Physical and chemical characteristics of slag produced during Pb refining and the environmental risk associated with the storage of slag.

Metallurgical waste originating from the Zn and Pb refining process presents varying chemical composition and physical properties and contains varying quantities of pollutants. In the study, both fresh and weathered samples of production slag from the final Pb refining process were used to determine its physical parameters and chemical composition as well as to perform an environmental risk assessment (RAC, mRAC) related to its storage. This paper focuses on determining parameters such as natural humidity (1.8%) and bulk density (1267 kg/m3) of the slag. Also, its toxicity was analysed using bio-tests, its pH was measured (11.92) and the content of sulphates (3.5 wt%), chlorides (0.3 wt%) and selected heavy metals (Cd, Cu, Fe, Mn, Zn, Pb) was determined. The Individual Contamination Factor was determined, yielding the following order of the hazard level: Pb > Cu > Zn > Cd > Fe > Mn. Based on the mobility of metals determined using the Mobility Factor, it was concluded that the hazard level followed the sequence Cd > Pb > Zn > Mn > Fe > Cu. The obtained water leaching results were compared to the values found in the legal regulations in force. Based on this comparison, it was established that the slag studied constitutes toxic waste containing considerable quantities of sulphides and chlorides. The material is also a considerable source of readily leaching elements (Cd, Zn and Pb), and thus any product created using the slag may become hazardous to the environment. Also, the waste studied must not be used in the form in which it is currently stored due to the leaching of particularly toxic elements (Cd and Pb) in water solutions with increasing acidity.

Micro- and macroelement contents in the liver of farm and wild animals and the health risks involved in liver consumption.

The paper presents the macroelement (Al, Ca, Cu, Fe, K, Mg, Mn, Na, P, and Zn) and microelement (As, Cd, Co, Cr, Hg, Mo, Ni, Pb, and Sn) contents found in the liver of wild animals (boar and deer) and farm animals (rabbit, chicken, duck, cow, goat, and turkey). Statistically, the differences in element contents between the two groups were not significant (at p = 0.05), with the exception of Fe, K, Mg, Cd, Hg, Mo, and Pb. The liver of farm animals contained more Al, Cu, K, Mg, Na, Cr, and Sn, while the content of the remaining elements was higher in wild animals. An analysis of correlations between element content and age in wild animals (boar) showed that Pb and Al content increases with age, while Na and Cr contents decrease significantly. Comparisons between the test results and the maximum limits allowed by law showed that, in the case of wild animals, the regulatory limits were exceeded in 18% (for Cd and Cu) and 9% (for Hg) of the liver samples analyzed. In the case of farm animals, the limits for micro- and macroelement contents were not exceeded. The hazard index (HI) values for farm animals were lower than for wild animals, with regard to consumption by both children and adults. Based on the HI values calculated, it seems recommendable that consumption of the liver (preferably from farm animals) by children be limited to once weekly. For adults, the liver can be a valuable source of elements such as Zn, Fe, and Cr, which may be an indication for more frequent consumption.

Evaluating Potential for Using Municipal Sewage Sludge in the Rehabilitation of Ground Degraded by the Sodium Processing Industry.

The paper attempts at evaluating potential for the use of sewage sludge produced in a rural area for the rehabilitation of ground degraded by the sodium processing industry. The results demonstrated that the studied sewage sludge conforms to the current regulatory standards, enabling its use in land rehabilitation, both for agricultural and non-agricultural purposes. Ground in areas degraded by the KZS "Solvay" industrial plant has poor parameters in terms of pH, and moderate parameters in terms of humic substance content. An experiment using the bearded iris (Iris barbata) demonstrated that sewage sludge from the "Stróze" treatment plant stimulates plant growth. Therefore, it can be used both for ground rehabilitation, and for fertilization. Considering its properties and its broad spectrum of potential uses, sewage sludge should be viewed as a resource rather than a waste product.

Metals and mineral phases of dusts collected in different urban parks of Krakow and their impact on the health of city residents.

