. Based on a canonical correspondence analysis, pH was the only factor that was clearly correlated with the floristic composition of plant communities associated to V. calaminaria. This study confirmed the ecological endemic status of V. calaminaria and the importance of the conservation of metalliferous sites.
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Commentary In search of the Holy Grail – a further step in understanding metal hyperaccumulation? Hyperaccumulation of heavy metal ions is a striking phenomenon exhibited by < 0.2% of angiosperms. These hyperaccumulator plants are considered endemic to metalliferous substrates, and are characterized by their tolerance and sequestration of exceptional quantities of metals like Zn, Ni and Cd in their shoots at concentrations that would be toxic to 'normal' plants. The last decade has seen an exponentially increasing interest in the phenomenon of metal hyperaccumulation since the property has been proposed as harnessable in the emerging technology of phytoextraction, both in terms of clean-up of contaminated land and phytomining otherwise noneconomic mineral deposits. Most recently, there has been a plethora of papers attempting to dissect the mechanisms of metal uptake, transport and accumulation, both at the physiological and molecular level, largely in the 'model' plant Thlaspi caerulescens and its close relatives. In this relentless race to identify the genes responsible, certain important issues have largely been cast to one side – notably, plant performance under natural field conditions and the need for more conventional genetic analysis of the hyperaccumulator trait for phytoextraction to become a commercial reality rather than the justification for even more sophisticated experimentation.
Article
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Two endemic zinc violets of the section Melanium Ging. occur on heavy metal soils of Central Europe. The form with yellow flowers is restricted to the area between Aachen, Germany, and Liège, Belgium, whereas the blue zinc violet exclusively thrives on a very small location at Blankenrode, Germany. Both violets are currently treated as separate species. Sequences of altogether 674 bp of the ITS1-5.8S rDNA-ITS2 regions of 61 different specimens of six taxa indicated that both violets are closely related to each other and also to Viola lutea Huds. Therefore these two zinc violets are, at best, subspecies or even only varieties of V. lutea. Thus they are termed V. lutea ssp. westfalica and V. lutea ssp. calaminaria in the present manuscript. Microsporogenesis, pollen morphology and viability of the zinc violets, particularly of the blue violet of Blankenrode, are often defective due to disturbed meiosis. The population of the blue violet might not yet be stabilized genetically but can cope with the adverse effects of the heavy metal elements.
Article
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The results of tectono-metallogenic, geological-structural, mineralogical, isotopic, and hermobarogeochemical studies at the Alshar deposit and in the adjacent area are discussed. The data obtained show that the gold mineralization at the deposit is similar to that observed at the Carlin-type deposits in the western United States. Similar characteristics include the Au-As-Sb-Tl-Hg geochemical assemblage; low Pb, Zn, Cu, and Ag contents in ore; widespread jasperoid and argillic metasomatic alterations of host siliciclastic-carbonate sedimentary rocks; and the spatial relations to fault zones. At the same time, the Alshar deposit differs from the Carlin-type deposits by the following features: (1) Pliocene age of mineralization, (2) expansion of mineralization over younger volcanics, (3) a high Tl grade in ore, and (4) localization of the ore field in a long-lived central-type magmatic structure. The results obtained can be used as an exploration model.
Article
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 In order to ensure quality assurance in large-scale environmental contamination studies involving many different analytical laboratories, the use of calibrated reference materials is essential. Prior to a survey of atmospheric metal deposition in 1995 comprising 20 countries and covering large parts of Europe, the lack of suitable reference materials of moss and organic-rich soil was apparent. In order to improve the quality of analytical data to be produced in this international survey, candidate analytical laboratories were invited to participate in an intercomparison exercise. Three moss and three soil humus reference samples specifically prepared for this purpose were distributed anonymously among the laboratories, which were asked to report data for ten priority elements (V, Cr, Fe, Ni, Cu, Zn, As, Cd, Hg, Pb) and as many additional elements as they determined normally. In this paper the analytical data from the intercomparison are evaluated, and recommended values for the ten priority elements and 17 additional elements (B, Na, Mg, Al, S, K, Ca, Mn, Co, Se, Rb, Sr, Sb, Cs, Ba, La, Th) in each of the six reference samples are established. These samples should be useful for similar future studies including areas where the contamination levels are very low.
