Sustainable use of composted sewage sludge: Metal(loid) leaching behaviour and material suitability for application on degraded soils.

Composted sewage sludge was investigated as a promising material for the reclamation or remediation of degraded sites. Using sewage sludge as soil amendment provides environmental benefits and risks while supporting circularity and waste minimisation. This study aims to comprehensively assess the suitability of locally available low-cost sludge treatment for sustainable and environmentally safe topsoil disposal in a brownfield area affected by coal mining. A nine-month composting was conducted before field application to the soil environment. The objectives were to assess: (i) composting time-dependent and pH-dependent metal(loid) leachability from composted sludges, (ii) the effect of sludges on metal(loid) leachability from soil over the first six months, and (iii) metal(loid) plant uptake during the first vegetation season as well as the bioaccumulation and translocation factors. The set of standardised leaching experiments confirmed the positive effect of compost maturity, i.e. despite some fluctuations over time, metal(loid) availability from the final composts was very low. Some metals showed unusual pH-dependent behaviour with the highest leachability at pH 8 due to excessive release of dissolved organic matter from the not-yet-stabilised matrix. Ecotoxicity testing confirmed the safety of the final composts for further soil application. The sludge-amended plots displayed similar metal(loid) leaching and pH evolution in time compared to the control biomass-amended plot. However, plant species (Artemisia vulgaris L.) that formed the natural vegetation cover of the experimental plots showed cumulative metal(loid) uptake. Cadmium and zinc were identified as the critical metals possibly related to the applied sludges, yielding high bioaccumulation and translocation factors. Yet, the quality of the compost feedstock, heterogeneity, and background values of the brownfield site need to be considered. Nevertheless, soil respiration indicated no adverse effects on soil health six months after sludge application. Overall, the composted material demonstrated potential suitability for remediation application in the studied area.

Evaluating the effectiveness of sulfidated nano zerovalent iron and sludge co-application for reducing metal mobility in contaminated soil.

Sewage sludge has long been applied to soils as a fertilizer yet may be enriched with leachable metal(loid)s and other pollutants. Sulfidated nanoscale zerovalent iron (S-nZVI) has proven effective at metal sorption; however, risks associated with the use of engineered nanoparticles cannot be neglected. This study investigated the effects of the co-application of composted sewage sludge with S-nZVI for the stabilization of Cd, Pb, Fe, Zn. Five treatments (control, Fe grit, composted sludge, S-nZVI, composted sludge and S-nZVI), two leaching fluids; synthetic precipitation leaching procedure (SPLP) and toxicity characteristic leaching procedure (TCLP) fluid were used, samples were incubated at different time intervals of 1 week, 1, 3, and 6 months. Fe grit proved most efficient in reducing the concentration of extractable metals in the batch experiment; the mixture of composted sludge and S-nZVI was the most effective in reducing the leachability of metals in the column systems, while S-nZVI was the most efficient for reducing about 80% of Zn concentration in soil solution. Thus, the combination of two amendments, S-nZVI incorporated with composted sewage sludge and Fe grit proved most effective at reducing metal leaching and possibly lowering the associated risks. Future work should investigate the longer-term efficiency of this combination.

Nano zerovalent Fe did not reduce metal(loid) leaching and ecotoxicity further than conventional Fe grit in contrasting smelter impacted soils: A 1-year field study.

