Search Results (53)

The presence of heavy metals in soils poses a serious threat due to these harmful elements being transported into the food chain. The aim of the presented research was to evaluate the effect of the extraction of selected heavy metals from soil with a 1 M aqueous solution of citric acid (CA) on the chemical (including mobile) forms of these elements and their bioavailability. A soil sample taken in an industrial area was extracted. Then the total content of selected heavy metals (Pb, Zn, Cu, Cd, Ni), their chemical forms (determined by sequential extraction according to the BCR procedure) and bioavailable forms (determined by one-step extraction with a 1 M HCl) were determined in both types of soil, before and after extraction. The tested soil contained significant amounts of the tested metals, and the amounts can be compared as follows: Pb ≥ Zn > Cu ≥ Cd > Ni. The greatest threat to the environment is associated with the presence of cadmium and lead in the tested soil, the content of which exceeds the limits set for soils in industrial areas. In addition, the level of presence of heavy metals in bioavailable and mobile chemical forms, was considered significant. No clear correlation was observed between the content of the analyzed metals in mobile and bioavailable forms. The tested soil contained significant concentrations of Pb (2141 mg/kg), Zn (2030 mg/kg), Cu (68 mg/kg), Cd (63 mg/kg), and Ni (23 mg/kg), which were reduced to 857, 589, 42, 28, and 14 mg/kg, respectively, after extraction with 1 M CA. The extraction process with a CA solution reduced the content of all metals, and the efficiency of the process can be compared as follows: Zn > Pb > Cd > Ni ≥ Cu, with efficiencies of 71%, 60%, 55%, 41% and 39%, respectively. The extraction process reduced the metal content of all the bioavailable and chemical fractions. The shares of metals in the mobile fractions decreased in favor of the immobilized fractions and ones more stable in the environment. After the process of leaching metals from the soil, a clear tendency towards equalization of the heavy metal content in the mobile and bioavailable fractions was observed. Full article

Ore mining and smelting are often related to environmental pollution. This study provides information about the geochemical features of Technosols at historical mining and metallurgical sites in the Tatra Mountains, southern Poland, evaluating the contents of potentially toxic trace elements (PTTE) and their behaviours in soils, as well as the influence of soil properties on PTTE mobility. Thirteen soil profiles were studied in eight abandoned mining and smelting sites. PTTE concentrations, including rare earth elements (REE), were measured using ICP-MS and ICP-OES. Selected elements (Cu, Zn, Pb, Cd, As, Sb, Ba, Sr, Co, Ni, Mn and Cr) were fractionated using the modified European Community Bureau of Reference (BCR) four-step sequential extraction. Contamination of soils with PTTE was compared against Polish regulatory limits, which were exceeded for Cu, Zn, Pb, Mo, Hg, As, Co, Ni and Ba, with concentrations exceeding limits by 16, 18, 34 and 160 times for Cu, Hg, As and Ba, respectively, in some profiles. Based on geochemical features depending on parent material properties, the soils examined were divided into three groups. Group I Technosols (near-neutral soils developed from Fe/Mn-ore and carbonate-bearing mining waste) were particularly enriched in Co, Ni, Mn and REE. Group II Technosols (acidic soils developed from polymetallic ore-bearing aluminosilicate mining waste) contained elevated concentrations of Cu, Zn, Hg, As, Sb, Bi, Co, Ag, Ba, Sr, U and Th; they contained lower contents of REE than Group I Technosols. Group III Technosols (soils developed in smelting-affected areas and containing metallurgical waste) were rich in Cu, As, Sb, Ba, Hg, Co and Ag and contained the lowest REE contents among the studied soils. Sequential BCR extraction revealed that PTTE mobility varied strongly according to soil group, with higher mobility of Mn, Cu and Zn in acidic polymetallic ore-derived soils (Group II), while carbonate-rich soils (Group I) showed mainly immobile forms. Metallurgical slag-derived soils (Group III) exhibited complex PTTE behaviour controlled by organic matter and Fe/Mn oxides. Soil properties (pH, carbonates and TOC) seem to control PTTE mobility. Full article