Article
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Arsenic contents of soils and higher plants were surveyed in two former Sb-mining areas and in an old quarry once used for ochre extraction. Total As in the soils ranged from 5.3 to 2035.3 mg kg−1, soluble and extractable As from 0.01 to 8.5 and from 0.04 to 35.8 mg kg−1, respectively. The As concentrations in the different fractions of soil were correlated significantly or very significantly. Sixty-four plant species were analyzed. The highest As contents were found in roots and leaves of Mentha aquatica (540 and 216 mg kg−1, respectively) and in roots of Phragmites australis (688 mg kg−1). In general, the As contents of plants were low, especially in crops and in the most common wild species. In the analyzed species, roots usually showed the highest content followed by leaves and shoots. Arsenic levels in soils and plants were positively correlated, while the ability of the plants to accumulate the element (expressed by their Biological Accumulation Coefficients and Concentration Factors) was independent of the soil As content. Comparison with the literature data, relationships between the As contents in plants and soils, and biogeochemical and environmental aspects of these results are discussed.
Chapter
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The Allchar Sb-As-Tl-Au volcanogenic hydrothermal deposit is situated at the northwestern margins of Kožuf Mts. (Republic of Macedonia), close to the border between Republic of Macedonia and Greece (Fig.1). From the geotectonic point of view, ore mineralization is related to a Pliocene volcano-intrusive complex located between the rigid Pellagonian block in the west, and the labile Vardar zone in the east. From the metallogenic point of view, the Allchar deposit belongs to the Kožuf ore district as part of the Serbo-Macedonian metallogenetic province.
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The aim of this study was to assess thallium (Tl) uptake into the aerial parts of selected crop species grown on French soils with high Tl content of pedogeochemical origin (0.3-40 mg Tl kg(-1) on a dry wt (DW) basis). Husked wheat and maize grains contained less than 4 microg Tl kg(-1) DW, but rape shoots accumulated Tl with a shoot-soil partition coefficient (PC) > 1, and rape seeds had PC > 3. Tl content of rape seed reached 33 mg Tl kg(-1) DW and higher concentrations in soil corresponded to increased concentrations in rape seeds. It is argued that parent material of the soil and pedogenesis have a considerable effect on Tl accumulation in rape seeds. These results show enhanced phytoavailability of Tl of pedogeochemical origin and prompt questions on the potential for food chain contamination by Tl in rape cattle cakes.
Article
Two endemic zinc violets of the section Melanium Ging. occur on heavy metal soils of Central Europe. The form with yellow flowers is restricted to the area between Aachen, Germany, and Liège, Belgium, whereas the blue zinc violet exclusively thrives on a very small location at Blankenrode, Germany. Both violets are currently treated as separate species. Sequences of altogether 674 bp of the ITS1-5.8S rDNA-ITS2 regions of 61 different specimens of six taxa indicated that both violets are closely related to each other and also to Viola lutea Huds. Therefore these two zinc violets are, at best, subspecies or even only varieties of V. lutea. Thus they are termed V. lutea ssp. westfalica and V. lutea ssp. calaminaria in the present manuscript. Microsporogenesis, pollen morphology and viability of the zinc violets, particularly of the blue violet of Blankenrode, are often defective due to disturbed meiosis. The population of the blue violet might not yet be stabilized genetically but can cope with the adverse effects of the heavy metal elements.
Book
The Group 12 consists of zinc (Zn), cadmium (Cd), and mercury (Hg). These metals have quite a low abundance in the Earth’s crust. These metals form compounds in which their oxidation states are usually not higher than +2 and easily form metal-metal (+M-M+) bonds (Table II-12.1). The strength of the bond increases down the group, in the following order: Hg < Cd < Zn. The Zn 2 2+ and Cd 2 2+ ions are highly unstable, however, the +1 state of Hg is quite stable compared with the other two elements. The toxicity of Cd and Hg is well known, whereas Zn has enormous biological importance.