The majority of the studies on nanoscale zero-valent iron (nZVI) are conducted at a laboratory-scale, while field-scale evidence is scarce. The objective of this study was to compare the metal(loid) immobilization efficiency of selected Fe-based materials under field conditions for a period of one year. Two contrasting metal(loid) (As, Cd, Pb, Zn) enriched soils from a smelter-contaminated area were amended with sulfidized nZVI (S-nZVI) solely or combined with thermally stabilized sewage sludge and compared to amendment with microscale iron grit. In the soil with higher pH (7.5) and organic matter content (TOC = 12.7 %), the application of amendments resulted in a moderate increase in pH and reduced As, Cd, Pb, and Zn leaching after 1-year, with S-nZVI and sludge combined being the most efficient, followed by iron grit and S-nZVI alone. However, the amendments had adverse impacts on microbial biomass quantity, S-nZVI being the least damaging. In the soil with a lower pH (6.0) and organic matter content (TOC = 2.3 %), the results were mixed; 0.01 M CaCl2 extraction data showed only S-nZVI with sludge as remaining effective in reducing extractable concentrations of metals; on the other hand, Cd and Zn concentrations were increased in the extracted soil pore water solutions, in contrast to the two conventional amendments. Despite that, S-nZVI with sludge enhanced the quantity of microbial biomass in this soil. Additional earthworm avoidance data indicated that they generally avoided soil treated with all Fe-based materials, but the presence of sludge impacted their preferences somewhat. In summary, no significant differences between S-nZVI and iron grit were observed for metal(loid) immobilization, though sludge significantly improved the performance of S-nZVI in terms of soil health indicators. Therefore, this study indicates that S-nZVI amendment of soils alone should be avoided, though further field evidence from a broader range of soils is now required.

Measuring Pb isotope ratios in fresh snow filtrate refines the apportioning of contaminant sources in the Arctic.

The remoteness and low population in the Arctic allow us to study global environmental processes, where the analysis of indicators can provide useful information about local and distant pollution sources. Fresh snow represents a convenient indicator of regional and transboundary atmospheric contamination sources, entrapping aerosols, and particulates like a natural autosampler of the environment. Lead stable isotopes are widely used to trace and monitor local and distant pollution sources. However, the behavior of Pb within different snow components is still not thoroughly studied, and its significance could be underestimated if only larger particulates are accounted for. We collected snow and samples from potential sources (fuel, rocks, coal) in three Arctic localities: Nuuk (Greenland), Reykjavik (Iceland), and Longyearbyen (Svalbard). We separated the filtrate from the filter residue through 0.45 µm nitrocellulose membranes to isolate the low-diameter particles associated with long-range transport from larger particles of mostly local natural origin. Filtrates yielded higher EFs (enrichment factor as the Pb/Al ratio relative to the upper crust) than filtration residues (80 ± 104 and 2.1 ± 1.1, respectively), and Pb isotope signals similar to fuel and coal (206Pb/207Pb are 1.199 ± 0.028 in coal, 1.168 ± 0.029 in filtrates, 1.163 ± 0.013 in fuel, 1.137 ± 0.045 in residues, and 0.985 ± 0.020 in rocks). In contrast to filtrates, the filter residues present wider ranges of Pb isotope compositions and crustal contributions and lower EFs, so we suggest that filtrate contains Pb from fuel combustion more selectively, while the residue carries a more considerable contribution of local mineral dust that can mask the contribution of other anthropogenic or distant natural sources. These findings add weight to the notion that filtrates are a more selective measure of metal deposition from long-range anthropogenic emissions compared to analyzing bulk melted snow or only filter residues.

Pyrolysed sewage sludge for metal(loid) removal and immobilisation in contrasting soils: Exploring variety of risk elements across contamination levels.

Efficient treatment of sewage sludge may transform waste into stable materials with minimised hazardous properties ready for secondary use. Pyrolysed sewage sludge, sludgechar, has multiple environmental benefits including contaminant sorption capacity and nutrient recycling. The properties of five sludgechars were tested firstly for adsorption efficiency in laboratory solutions before prospective application to soils. A wide variety of metal(loid)s (As, Cd, Co, Cr, Cu, Ni, Pb, Sb, and Zn) was involved. Secondly, the sludgechars (3 % v/v) were incubated in five soils differing in (multi)-metal(loid) presence and the level of contamination. The main aim was to evaluate the metal(loid) immobilisation potential of the sludgechars for soil remediation. Moreover, nutrient supply was investigated to comprehensively assess the material's benefits for soils. All sludgechars were efficient (up to 100 %) for the removal of metal cations while their efficiency for metal(loid) anions was limited in aqueous solutions. Phosphates and sulphates were identified crucial for metal(loid) capture, based on SEM/EDS, XRD and MINTEQ findings. In soils, important fluctuations were observed for Zn, being partially immobilised by the sludgechars in high-Zntot soils, while partially solubilised in moderate to low-Zntot soils. Moreover, pH showed to be crucial for material stability, metal(loid) adsorption ability and their immobilisation in soils. Although metal(loid) retention was generally low in soils, nutrient enrichment was significant after sludgechar application. Long-term evaluation of the material sorption efficiency, nutrient supply, and ageing in soil environments will be necessary in future studies.