The authors present the results of chemical and mineralogical analyses of urban dusts collected in the spring seasons of 2015 and 2016 in three different parks of the Cracow agglomeration. The parks are located in the city centre, in the Nowa Huta industrial district and in a new housing development situated around 9 km west of the city centre. Mineralogical instrumental analyses included the SEM, FTIR and XRD methods and revealed that the dusts of Cracow are highly amorphous and contain significant amounts of hydrocarbons, whereas quartz, feldspars, kaolinite and gypsum are their crystalline phases. Chemical analyses were carried out using the ICP-MS method on aqua regia extracts of the starting samples. The contents of selected toxic elements are: As 5-123; Cd 1-14; Pb 56-258; Zn 486-1891 mg/kg and Fe 0.74-4.02 wt%. The health risk of these elements imposed on the residents of Cracow frequently visiting the three urban parks was assessed on the basis of the health quotient index HQ. At its values exceeding 1, adverse health effects are probable in humans. The HQ values calculated for As and Tl contained in the Cracow Park dusts in the case of adults are 3.42E-01 and 3.00E-01, respectively. They are significantly higher (one order of magnitude) in the case of children 3.19E+00 and 2.27E+00, respectively.

Long-term changes of metal contents in two metallophyte species (Olkusz area of Zn-Pb ores, Poland).

The authors present the changes of the As, Cd, Fe, Mn, Pb and Zn contents in two plant-considered metallophytes: common bent Agrostis capillaris (blades) and birch Betula pendula (leaves and seeds), recorded in a Zn-Pb industrial region of Olkusz (Poland) in 1994 and 2014. The highest amounts of Cd (12 ppm) and Zn (2524 ppm) in the common bent occur in the vicinity of the mining and metallurgical works 'Boleslaw' in Bukowno. However, these values are significantly lower than those in 1994: Cd by 87 % and Zn by 52 %. The highest contents of Fe (2674 ppm), Mn (130 ppm) and Pb (334 ppm) in this grass species are in the vicinity of the closed Olkusz mine. These contents have increased in comparison with the 1994 figures: Fe by 56 %, Mn by 120 % and Pb by 6 %. In the birch leaves, the metal contents averaged for four sites are the following: As 2.1, Cd 6.5, Fe 261, Mn 110, Pb 70 and Zn 1657 ppm, being lower from the figures in 1994. The highest As, Fe and Pb contents of birch leaves occur in the habitat closest to the former Olkusz mine, while those of Cd, Mn and Zn in the habitat distant at 100 m from the active plant in Bukowno. The common bent grass generates better resistance mechanisms against the metals than does the birch. In the birch leaves, the contents of the metals are significantly lower than those of the grass blades, but higher from those of the birch seeds collected from the same tree individuals. It is a proof of good functioning of the mechanisms preventing excessive metal amounts from the cell metabolism and of the presence of physiological barriers protecting birch seeds as the generative organs.

Anthropogenic impact on soils of protected areas-example of PAHs.

The following study presents the concentrations of 10 individual polycyclic aromatic hydrocarbons (PAHs10) and the total concentration of PAHs (ΣPAHs) determined in soils of protected areas in Southern Poland (EU). The protected areas discussed here include 5 landscape parks and 5 nature reserves located in the Malopolska region. Surface soil samples were collected at 39 locations characterised by different natural conditions and different human pressure level. The samples were used to determine the contents of anthracene, benzo[a]pyrene, benz[a]anthracene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[g,h,i]perylene, chrysene, dibenz[a,h]anthracene, indeno[1,2,3-cd]pyrene and naphthalene. These concentrations of individual PAHs ranged from < 0.005 to 6.34 mg/kg. When considering the legal regulations currently in force, this meant that permissible values were exceeded in 23% of the samples analysed, while increased concentrations were found in another 26% of the samples. The limit values were exceeded most in the case of benzo[b]fluoranthene and benzo[a]pyrene. This occurred with samples collected in the vicinity of transportation routes, mainly local roads. In the case of naphthalene and anthracene, the limit values were not exceeded. Increased or excessive PAHs concentrations do not occur in the vicinity of major industrial plants located near the boundaries of individual landscape parks, which indicates how these pollutants spread. The paper also points to the need to develop new legal solutions to improve the method for assessing PAHs concentrations and their impact on valuable natural areas.

Incongruent dissolution of silicates and its impact on the environment: an example of a talc mine.