Revegetation is considered a sustainable option for mine area remediation. However, the sustainability and risk evolution of revegetation for large antimony mine slag remain incompletely understood. In this study, we focused on the revegetation project of the waste slag heap of XKS, the world’s largest antimony mine. Systematically analyzed the physicochemical properties, total metal(loid) content, and BCR sequential extraction and applied the modified comprehensive pollution risk assessment (MCR) method to evaluate ecological risk evolution. The results showed that revegetation can effectively increase the nutrient content, and the total content of nitrogen and phosphorus maximally increased by 5.15 and 1.89 times, respectively, after 10 years of remediation. Long-term revegetation could mitigate the metal(loid) contamination, and the average contents of As and Sb decreased by 88.72–93.18% and 93.47–89.87%, respectively. BCR analysis showed that the percentage of residual As and residual Sb increased from 64.75% and 85.88% to 78.38% and 91.58%, respectively. The MCR assessment method showed that revegetation could effectively reduce the ecological risk level. This study provides important multidimensional evidence for the ecological restoration of antimony mining areas, which can provide practical guidance for subsequent slag management and risk control. Full article

In order to comprehensively understand the content, source, speciation characteristics, and risk of heavy metals in cultivated soil of Pingshui Village, Zhaoping County, Hezhou City, this study conducted measurements on the total amounts of Cr, Ni, Cu, Zn, As, Cd, Pb, and Hg in 34 soil samples within the study area. Correlation analysis and principal component analysis were employed to investigate their sources. An improved BCR sequential extraction procedure was utilized to analyze the occurrence forms of eight heavy metals in soil samples. Ecological risks were evaluated using the geo-accumulation index (I_geo), potential ecological risk index (RI), and risk assessment code (RAC). The findings revealed that: (1) The soil heavy metals in the study area exhibited varying degrees of enrichment, primarily attributed to anthropogenic activities. (2) There was no significant difference in the speciation characteristics of the eight heavy metals in the soil of each sampling site in the study area, and the main components were all residual fraction, and the mild acid-soluble fraction of Cd and Zn accounted for a relatively high proportion in individual sampling sites, which should be paid attention to. (3) Through the results of three risk assessment methods, it is concluded that the heavy metal pollution of soil in the study area is serious, and continuous attention should be paid to the corresponding pollution prevention measures. Full article

Slow pyrolysis was carried out in biosolids under three different temperatures (400, 500 and 600 °C) and two different carrier gases (CO₂ and N₂) on a fluidized bed reactor. The total concentration, chemical fractionation, and plant availability of the heavy metals in biochar were assessed by standard methods. The total concentration of Fe, Zn, Cu, Mn, Cr, Ni and Pb increased with the conversion of biosolids to biochar and with increasing pyrolysis temperature. The community’s Bureau of Reference (BCR) sequential extraction identified the migration of metals from toxic and bioavailable to potentially stable available or non-available forms at higher pyrolysis temperatures. Diethylenetriamine penta-acetic acid (DTPA)-extractable metals (Cu, Zn, Cd, Cu, Fe and Pb) were significantly lower in biochar compared to biosolids. By replacing N₂ with CO₂, the total metal concentration of heavy metals was significantly different for Mn, Ni, Cd, Pb and As. There were larger amounts of metals in the residual and oxidizable fractions compared to when N₂ was used as a carrier gas. Consequently, the biochar produced at higher temperatures (500 and 600 °C) in the N₂ environment exhibited lower potential ecological risks than in CO₂ environments (69.94 and 52.16, respectively, compared to values from 75.95 to 151.38 for biochars prepared in N₂). Overall, the results suggest that the higher temperature biochar can support obtaining environmentally safe biochar and can be effective in attenuating the ecological risks of biosolids. Full article

This study aims to explore the effects of biochar ageing on its surface properties and the bioavailability of heavy metals in soil. The biochar was subjected to chemical oxidation/dry–wet cycles (CDWs), chemical oxidation/freeze–thaw cycles (CFTs), and natural ageing (NT) to analyze changes in the elemental composition, pH, specific surface area, pore volume, and surface functional groups. Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) were applied to characterize the functional groups and microstructure, and the BCR sequential extraction method was employed to demonstrate the fractionation distribution of Cu, Cd, and Pb. The results showed that the CDWs and CFTs treatments significantly reduced the carbon content of the biochar (with a maximum reduction to 47.70%), increased the oxygen content (up to 49.17%), and notably increased the specific surface area and pore volume. The pH decreased significantly from 9.91 to 4.92 and 4.99 for the CDWs and the CFTs, respectively. The FTIR analysis indicated notable changes in hydroxyl and carboxyl functional groups, and the SEM revealed severe microstructural damage in biochar after the CDWs and CFTs treatments. The heavy metal fractionation analysis indicated that exchangeable Cu, Cd, and Pb significantly increased after the CDWs treatment, reaching 31.40%, 5.25%, and 6.79%, respectively. In conclusion, biochar ageing significantly affects its physicochemical properties and increases the bioavailability of heavy metals, raising concerns about its long-term remediation effectiveness. Full article