Critically raw materials as potential emerging environmental contaminants, their distribution patterns, risks and behaviour in floodplain soils contaminated by heavy metals.

The expanding demand for new critical raw materials can lead to their increased release to the environment in the form of emerging environmental contaminants (EECs). However, there has never been a comprehensive study that takes into account the total EEC content, the content of various EEC fractions, their behaviour in floodplain soils, and potential ecological and human health risks. The occurrence, fractions, and influencing factors of the seven EECs (Li, Be, Sr, Ba, V, B, Se) originating from historical mining in floodplain soils of various ecosystems (arable lands, grasslands, riparian zones, contaminated sites) were investigated. Based on the evaluation of the overall levels of EECs (potentially toxic elements) in comparison to the soil guideline values set by European legislation for Be, Ba, V, B, and Se, it was found that only Be did not exceed the recommended limits. Among the elements analyzed, Li had the highest average contamination factor (CF) of 5.8, followed by Ba with 1.5 and B with 1.4. Particularly concerning was the discovery of a potential serious health risk associated with Li exposure for children, as indicated by hazard quotients ranging from 0.128 to 1.478. With the exception of Be and Se, the partitioning of the EECs into the different fractions revealed that the EECs are primarily bound with the residual fraction. Be (13.8%) had the highest percentage of exchangeable fraction as the most bioavailable in the first soil layer, followed by Sr (10.9%), Se (10.2%), Ba (10.0%), and B (2.9%). The most frequently observed correlations were between EEC fractions and pH/KCl, followed by soil organic carbon and manganese hydrous oxides. Variance analyses confirmed the impact of different ecosystems on EEC total content and fractions.

Remedial trial of sequential anoxic/oxic chemico-biological treatment for decontamination of extreme hexachlorocyclohexane concentrations in polluted soil.

During production of γ-hexachlorocyclohexane (γ-HCH), thousands of tons of other isomers were synthesized as byproducts, and after dumping represent sources of contamination for the environment. Several microbes have the potential for aerobic and anaerobic degradation of HCHs, and zero-valent iron is an effective remediation agent for abiotic dechlorination of HCHs, whereas the combination of the processes has not yet been explored. In this study, a sequence of anoxic/oxic chemico-biological treatments for the degradation of HCHs in a real extremely contaminated soil (10-30 g/kg) was applied. Approximately 1500 kg of the soil was employed, and various combinations of reducing and oxygen-releasing chemicals were used for setting up the aerobic and anaerobic phases. The best results were obtained with mZVI/nZVI, grass cuttings, and oxygen-releasing compounds. In this case, 80 % removal of HCHs was achieved in 129 days, and 98 % degradation was achieved after 1106 days. The analysis of HCHs and their transformation products proved active degradation when slight accumulation of the transformation product during the anaerobic phase was followed by aerobic degradation. The results document that switching between aerobic and anaerobic phases, together with the addition of grass, also created suitable conditions for the biodegradation of HCHs and monochlorobenzene/benzene by microbes.

A perspective on the recovery mechanisms of spent lithium iron phosphate cathode materials in different oxidation environments.