The paper analyzes the process of incongruent dissolution of silicates taking place in close proximity to a talc mine. The chemical and phase composition as well as the concentrations and mobility of potentially toxic elements (PTE) in research material with varying levels of weathering were determined using instrumental (XRF, XRD) and chemical methods (extractions: BCR, aqua regia, water leaching, 0.05 M EDTA). It was demonstrated that the predominant minerals in the weathering crust include weathering-resistant minerals (i.e. quartz and muscovite) and secondary minerals (kaolinite, illite and interstratified minerals, vermiculite/chlorite) and that the predominant processes are hydrolysis and oxidation. The weathering process has an impact on the complexity of the chemical and mineral composition and the diverse structure of the weathering crust. A layer of Fe and Al oxides and hydroxides forms in the upper part of the weathering crust, while the amount of silica decreases. Low-mobility elements (i.e. Si, Al and Fe) react on the phase separation surface, causing the formation of clay minerals (i.e. vermiculite, montmorillonite) or Al and Fe hydroxides (e.g. goethite). The duration of weathering causes an increase in the content of PTEs in solid materials: multifold in the case of Cr (15), Ba (9), Pb (7), Zn (6) and considerably lower in the case of V (1.3), Sr (0.8) and Co (0.4). It was demonstrated that PTEs co-occur in several chemical fractions in the weathering crust and that the highest share of their total concentration are cations incorporated in the crystal lattice of minerals and bound by strong crystalline bonds (F4 46%). The lowest share was observed for the reducible fraction (9%) and the share of the oxidizable fraction was 29% The most mobile cations connected by the weakest bonds comprised only 16% of the total concentration. Based on the content of the readily soluble fraction of PTEs, it was concluded that the degree of weathering does not increase the environmental risk, but actually reduces it for Cr, Cr and Pb. The obtained Ecological Risk Index (ERI) values indicate that the ecological risk associated with the elements tested is low for the entire area, which means that natural weathering processes do not have any impact on environmental pollution.

Ecological Risk Assessment Related to the Presence and Toxicity of Potentially Toxic Elements in Ashes from Household Furnaces.

The study material was comprised of 23 samples of ashes generated after the combustion of conventional and alternative fuels combined with selected fractions of municipal waste. The analyses performed involved determining the total concentration of As, Al, Cr, Fe, Ni, and their bioaccessible, ion-exchange, and carbonate-bound fractions. It was found that all of the samples analysed may display an elevated level of susceptibility to the reduction processes, which undoubtedly increases the mobility of trace elements, including the toxic ones. The predominant elements were Al and Fe, whereas considerably lower concentrations were observed for Ni, Cr, and As. The percentage share of the ion-exchange and carbonate-bound fraction ranged from 49% of the total concentration for As to as much as 0.35% in the case of Fe. The calculated Risk Assessment Code index points to a high risk related to the presence of As, medium to low risk related to the presence of Ni and Cr, and low to no risk related to the presence of Fe and Al. The calculated values of the Ecological Risk Index, associated with the combustion of selected municipal waste fractions and low-quality hard coals, combusted individually or in combination with different types of wood, point to a very high ecological risk. This is mainly related to the high concentrations and toxicity of As.

The effect of fertilizing soils degraded by the metallurgical industry on the content of elements in Lactuca sativa L.

The aim of the study was to determine the content of macroelements (Ca, K, P, S, Mg) and microelements (Fe, Cr, Ni, Mn, Zn, Pb, Zn, Ti) in the leaves of Lactuca sativa grown in soils contaminated by the mining and metallurgical industry. The plants were cultivated using four fertilization variants: (a) unfertilized soil, (b) mix of straight fertilizers, (c) multinutrient fertilizer and (d) organic fertilizer, namely granular cattle manure. The study also involved an analysis of metal accumulation degree in the edible parts of lettuce by means of calculating a bioaccumulation index-transfer factor (TF). The analysis of the impact of fertilization on the content of the elements in the edible parts of fertilized versus unfertilized lettuce demonstrated that phytoavailability of the metals was most effectively limited by the multinutrient fertilizer and the mix of straight fertilizers. The organic fertilizer proved to be the least effective. The highest TF values (> 0.1) were recorded for macroelements, which denotes their intense and moderate accumulation. Poor bioaccumulation was observed for Cr, Mn, Ni and Zn (0.01 ≤ TF < 0.1), whereas in the case of Fe, Pb and Ti-trace bioaccumulation or no bioaccumulation was found (TF ≤ 0.01).

Chemical and mineral composition of fly ashes from home furnaces, and health and environmental risk related to their presence in the environment.

The study presents the results of an analysis of fly ashes produced from burning of solid fuels mixed with municipal waste and assesses the environmental and health risk associated with infiltration of the selected metals to the environment. The phase composition suggests that the material is extremely mixed and diverse. Low-temperature components were mixed with substances formed in high temperatures. The variable composition of waste from different home furnaces with high content of the amorphous phase (which dissolves in water more easily than its crystalline equivalents) may be harmful to the environment and for the people. The dominant elements were silicates and aluminosilicates, such as: quartz, feldspar and plagioclase (albite). Clay minerals (kaolinite and mullite), carbonates (calcite), oxides/oxidehydroxides of iron and sulfate minerals (gypsum and anhydrite) were also abundant. The particles' major constituents were Si, Al, Ca and Fe oxides (85.5%), while S, Mg, Na, K and Ti oxides accounted for 12.6% of the total content. The risk assessment code suggested: Low Risk for As, Co, Cr, Ni, Medium Risk for Cd, Cu and Pb, and High Risk for Zn. Hazard Index (HI) calculated for non-cancerogenic substances for children was 2.35E+00. The total Risk index for children was 4.88E-05. As for adults, HI was 2.42E-01 for women, and 2.89E-01 for men, while the Risk index value was 6.85E-05 for women, and 8.48E-05 for men. The value HI > 1 points to the risk of adverse health impact on children exposed to fly ashes.