The composting of sewage sludge (SS) with structure-forming additives is a popular and inexpensive method for the management of biodegradable waste. During this process, a number of transformations of organic matter and nutrients occur. This study presents the rates and directions of quantitative changes in Cu, Zn, and Ni during the composting of various mixtures. The following substances were used for preparing compost mixtures: SS, sawdust, straw, and bark. These substances were mixed together in appropriate proportions as follows: C1: 45% SS + 50% sawdust + 5% straw; C2: 45% SS + 50% bark+ 5% straw; and C3: 45% SS + 35% bark + 15% sawdust + 5% straw. Single (DTPA solution) and sequential extraction methods (BCR protocol) were used for microelement mobility assessment. Compost valorization was performed in each individual composting phase. The chain relative increment analysis was used for such assessment. Additionally, the potential metal pollution in the composts was evaluated by applying the following indices: the pollutant accumulation index (PAI), heavy metal enrichment index (HMEI), and heavy metal pollution load index (HMPLI). During composting, generally, the amounts of Ni, Cu, and Zn increased in the various extracted combinations, which was independent of their susceptibility to decomposition. Despite of this, the tested composts should be considered as a source of slowly available microelements for plants. The most intense quantitative changes in metals occurred in the thermophilic phase, and the weakest changes occurred in the cooling phase. At the same time, the calculated indices indicated a lack of contamination of the composts with the analyzed metals, emphasizing their environmental safety and lack of negative impact. The bulking agents used for composting with SS did not significantly influence the intensity of the quantitative changes in the tested metals. Full article

The aim of this study was to evaluate the mobility of copper (Cu) and zinc (Zn) and their impact on the properties of bentonites and unfrozen water content. Limited research in this area necessitates further analysis to prevent the negative effects of metal interactions on bentonite effectiveness. Tests involved American (SWy-3, Stx-1b) and Slovak (BSvk) bentonite samples with Zn or Cu ion exchange. Sequential extraction was performed using the Community Bureau of Reference (BCR) method. Elemental content was analyzed via inductively coupled plasma optical emission spectrometry (ICP-OES). Unfrozen water content was measured using nuclear magnetic resonance (¹H-NMR) and differential scanning calorimetry (DSC). Results showed a significant influence of the main cation (Zn or Cu) on ion mobility, with toxic metal concentrations increasing mobility and decreasing residual fractions. Mobile Zn fractions increased with larger particle diameters, lower clay content, and shorter interplanar spacing, while the opposite was observed for Cu. Zn likely accumulated in larger clay pores, while Cu was immobilized in the bentonite complex. The stability of Zn or Cu ions increased with higher clay content or specific surface area. Residual Zn or Cu fractions were highest in uncontaminated bentonites with higher unfrozen water content, suggesting the potential formation of concentrated solutions in sub-zero temperatures, posing a threat to the clay–water environment, especially in cold regions. Full article

This paper discusses approaches for verification of methods of measurements of chemical and physical characteristics of specific samples. The limitations of well-known approaches are discussed. Some examples of alternatives are given to demonstrate specific issues encountered in the research laboratory analyzing new materials or characterizing new properties of materials. Application of sequential procedure using lower quantities of samples and reagents is presented. A standard addition to solid samples is discussed. The approach of control charts for estimation of method uncertainty for determination of plant available phosphorus is presented. The method comparison is applied as an approach to verification of alkaline reactivity by inductively coupled plasma–optical emission spectroscopy (ICP-OES) measurement, as well as density of newly synthesized chalcogenide glass materials. The presented examples demonstrated that alternative approaches are needed in order to verify the methods applied due to the great variety of activities and corresponding tasks in a research laboratory. Full article