Oxidative extraction has become an economically viable option for recycling lithium (Li) from spent lithium iron phosphate (LiFePO4) batteries. In this study, the releases behaviour of Li from spent LiFePO4 batteries under different oxidizing conditions was investigated with sodium hypochlorite (NaClO) as the solid oxidant. We revealed that, due to the intervention of graphitic carbon, the generated species of Li in mechanochemical oxidation (NaClO:LiFePO4 at a molar ratio of 2:1, 5 min, and 600 rpm) was lithium carbonate (Li2CO3). The graphite layer provided a channel for the conversion of Li species released by mechanochemical oxidation. While in hydrometallurgical oxidation (NaClO:LiFePO4 at a molar ratio of 2:1 and 12.5 min), the presence of hydrogen species led to the formation of lithium chloride (LiCl). Moreover, life cycle assessment (LCA) demonstrated that for recycling 1.0 kg of spent LiFePO4 batteries, mechanochemical and hydrometallurgical oxidation could reduce carbon footprints by 2.81 kg CO2 eq and 2.88 kg CO2 eq, respectively. Our results indicate that the oxidative environment determines the release pathway of Li from the spent LiFePO4 cathode material, thereby regulating the product forms of Li and environmental impacts. This study can provide key technical guidance for Li recycling from spent LiFePO4 batteries.

Assessment of natural and anthropogenic contamination sources in a Mediterranean aquifer by combining hydrochemical and stable isotope techniques.

The Atalanti basin is an intensively cultivated area in central Greece, facing groundwater quality deterioration threats due to natural and anthropogenic-related contamination sources. A combination of statistical and hydrogeochemical techniques, and stable isotope compositions (δ2H-H2O and δ18Ο-Η2Ο, δ15Ν-ΝΟ3- and δ18Ο-ΝΟ3-, δ34S-SO42- and δ18O-SO42-) were applied to elucidate the origin of salinity and nitrate contamination, and shed light on the potential associations between geogenic Cr(VI) and NO3- sources and transformations. Nitrate and Cr(VI) concentrations reached up to 337 mg L-1 and 76.1 µg L-1, respectively, exceeding WHO threshold values in places. The cluster of samples with the high salinity was mostly influenced by irrigation return flow and marine aerosols, and less by seawater intrusion, as evidenced by the ionic ratios (e.g., Na+/Cl-) and the stable isotopes of oxygen and hydrogen in water, and sulphur and oxygen in sulphates. The δ15Ν-ΝΟ3- and δ18O-NO3- values ranged from +2.0 ‰ to +14.5 ‰ and + 0.3 ‰ to +11.0 ‰, respectively. We found that the dominant sources of NO3- in groundwater were fertilizers in the central part of the area and sewage waste in the northern part around the residential area of Livanates. The occurrence of denitrification was evident in the northern part of the basin, where the DO levels were lowest (≤ 2.2 mg L-1), whereas nitrification of NH4+-fertilizers prevailed in the central part. Elevated Cr(VI) values (≥ 20 µg/l) were associated with the lowest deviation of the measured from the theoretical nitrification δ18Ο-NO3- values, whereas the lowest Cr(VI) values were observed in the denitrified water samples. Our isotope findings revealed the strong influence of redox conditions on the biogeochemical transformations of N species and the mobilization of Cr(VI) that will help improve the understanding of the fate of these contaminants from the unsaturated zone to the groundwater in areas of agricultural and urban land use.

Electroactive Fe-biochar for redox-related remediation of arsenic and chromium: Distinct redox nature with varying iron/carbon speciation.

Electroactive Fe-biochar has attracted significant attention for As(III)/Cr(VI) immobilization through redox reactions, and its performance essentially lies in the regulation of various Fe/C moieties for desired redox performance. Here, a series of Fe-biochar with distinct Fe/C speciation were rationally produced via two-step pyrolysis of iron minerals and biomass waste at 400-850 °C (BCX-Fe-Y, X and Y represented the first- and second-step pyrolysis temperature, respectively). The redox transformation of Cr(VI) and As(III) by Fe-biochar was evaluated in simulated wastewater under oxic or anoxic conditions. Results showed that more effective Cr(VI) reduction could be achieved by BCX-Fe-400, while a higher amount of As (III) was oxidized by BCX-Fe-850 under the anoxic environment. Besides, BCX-Fe-400 could generate more reactive oxygen species (e.g.,•OH) by reducing the O2, which enhanced the redox-related transformation of pollutants under the oxic situation. The evolving redox performance of Fe-biochar was governed by the transition of the redox state from reductive to oxidative related to the Fe/C speciation. The small-sized amorphous/low-crystalline ferrous minerals contributed to a higher electron-donating capacity (0.43-1.28 mmol g-1) of BCX-Fe-400. In contrast, the oxidative surface oxygen-functionalities (i.e., carboxyl and quinoid) on BCX-Fe-850 endowed a stronger electron-accepting capacity (0.71-1.39 mmol g-1). Moreover, the graphitic crystallites with edge-type defects and porous structure facilitated the electron transfer, leading to a higher electron efficiency of BCX-Fe-850. Overall, we unveiled the roles of both Fe and C speciation in maneuvering the redox reactivity of Fe-biochar, which can advance our rational design of electroactive Fe-biochar for redox-related environmental remediation.