Article
The uptake and distribution of arsenic (As) and some heavy metals was determined in three Viola endemic species from As‐overloaded soil in an abandoned mine at Alchar, Republic of Macedonia (FYROM – The Former Yugoslav Republic of Macedonia). Some essential elements were also analyzed in order to characterize the common geochemical properties of this site. Total As content in soil ranged from 3347 to 14,467 mg kg−1, and plant available As from 23 to 1589 mg kg−1. The concentration of As in roots ranged from 783 mg kg−1 in Viola macedonica to 2124 mg kg−1 in Viola arsenica. Only a small amount of As accumulated in the aboveground parts of these species (<100 mg kg−1), while in shoots of Viola allchariensis, As accumulated in the range 187–439 mg kg−1. Arsenic accumulation in the roots of these Viola species may make these plants valuable tools for the bioindication and phytoremediation (phytostabilization) of As in naturally loaded and anthropogenically contaminated soils.
Article
The paper is a summary of investigationis carried out on minerals of the Allchar deposit. It discusses the TI-As-Sb-Au mineral assemblage after detailed and intense research work. Four types of mineralization have been distinguished based on the mineral assemblage present: I. The first lype is characterised by high c ment of iron and sulphur, but lower arsenic and thalli um contenl. The pyrite-marcasite mineral assemblage is characterized by the presence of some quantities of arsenic-pyrite. 2. The second type is characterized by the high antimony and low iron and thallium content. Stibnite is the most common mineral in the group. 3. The third type is characterized by the high arsenic and sulphur and relatively low thallium content. Orpiment is the most common mineral in this group. 4. The fourth type of minerals is characterized by the high content of arsenic, sulphur. iron and thallium. This type of minerals is accompanied by the high content of manganese and zinc.
Article
The concentration of thallium was determined in samples from the Allchar deposit by flame and flameless atomic absorption spectrometry . Interferences of various elements were investigated . A concentration of 10-2000 ppm was found in samples from Allchar ore.
Chapter
IntroductionCobalt and CopperNickelZincConclusion
Article
Arsenic absorption by rice (Oryza sativa, L.) in relation to the chemical form and concentration of arsenic added in nutrient solution was examined. A 4 3 2 factorial experiment was conducted with treatments consisting of four arsenic chemical forms [arsenite, As(III); arsenate, As(V); monomethyl arsenic acid, MMAA; and dimethyl arsenic acid, DMAA], three arsenic concentrations [0.05, 0.2, and 0.8 mg As L-1], and two cultivars [Lemont and Mercury] with a different degree of susceptibility to straighthead, a physiological disease attributed to arsenic toxicity. Two controls, one for each cultivar, were also included. Arsenic phytoavailability and phytotoxicity are determined primarily by the arsenic chemical form present. Application of DMAA increased total dry matter production. While application of As(V) did not affect plant growth, both As(III) and MMAA were phytotoxic to rice. Availability of arsenic to rice followed the trend: DMAA<As(V)<MMAA<As(III). Upon absorption, DMAA was readily translocated to the shoot. Arsenic(III), As(V), and MMAA accumulated in the roots. With increased arsenic application rates the arsenic shoot/root concentration decreased for the As(III) and As(V) treatments. Monomethyl arsenic acid (MMAA), however, was translocated to the shoot upon increased application. The observed differential absorption and translocation of arsenic chemical forms by rice is possibly responsible for the straighthead disorder attributed to arsenic.
Chapter
This handbook is a reference guide for selecting and carrying out numerous methods of soil analysis. It is written in accordance with analytical standards and quality control approaches. It covers a large body of technical information including protocols, tables, formulae, spectrum models, chromatograms and additional analytical diagrams. The approaches are diverse, from the simplest tests to the most sophisticated determination methods in the physical chemistry of mineralogical and organic structures, available and total elements, soil exchange complex, pesticides and contaminants, trace elements and isotopes.As a basic reference, it will be particularly useful to scientists, engineers, technicians, professors and students, in the areas of soil science, agronomy, earth and environmental sciences. It is also relevant to those in related fields such as analytical chemistry, geology, hydrology, ecology, climatology, civil engineering and industrial activities associated with soil.