Lithium belongs to the critical elements and is used in a variety of high-tech applications. In the context of the circular economy, demand has arisen for technologies that are able to recover high-tech metals from wastes and byproducts. To achieve efficient recovery, apart from assessing metal enrichment, extensive knowledge of metal binding and leaching characteristics is required. The aim of the present study is to investigate the Li contents and mode of occurrence in Greek coal fly ashes. Eight coal fly ashes from different power plants in Greece were collected, and their major constituents were analyzed by X-ray fluorescence spectroscopy (XRF); their mineralogy was studied by X-ray powder diffraction (XRD), and their Li content was determined by ICP–MS. To identify Li binding and leaching characteristics, two sequential extraction methods (Tessier and BCR) were employed. The results showed that the Li content in the samples studied was between 95 and 256 μg/g and could be mainly attributed to the amorphous material encountered in the samples. The sequential extraction experiments revealed that 70–90% of Li is included in the residual fraction, indicating that it is strongly bound to the fly ash matrix. Full article

This manuscript focuses on the sustainable utilization of municipal waste incineration ashes in construction, taking into account their substantial concentration of beneficial elements and the potential environmental pollution caused by the leaching of toxic elements due to naturally occurring processes. To assess heavy metal mobility in ashes, a sequential extraction method based on the European Community Bureau of Reference (BCR) was applied. It enables the determination of heavy metal fractions and provides valuable insights into their potential environmental impact and bioavailability. More than 80% of Cd, and Zn, and over 75% of Cu, exhibited strong associations with the most mobile exchangeable fraction, while over 60% of Al and Fe were predominantly bound to reducible. The distribution of As and Cr was relatively balanced between exchangeable and oxidizable fractions, whereas 100% of Pb was exclusively associated with oxidizable fractions, indicating immobilization of this element in the ash. The calculated Risk Assessment Codes and Individual Contamination Factors indicated a quite high to very high risk level for the element’s mobility and environmental contamination. For elements like Pb, Cd, Cu, and Zn, higher concentrations in the samples are associated with higher overall environmental risk. For elements like As and Cr, higher concentrations in the samples are associated with lower overall environmental risk. Studied ash exhibits potential as a resource, but equally it demands rigorous environmental management to ensure responsible utilization. The observed metal mobilization underscores the necessity for stringent containment and treatment measures to mitigate the risk of environmental contamination. Full article

The gradually increasing presence of arsenic, a highly toxic heavy metal, poses a significant threat to both soil environmental safety and human health. Pteris vittata has long been recognized as an efficient hyperaccumulator plant for arsenic pollution. However, the pattern of arsenic accumulation in soil impacts its bioavailability and restricts the extraction efficiency of Pteris vittata. To address this issue, microorganisms have the potential to improve the arsenic accumulation efficiency of Pteris vittata. In this work, we employed anthropogenic enrichment methods to extract functional iron–sulfur-reducing bacteria from soil as a raw material. These bacteria were then utilized to assist Pteris vittata in the phytoremediation of arsenic-contaminated soil. Furthermore, the utilization of organic fertilizer produced from fermented crop straw significantly boosted the remediation effect. This led to an increase in the accumulation efficiency of arsenic by Pteris vittata by 87.56%, while simultaneously reducing the content of available arsenic in the soil by 98.36%. Finally, the experimental phenomena were studied through a soil-microbial batch leaching test and plant potting test. And the mechanism of the microorganism-catalyzed soil iron–sulfur geochemical cycle on arsenic release and transformation in soil as well as the extraction effect of Pteris vittata were systematically investigated using ICP, BCR sequential extraction and XPS analysis. The results demonstrated that using iron–sulfur-reducing microorganisms to enhance the phytoremediation effect is an effective strategy in the field of ecological restoration. Full article