Innovative in situ remediation of mine waters using a layered double hydroxide-biochar composite.

The current demand for alternative water sources requires the incorporation of low-cost composites in remediation technologies. These represent a sustainable alternative to more expensive, commercially used adsorbents. The main objective of this comprehensive field-scale study was to incorporate the layered double hydroxides (LDHs) into the hybrid biochar-based composites and apply an innovative material to remediate As/Sb-rich mine waters. The presence of hydrous Fe oxides (HFOs) within the composite enhanced the total adsorption efficiency of the composite for As(V) and Sb(V). The kinetic data fitted a pseudo-second order model. Equilibrium experiments confirmed that the composite had a stronger interaction with As(V) than with Sb(V). The efficient removal of As(V) from mine water was achieved in both batch and continuous flow column systems, reaching up to 98% and 80%, respectively. Sb(V) showed different behavior to As(V) during mine water treatment, reaching adsorption efficiencies of up to 39% and 26% in batch and column experiments, respectively. The migration of Sb(V) in mine water was mostly attributed to its dispersion before it was able to show affinity to the composite. In general, the proposed column technology is suitable for the field remediation of small volumes of contaminated water, and thus has significant commercial potential.

Contaminated soils of different natural pH and industrial origin: The role of (nano) iron- and manganese-based amendments in As, Sb, Pb, and Zn leachability.

Soils containing a large proportion of industrial waste can pose a health risk due to high environmentally available concentrations of toxic metal(loid)s. Nano zero-valent iron (nZVI) and amorphous manganese oxide (AMO) were applied as immobilising amendments (1 wt%) to soils with different industrial origin of As and Sb, and leaching of As, Sb, Pb, and Zn was investigated using a single extraction with deionised water. The different industrial impact was reflected in the mineralogy, chemical composition and pH of these soils. Water-soluble As ratios positively correlated with pH in all experimental treatments. A significant decrease of water-soluble As ratios was observed in all nZVI-amended soils (~65-93% of the control) except for one sample with the lowest solution pH. Nano zero-valent iron was also successful in Sb immobilisation (~76-90% of the control). Highly variable results were obtained for AMO, which only led to a decrease of water-soluble As in soils with solution pH of ≥7 (~70-80% of the control), probably due to lower stability of AMO in acidic conditions. In each case, nZVI was more efficient at decreasing water-soluble As ratios than AMO. Dissolved Pb concentrations remained unchanged after the application of nZVI and AMO, and the decrease of Zn leaching using AMO was controlled mainly by soil pH increase induced by its application. According to the calculated saturation indices, tripuhyite (FeSbO4) was predicted to be the key mineral controlling Sb solubility in mine soils. Secondary Fe (hydr)oxides either originally present or newly formed due to nZVI oxidation were instrumentally identified at different stages of their transformation and metal(loid) retention. To conclude, nZVI is suitable for application to contaminated soils at a wide pH range, while the use of AMO for decreasing As leaching is limited to soils with pH ≥ 7.

Cadmium Isotope Fractionation during Complexation with Humic Acid.