Environmental risk related to presence and mobility of As, Cd and Tl in soils in the vicinity of a metallurgical plant - Long-term observations.

Analysis of the content of As, Cd and Tl accompanying Zn-Pb ores was performed using soil material sampled around the zinc-works in Miasteczko Slaskie. It was found that the total content of As, Cd and Tl was considerably higher than the values recorded at the same sites 20 years earlier. This clearly confirms considerable pollution of the environment which continues despite pro-ecological actions taken by the zinc-works. The analysis of the spatial distribution of pollution revealed that the zinc-works itself is no longer the main source of contamination as was the case in 1998. Instead, in 2018 the main sources of As, Cd and Tl emissions were the erosion and deflation processes in old, unprotected mining and industrial waste dumps located near the zinc-works. The most polluted soil layers are the top layers in the soil profile. The content of As, Cd and Tl determined in them was 10 times greater than in the deep layers. There was also a positive change in environmental conditions, which occurred over the preceding 20 years, namely an increase in the content of sparingly soluble fractions, fractions bound with organic matter, and residual fractions. It was also found that depending on the geochemical background and readily mobile fraction values used in the calculations, there is still very high contamination and very high ecological risk with respect to As, Cd and Tl after 20 years. However, when using the quantity of phytoavailable elements as well as the quantity of cations on ion exchange positions and bound to carbonates to calculate the risk assessment code, the analysis showed that environmental conditions improved.

Heavy metals in sands of sandboxes: health risk associated with their quantities and form of occurrence in some spas of Poland.

The authors dealt with some hazardous elements, i.e. As, Cd, Co, Cr, Cu, Ni, Pb and Zn, contained in sands of the sandboxes localized in playgrounds of seven spas in southern Poland (CEE). The following determinations were made: the total contents of metals, the most mobile metals (water-leachable fraction) and the metals available to plants and organisms (CaCl2- and EDTA-extractable fractions). The totals of the metals are below the upper limits of the values recommended for soils of the protected areas (type A). The mobility of the metals is low: the forms leachable with water range from 0.7% of the total content (TC) of Pb to 13.4% TC of Cd. The forms available to living organisms contain considerably higher quantities of the metals: from 2.3% TC of Ni to 22.6% TC of As in CaCl2-extractable fractions and from 0.7% TC of Cr to 82% TC of As in EDTA-extractable fractions. An assessment of the health risk indicates that children are exposed to the metals present in the sandboxes mostly due to inadvertent swallowing of "dirt" from their hands. The highest are the HQingestion indexes of As and Cr, both for the 3-year-old permanent spa residents (5.74E-02 and 1.71E-02, respectively) and the spa visitors of the same age (7.47E-03 and 2.22E-03, respectively) and the 6-year-old residents (4.31E-02 and 1.28E-02, respectively) and visitors (5.60E-03 and 1.66E-03, respectively). The health risk indexes HI in the case of non-cancerogenic substances for children 3 and 6 years old are for spa residents, 9.59E-02 and 7.19E-02, respectively, and for children visitors, who are exposed to environmental factors for a much shorter time than the residents, 1.25E-02 and 9.35E-03, respectively. All the risk indexes have their values significantly below 1, which proves the lack of deleterious effects resulting from the exposition of children to the elements considered. The children of both age groups, exposed to the cancerogenic substances, are endangered mainly by As. The risk values of the cancerogenic As for 3- and 6-year-old children residents are 1.27E-06 and 1.90E-06, respectively, and for children visitors of the same ages 1.65E-07 and 2.47E-07, respectively. These values are significantly lower than a permissible level of "1∙10E-05" and means that also in this case, the health risk is minimal. The risk values calculated for the remaining metals are much lower and follow the sequence Cr > Co > Cd. However, an adverse impact of some sand-contained pollutants that are attributed to the motor traffic (Cu, Zn, Ni, Cr, Co and Pb) and low emissions (mainly As and Cd) has been established in the spa resorts in question.