Agricultural soils close to mining establishments may suffer from airborne pollution, due to excavation and transportation activities. To assess the impact of soil pollution from potentially toxic elements (PTEs) on soil and human health in agricultural areas close to Fe-Ni mines, 36 composite topsoil samples were collected from central Euboea Island, Greece. The soils were analyzed for their physicochemical properties and for total and bioavailable Ni, Cr, Co, Mn, Fe, Pb, Cu, and Zn concentrations; the BCR sequential extraction protocol was additionally applied to all samples. Soil enrichment caused by the metals and the implications of soil degradation on the ecosystem were evaluated using the calculation of single pollution indices (PI) and the potential ecological risk index (RI), respectively. The hazard index (HI) for non-carcinogenic metals and life cancer risk (LCR) for carcinogenic metals were used to appraise the human health risks. Extremely high, very high, and considerably high total concentrations of Ni, Cr, and Mn, respectively, were determined. Though most of the total amounts of metals in soil samples were found to be related to the residual fraction, the considerable portion extracted in the first two steps of the BCR process can be regarded as able to introduce toxicity issues in the local biota. High PI values of Cr, Co, and especially Ni point to severely polluted soils, and the mean RI values indicate a considerable risk for biota. HI values > 1 show increased possibilities for non-carcinogenic health issues in children, whereas the LCR values of Ni were above the critical limit, 1 × 10⁻⁴, for both children and adults. Full article

This article presents the results of experimental research on the possible use of construction and demolition waste (CDW) to improve the properties of unburnt tailings originating from the thermally active spoil heap in Heřmanice (Ostrava, Czech Republic). Mining activity anywhere in the world generally entails a lot of negative impacts on the environment, which are of a long-term nature. One of the most pressing challenges in the remediation of the consequences of mining activity is the thermal activity of spoil heaps associated with the high acidity of the tailings. Active acidity (pH/H₂O), exchangeable acidity (pH/CaCl₂), hydrolytic acidity (H_a), and elemental composition of tailings and CDW have been monitored. Based on an acidity study, it has been proven that compared to burnt tailings (pH/H₂O = 8.4, pH/CaCl₂ = 8.9 and H_a = 1.4 mmol kg⁻¹), unburnt tailings show acidic properties (pH/H₂O = 3.7, pH/CaCl₂ = 3.6 and H_a = 205 mmol kg⁻¹). The bioavailability of two selected potentially toxic elements (PTEs), namely Al and Fe, was examined based on the elemental composition. BCR sequential extraction analysis was used to determine their bioavailability. It has been proven that mixing CDW with tailings has a positive effect on the pH value, which has a positive effect on the further development of the entire site. The increase in the pH value is provably dependent on the amount of construction waste added, so it can be said that the increasing amount of construction waste will result in improved parameters of the burnt tailings. The results of the BCR analysis show that aluminum from the tailings will be released both from the reducible and oxidisable fractions, where it will be mainly bound to sulphides. The relatively high concentration of Fe in the oxidisable fraction (2002 mg Fe kg⁻¹) suggests that Fe is bound to sulphides in the tailings, and it is due to the high residual pyrite and sulphide content in the dumped material, as expected. This work has found no limits where CDW no longer positively affects the acidity of unburnt tailings. For practical application, however, it is important that the mixture of CDW and tailings is properly mixed and then used for remediation. Full article

This work aimed to detect changes in trace element chemical speciation in sewage sludge (SS) after the ozonation process. The modified Community Bureau of Reference (BCR) sequential extraction procedure was performed to determine the chemical speciation of trace elements in SS after the ozonation process. To assess potential soil contamination with trace elements from sewage sludge after the ozonation process, the risk assessment code (RAC) coefficient was used. The bioaccumulation factor (BAF) and translocation factor (TF) values were also calculated to characterize the efficiency of trace element accumulation in the studied plant species from soil fertilized with sludges after the ozonation process. Generally, the mean concentration of total trace elements in the SS after the ozonation process was higher, but the differences were statistically significant only in the case of Mn, Cu, Pb, and Cd. The dominant fraction of Fe, Cr, Pb, and Cd was the residual fraction F4, while the extractable/exchangeable fraction F1 was present in the smallest amount. Therefore, in the case of Mn, Zn, and Ni, the ozonation process had a significant impact on the increase in the content of these elements in the F1 fraction. The application of the SS stabilized by ozonation process for maize and wheat fertilization did not significantly affect the bioaccumulation of most of the analyzed metals in aboveground biomass. Higher values of BAF coefficients after the application of ozonated SS were found only in the case of Cu and Ni. In turn, the determined TF coefficients were lower than 1 in most cases. The obtained results showed that the slight change in the concentration of Zn, Mn, and Ni in fraction F1 causes a specific risk of their mobility in the soil environment. It should be noted that due to the variable composition of sewage sludge, an analysis of the content of individual trace elements in chemical fractions should be carried out to assess its actual impact on the environment. This can help to indicate further actions that should be undertaken to limit their negative impact on the environment. Full article