Cadmium (Cd) isotopes are known to fractionate during complexation with various environmentally relevant surfaces and ligands. Our results, which were obtained using (i) batch experiments at different Cd concentrations, ionic strengths, and pH values, (ii) modeling, and (iii) infrared and X-ray absorption spectroscopies, highlight the preferential enrichment of light Cd isotopes bound to humic acid (HA), leaving the heavier Cd pool preferentially in solution (Δ114/110CdHA-Cd(aq) of -0.15 ± 0.01‰). At high ionic strengths, Cd isotope fractionation mainly depends on its complexation with carboxylic sites. Outer-sphere complexation occurs at equilibrium together with inner-sphere complexation as well as with the change of the first Cd coordination and its hydration complexes in solution. At low ionic strengths, nonspecific Cd binding induced by electrostatic attractions plays a dominant role and promotes Cd isotope fractionation during complexation. This significant outcome elucidates the mechanisms involved in HA-Cd interactions. The results can be used during (i) fingerprinting the available Cd in soil solution after its complexation with solid or soluble natural organic matter and (ii) evaluating the contribution of Cd complexation with organic ligands and phytoplankton-derived debris versus Cd assimilation by phytoplankton in seawater.

Tracing the sources of bioaccessible metal(loid)s in urban environments: A multidisciplinary approach.

Understanding the links between sources of magnetic particles and bioaccessibility of metal(loids) in environmental sampling media is crucial for better evaluating human health risks, although relevant information in the scientific literature is scarce. Here, soil, road and house dust samples from a heavy industrial area in Greece were characterized in a multidisciplinary study combining magnetic measurements, SEM/EDS analyses, bioaccessibility measurements and Pb isotopic analyses of bioaccessible Pb. The oral and inhalable bioaccessible fractions of As, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn were assessed by applying simulated gastric and lung solutions. SEM/EDS analysis revealed the abundant presence of anthropogenic Fe-containing spherules of industrial origin in all sampling media, often containing minor contents of Cr, Cu, Mn, Pb and Zn. The inhalation bioaccessibility (%) in all environmental compartments was higher than the oral one for most elements analyzed in the present study. Clear associations between magnetic susceptibility and bioaccessible amounts of most of analyzed elements were encountered for the soil and road dust. The isotopic analyses of bioaccessible Pb showed that there are significant differences in the isotopic ratios between total and bioaccessible Pb. We conclude that Pb solubilized by the simulated gastric and lung extractions is principally anthropogenic, representing a mixture of industrial Pb and Pb related to the past usage of leaded petrol. Low values of 206Pb/207Pb were accompanied by high bioaccessible contents of Cd, Pb and Zn indicating that anthropogenic (mostly industrial) sources exert influence on the bioaccessible forms of these metals. Coupling magnetic and bioaccessibility measurements with stable isotopic technique of bioaccessible Pb is more reliable for determining Pb and other metal sources with high oral and inhalation bioaccessibility.

Nanoscale Zero-Valent Iron Has Minimum Toxicological Risk on the Germination and Early Growth of Two Grass Species with Potential for Phytostabilization.

Two Poaceae species, Agrostis capillaris and Festuca rubra, were selected for their potential as phytostabilizing plants in multicontaminated soils. These species are resistant to contamination and maintain high concentrations of contaminants at the root level. Nanoscale zero-valent iron (nZVI) is an engineered nanomaterial with the ability to stabilize metal(loid)s in soils; its potential toxicological effects in the selected species were studied in a germination test using: (i) control variant without soil; (ii) soil contaminated with Pb and Zn; and (iii) contaminated soil amended with 1% nZVI, as well as in an hydroponic experiment with the addition of nZVI 0, 25, 50 and 100 mg L-1. nZVI had no negative effects on seed germination or seedling growth, but was associated with an increase in shoot growth and reduction of the elongation inhibition rate (root-dependent) of F. rubra seedlings. However, applications of nZVI in the hydroponic solution had no effects on F. rubra but A. capillaris developed longer roots and more biomass. Increasing nZVI concentrations in the growing solution increased Mg and Fe uptake and reduced the Fe translocation factor. Our results indicate that nZVI has few toxic effects on the studied species.

Metal(loid) and isotopic tracing of Pb in soils, road and house dusts from the industrial area of Volos (central Greece).