Article
The technique of phytomining involves growing a crop of a metal-hyperaccumulating plant species, harvesting the biomass and burning it to produce a bio-ore. The first phytomining experiments were carried out in California using the Ni-hyperaccumulator Streptanthus polygaloides and it was found that a yield of 100 kg/ha of sulphur-free Ni could be produced. We have used the same technique to test the phytomining potential of the Ni-hyperaccumulators Alyssum bertolonii from Italy and Berkheya coddii from South Africa. The effect of different fertiliser treatments on growth of Alyssum bertolonii was established in situ in Tuscany and showed that the biomass of the plant could be increased by a factor of nearly 3 (4.5 t/ha to 12 t/ha) without significant loss of the Ni concentration (7600 mg/kg) in the plant. Analogous experiments have been carried out on Berkheya coddii where a biomass yield of over 20 t/ha can readily be achieved though the Ni concentration is not as high as in A. bertolonii. The total yield is, however, much greater. We have also been able to induce plants to hyperaccumulate Au by adding ammonium thiocyanate to the substrate. Up to 57 mg/kg Au (dry mass) could be accumulated by Indian mustard (Brassica juncea). Unusual hyperaccumulation (>500 mg/kg dry mass) of Tl has been determined in Iberis intermedia and Biscutella laevigata (Brassicaceae) from southern France. The Iberis contained up to 0.4% Tl (4000 mg/kg) in the whole-plant dry matter and the Biscutella over 1.5%. This unusually high accumulation of Tl has significance for animal and human health, phytoremediation of contaminated soils, and phytomining for Tl. We calculate that using Iberis, a net return of $ US 1200/ha (twice the return from a crop of wheat) would be possible with a biomass yield of 10 t/ha containing 0.08% Tl in dry matter. The break-even point (net yield of $ US 500/ha) would require 170 mg/kg (0.017%) Tl in dry matter. A model of a phytomining operation and its economics is presented and its advantages and disadvantages discussed.
Article
Thallium (TI) is a metal of great toxicological concern and its prevalence in the natural environment has steadily increased as a result of manufacturing and combustion practices. Due to its low natural abundance and increasing demand, TI is the fourth most expensive metal, thus, recovery and reuse could be a profitable endeavor. The hyperaccumulator Iberis intermedia was examined via in vivo micro-X-ray absorption near edge (micro-XANES) and micro-X-ray fluorescence (micro-XRF) spectroscopies to determine the speciation and distribution of TI within leaves of the plant. I. intermedia plants were cultivated under controlled conditions in 0, 10, and 20 mg TI kg(-1) soil leading to a shoot concentration of up to 13 430 mg TI kg(-1) dry weight plant mass during 10 weeks of growth. Live plant leaves were examined by micro-XANES and micro-XRF which determined aqueous TI(I) to be the model species distributed primarily throughout the vascular network. A direct relationship of vein size to TI concentration was observed. The high uptake of TI and high potential biomass of I. intermedia, combined with knowledge of TI speciation and compartmentation within the plant, are discussed in terms of accumulation/tolerance mechanisms, consequences for potential food chain contamination, and phytomining strategies to reclaim TI-contaminated soils, sediments, and waters.
Article
The main aim of the study was to determine the role of calcium in the amelioration of lead toxic effects in plants with accordingly high/low level of Pb-tolerance and high/low Ca-deficiency tolerance. The study was performed on maize, rye, tomato and mustard. Plants were cultivated in modified Knop's solution. They were subjected to Ca-deficiency, and to lead nitrate administered in the presence of four calcium nitrate concentrations 3.0, 2.4, 1.2, 0.3mM. Lead-tolerance and tolerance to Ca-deficiency were determined, as were concentration of the studied elements in plant tissues, and the Pb deposition pattern at the ultrastructural level (electron microscopy study, X-ray microanalysis). In all studied plants, lead toxicity increased as medium calcium content decreased, however, only in the Ca-deficiency sensitive mustard with low Pb-tolerance was it accompanied by a rise in tissue lead concentration. In contrast, lead root and shoot levels did not increase in the highly Ca-deficiency tolerant tomato, mustard and rye with high Pb-tolerance irrespective of the Ca(2+) regimens applied. Thus, in these plants, lead's unfavourable effects resulted only from the higher toxicity of the same amount of lead in tissues at low calcium in the medium. Of particular relevance is the finding by electron microscopy and X-ray microanalysis, that under low calcium in both highly Ca-deficiency tolerant and Ca-deficiency sensitive plants, less efficient Pb(2+) detoxification was accompanied by the restriction of the formation of large lead deposits in cell walls. Obtained results are novel in demonstrating calcium involvement in the lead deposition in the cell wall, thus in the regulation of the internal lead detoxification.