This study examines the metal(loid) contents (As, Cd, Cr, Cu, Mn, Ni, Pb, Sb, Tl and Zn) and Pb isotopes in different environmental compartments (soil, road dust, house dust) from the industrial vicinity of Volos, central Greece. The area surrounding two steel factories, a cement plant, an industrial area and the city core were considered as potential hot spots of metal(loid) contamination. Significant anthropogenic enrichments of Cd, Pb and Zn in relation to local baseline were identified for the soil (median Enrichment Factors of 7, 15 and 8, respectively) and road dusts around the steel factory located at Velestino area. The high contents of As, Sb and Tl in the soil and road dust around the cement plant are attributed to natural sources of contamination associated with adjacent mineralization. The soil samples in the city core exhibited moderate enrichments with respect to typical tracers (Pb, Zn) of anthropogenic contamination in urban areas. Anthropogenic influences in terms of metal(loid) concentrations were more pronounced for the road and house dust material. The Pb isotopic ratios of soil (206Pb/207Pb = 1.154 to 1.194), road dust (206Pb/207Pb = 1.144 to 1.174) and house dust (206Pb/207Pb = 1.129 to 1.171) were between those of the local bedrock and anthropogenic Pb sources. Industrial Pb from the steel plant was the predominant anthropogenic Pb source with relative contributions of ~49% for the soil, ~42% for the road dust and ~44% for the house dust samples. For the road and house dust material, the geochemical signature obtained from Pb isotopic compositions and elemental ratios suggests additional contributors from vehicular emissions. The results of this study demonstrate the suitability of soil to trace natural and anthropogenic impacts in industrial areas and the sensitivity of the road and house dust material to record anthropogenic (industrial and vehicular-derived) contamination in such environments.

Health risk assessment of metal(loid)s in soil and particulate matter from industrialized regions: A multidisciplinary approach.

In this study, samples of soil and particulate matter obtained from the highly industrialized region of Ostrava, Czech Republic, are used for the toxicity evaluation of the selected metal(loid)s (Cd, Cr, Cu, Ni, Pb, Zn, As). We investigated the samples from sites supposedly affected the most by the local pollution sources using mineralogical techniques (XRD, SEM/EDS) to understand the solid speciation of the contaminants as the crucial factor affecting their release. Although the bulk composition was defined by common silicates and oxides that are rather resistant to leaching, the presence of tiny Ni, Pb, and/or Zn sulfate-like droplets indicated a potential increase of the solubility of these metals. In vitro tests simulating gastric and lung fluids were used to assess the exposure risk for humans, as well as metal(loid) bioaccessibility. Based on the results, the potential risk for the observed age group (3-year-old children) could be recognized, particularly in the cases of As, Pb and Cd for both oral and inhalation exposure. Arsenic exhibits high bioaccessibility (7.13-79.7%, with the median values of 10.6 and 15.6 for SGL and SLF, respectively), high daily intake (1.4- to 8.5-fold higher than the tolerable daily intake) and high concentrations in atmospheric PM10 (2.5 times the tolerable concentration in air). In contrast, Ni exceeded tolerable concentrations in the atmosphere up to 20-fold, but its bioaccessibility remained relatively low (0.1-22%), and Ni did not pose a major threat to human health. Cadmium, Pb and As originating from industrial activities and domestic heating have been suggested to be the most important pollutants (tolerable daily intake was exceeded by up to 74-, 34- and 8-fold for Cd, Pb and As, respectively).

Assessment of biochar and/or nano zero-valent iron for the stabilisation of Zn, Pb and Cd: A temporal study of solid phase geochemistry under changing soil conditions.

The remediation of a soil contaminated with Zn, Pb and Cd was tested by using biochar (BC), nano zero-valent iron (nZVI) and a combination of these two (BC + nZVI). Each amendment was individually applied to the soil at 2 wt%. We tested the influence of (i) the used amendments, (ii) time, and (iii) soil moisture conditions on the metal availability and soil physico-chemical parameters using various extraction methods, as well as soil pore water samplings. We found that metal availability was mainly affected by pH under the influence of time and water content. Among the tested treatments, BC was the most successful, resulting in the lowest amounts of the target metals in the pore water and the smallest temporal changes in metal concentrations and pH in the soil. The use of nZVI efficiently decreased water-extractable Pb in the short- and long-term. The BC + nZVI treatment also yielded promising results regarding the immobilisation of the studied metals. Time provoked a general decrease in pH, which occasionally increased the available metal concentrations. Raising the soil water content increased the pH and subsequently lowered the available metal concentrations in the pore water. The mechanisms of metal stabilisation were further investigated by SEM/EDS. The results indicated that the used soil amendments enhanced the binding of Zn, Pb, and Cd on Fe/Mn/Al oxides/hydroxides, which in turn resulted in the stabilisation of the target metals.

Seasonal fluctuations of Zn, Pb, As and Cd contents in the biomass of selected grass species growing on contaminated soils: Implications for in situ phytostabilization.

Phytostabilization aims to immobilize contaminants at the rhizosphere level using the root system of adapted plants. In order to exploit wild grasses with potential for phytostabilization, a screening throughout the year was conducted at a site contaminated by Pb and Zn. Three plant species were chosen: Agrostis capillaris, Arrhenatherum elatius and Calamagrostis epigeios. Rhizospheric soil and biomass was used for chemical characterization. Above- and below-ground was analyzed. For each sample, arbuscular mycorrhiza fungi colonization was determined. The highest concentrations of Pb were found in the A. capillaris rhizosphere (3417 mg kg-1), and in A. elatius for Zn (3876 mg kg-1). CaCl2-extractable Zn in the rhizosphere of C. epigeios was the lowest and Pb was lower for A. elatius. CaCl2-extractable Cd was neither species-dependent nor time-dependent. Arsenic was not species-dependent. The fractionation of target elements did not show differences between separate sampling campaigns and Pb was the only element that showed differences during the year. A. capillaris showed the best capacity to take up elements. The colonization by AMF did not show significant differences for different sampling times, or interactions between time and species, however differences were found for different species, i.e., C. epigeios showed significantly lower colonization by arbuscular mycorrhiza fungi. Our results indicate that A. capillaris appears to be a good indigenous candidate for phytostabilization.

The role of soil components in synthetic mixtures during the adsorption and speciation changes of Cr(VI): Conjunction of the modeling approach with spectroscopic and isotopic investigations.

This study investigates redox transitions associated with the adsorption of Cr(VI) on commonly occurring soil components (silicates, oxides and humic acids) and their synthetic mixtures by coupling the mechanistic surface complexation modeling with spectroscopic and isotopic analyses. The mixtures of soil components were prepared to reflect the composition of the real anthroposol sample, determined by X-ray Powder Diffraction (XRD), total organic carbon (TOC) measurement and extraction methods. The effect of different initial Cr(VI) concentrations (2×10-2, 5×10-4, 10-4, 10-5, and 10-6M), background electrolyte (10-3, 10-2, and 10-1M KNO3), pH values (3-9), and sorbate/sorbent ratios (2g/L - 20g/L) were investigated. Maghemite and ferrihydrite were confirmed to be the main phases controlling Cr(VI) adsorption with increasing Cr(VI) concentration. Humic acids were primarily responsible for Cr(VI) reduction, especially at low pH values. The reduction of Cr(VI) was also proved in case of illite and kaolinite by XAS and isotopic analyses. Illite revealed higher reduction capacity in comparison with kaolinite based on XAS measurements. Chromium isotopic fractionation, resulting from Cr(VI) reduction, was the highest in the case of humic acids, followed by kaolinite and illite. However, a dissolution of intrinsic Cr originally present within kaolinite and illite might affect the final Cr isotopic composition of the supernatants due to its different Cr isotopic signature. In general, the combination of three different approaches was confirmed to offer more comprehensive information about Cr(VI) adsorption and/or reduction in soils. Detailed studies using soil mixtures can help to predict how the soil components affect Cr(VI) behavior in natural soils and possibly could improve the environmental remediation processes.