Article
Untreated abandoned mines may result in hazards to ecosystems due to dispersion of various toxic elements such as arsenic (As) and lead (Pb). Phytoremediation is an alternative of remediation for large scale mine dumps. Plant species were sampled from two abandoned gold (Au) mines in South Korea. Plant samples were digested following the guidelines of US EPA Method 3050 (US-EPA, 1996) and analyzed by inductively coupled plasma mass spectrometry (ICP-MS). Concentrations and bioaccumulation factors of plants are reported and out-performing species are summarized. Poplar trees (Populus davidiana) growing on the Myoungbong tailings were suggested to be a potential species for revegetation of large scale Au mine tailings. Arsenic accumulations of bracken ferns (Pteridium aquilinum) sampled from the Duckum tailings were far lower than those of the reported hyperaccumulators, but the possible chronic adverse effects on residents through daily diet are of concern.
Article
Thallium is a scarce, highly toxic element. There are several investigations that report Tl accumulation in plants of the family Brassicaceae. These plants could pose a risk in areas where Tl is present at higher concentrations than normal soils. The present study reports analyses of two wild Brassicaceae, Hirschfeldia incana and Diplotaxis catholica, growing spontaneously at five sampling sites moderately polluted with Tl and other trace elements in the Green Corridor of the Guadiamar river, Seville, S. Spain. In general, trace element content was unremarkable in all part plants, despite the concentrations present in soil. Thallium was the only element whose concentration in both plant species was above normal for plants (maximum values of 5.00 mgkg(-1) in H. incana flowers). There were significant positive correlations between total Tl in soil and Tl in both plant species. Transfer Coefficients (TC) for all elements were, in general, <1 for both species, except for Tl in flowers and fruits at some sites. The highest Enrichment Factor (EF) was found for Tl in H. incana fruits (EF = 607) and D. catholica flowers (EF = 321). H. incana was studied in a previous growing season (2004) in the same area, although the rainfall was 3 times more than in the year of the present study (2005), giving a maximum Tl content of 46.5 mgkg(-1) in H. incana flowers. The data presented here show that Tl content of plants growing in semi-arid conditions can be significantly influenced by precipitation. In dry years, plant Tl accumulation may be significantly reduced.
Article
The cellular distributions of Pb and As in the leaves of co-hyperaccumulator Viola principis H. de Boiss. were inspected by synchrotron X-ray fluorescence spectroscopy (SRXRF). The results revealed that Pb and As had similar compartmentalization patterns in the leaves. Both elements were enriched in the bundle sheath and the palisade mesophyll. In comparison with the sheath and the mesophyll, the vascular bundle and the epidermis contained lower levels of Pb and As. The palisade enrichment of Pb and As indicated that V. principis H. de Boiss. may have a special mechanism on detoxification of toxic metals within the mesophyll cells. Relative concentrations of both Pb and As in trichome bases were higher than those in trichome rays. The results of hierarchical cluster analysis and correlation analysis confirmed that the distribution of Pb was similar to that of As in the leaves, and their distribution patterns were different from the nutrient elements, such as K, Ca, Mn, Fe, Ni, Cu and Zn. In vivo cellular localization of Pb and As in the leaves provides insight into the physiological mechanisms of metal tolerance and hyperaccumulation in the hyperaccumulators.
Concentration of As and heavy metals in vegetation at two abandoned mine tailings in South Korea
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