Valorization of steelmaking slag and coal fly ash as amendments in combination with Betula pubescens for the remediation of a highly As- and Hg-polluted mining soil.

Soil pollution by As and Hg is a pressing environmental issue given their persistence. The intricate removal processes and subsequent accumulation of these elements in soil adversely impact plant growth and pose risks to other organisms in the food chain and to underground aquifers. Here we assessed the effectiveness of non-toxic industrial byproducts, namely coal fly ash and steelmaking slag, as soil amendments, both independently and in conjunction with an organic fertilizer. This approach was coupled with a phytoremediation technique involving Betula pubescens to tackle soil highly contaminated. Greenhouse experiments were conducted to evaluate amendments' impact on the growth, physiology, and biochemistry of the plant. Additionally, a permeable barrier made of byproducts was placed beneath the soil to treat leachates. The application of the byproducts reduced pollutant availability, the production of contaminated leachates, and pollutant accumulation in plants, thereby promoting plant development and survival. Conversely, the addition of the fertilizer alone led to an increase in As accumulation in plants and induced the production of antioxidant compounds such as carotenoids and free proline. Notably, all amendments led to increased thiolic compound production without affecting chlorophyll synthesis. While fertilizer application significantly decreased parameters associated with oxidative stress, such as hydrogen peroxide and malondialdehyde, no substantial reduction was observed after byproduct application. Thermal desorption analysis of the byproducts revealed Hg immobilization mechanisms, thereby indicating retention of this metalloid in the form of Hg chloride. In summary, the revalorization of industrial byproducts in the context of the circular economy holds promise for effectively immobilizing metal(loid)s in heavily polluted soils. Additionally, this approach can be enhanced through synergies with phytoremediation.

A novel heuristic tool for selecting the best upgrading conditions for the removal of potentially toxic elements by soil washing.

Here, we propose two-parameter penalized attributive analysis, PPAA-U, a novel heuristic tool for selecting the best upgrading conditions (BUCs) for soil washing. Given a multi-component feed and a specific set of operating conditions, PPAA-U generates a quality index based on how well recoveries for key components are maximized while minimizing the yield. We demonstrate, through the calculation of families of curves, that this quality index is related linearly to recovery and to the inverse of the yield, meaning that reducing yield values is more important than maximizing recovery. To evaluate our method, electrostatic separation at 12 different voltages was carried out on soil samples from an ex-industrial site in Spain. Values of recovery, yield, and grade were analyzed using basic attributive analysis and PPAA-U with and without target-to-distance correction. Both methods identified the same optimal separation voltage, and the power of PPAA-U to correct for high variation in yields and recoveries was observed as a divergence between results produced by each method at low voltages where variation in these values was greatest. PPAA-U thus offers a convenient tool for soil washing optimization, and we suggest that it could be applied successfully to other industrial processes.

Assessment of co-contaminated soil amended by graphene oxide: Effects on pollutants, microbial communities and soil health.

Graphene oxide (GOx) is a nanomaterial with demonstrated capacity to remove metals from water. However, its effects on organic pollutants and metal(loid)s present in polluted soils when used for remediation purposes have not been extensively addressed. Likewise, few studies describe the effects of GOx on edaphic properties and soil biology. In this context, here we assessed the potential of GOx for remediating polluted soil focusing also on different unexplored effects of GOx in soil. To achieve this, we treated soil contaminated with concurrent inorganic (As and metals) and organic pollution (TPH and PAHs), using GOx alone and in combination with nutrients (N and P sources). In both cases increased availability of As and Zn was observed after 90 days, whereas Cu and Hg availability was reduced and the availability of Pb and the concentration of organic pollutants were not significantly affected. The application of GOx on the soil induced a significant and rapid change (within 1 week) in microbial populations, leading to a transient reduction in biodiversity, consistent with the alteration of several soil properties. Concurrently, the combination with nutrients exhibited a distinct behaviour, manifesting a more pronounced and persistent shift in microbial populations without a decrease in biodiversity. On the basis of these findings, GOx emerges as a versatile amendment for soil remediation approaches.

Hg and As pollution in the soil-plant system evaluated by combining multispectral UAV-RS, geochemical survey and machine learning.

The combination of a low-density geochemical survey, multispectral data obtained with Unmanned Aerial Vehicle-Remote Sensing (UAV-RS), and a machine learning technique was tested in the search for a statistically robust prediction of contaminant distribution in soil and vegetation, for zones with a highly variable pollutant load. To this end, a novel methodology was devised by means of a limited geochemical study of topsoil and vegetation combined with multispectral data obtained by UAV-RS. The methodology was verified in an area affected by Hg and As contamination that typifies abandoned mining-metallurgy sites in recent decades. A broad selection of spectral indices were calculated to evaluate soil-plant system response, and four machine learning techniques (Multiple Linear Regression, Random Forest, Generalized Boosted Models, and Multivariate Adaptive Regression Spline) were tested to obtain robust statistical models. Random Forest (RF) provided the best non-biased models for As and Hg concentration in soil and vegetation, with R2 and rRMSE (%) ranging from 0.501 to 0.630 and from 180.72 to 46.31, respectively, and with acceptable values for RPD and RPIQ statistics. The prediction and mapping of contaminant content and distribution in the study area were well enough adjusted to the geochemical data and revealed superior accuracy for As than Hg, and for vegetation than topsoil. The results were more precise than those obtained in comparable studies that applied satellite or spectrometry data. In conclusion, the methodology presented emerges as a powerful tool for studies addressing soil and vegetation pollution and an alternative approach to classical geochemical studies, which are time-consuming and expensive.

Magnetic separation for arsenic and metal recovery from polluted sediments within a circular economy.

Several metals and metalloids (e.g., As, Cd, Cu, Pb, Zn) are toxic at low concentrations, thus their presence in sediments can raise environmental concern. However, these elements can be of economic interest, and several techniques have been used for their recovery and some of them have been widely applied to mining or to industrial soils, but not to sediments. In this work, wet high-intensity magnetic separation (WHIMS) was applied for As, Cd, Cu, Pb and Zn recovery from polluted sediments. A composite sample of 50 kg was taken in the Avilés estuary (Asturias, North Spain) with element concentrations above the legislation limits. Element distribution was assessed using wet-sieving and ICP-MS analysis, revealing that the 125-500 µm grain-size fraction accounts for the 62 w% of the material and that element concentration in this fraction is lower than in the other grain size fractions. Subsequently, WHIMS was applied at three different voltage intensities for the 125-500 µm and <125 µm fractions, revealing excellent recovery ratios, especially for the coarser material. Furthermore, magnetic property measurements coupled to microscopy analysis revealed that the success of the technique derives from concentrating metal-enriched iron oxides particles (ferro- and para-magnetic material) in a mixture of quartz and other minerals (diamagnetic particles). These results indicate the feasibility of the magnetic separation for metal and metalloid recovery from polluted sediments, and thus offer a double benefit of coastal area restoration and valuable material recovery in the context of a circular economy.

Antagonistic Cd and Zn isotope behavior in the extracted soil fractions from industrial areas.

The remobilization of metals accumulated in contaminated soils poses a threat to humans and ecosystems in general. Tracing metal fractionation provides valuable information for understanding the remobilization processes in smelting areas. Based on the difference between the isotopic system of Cd and Zn, this work aimed to couple isotope data and their leachability to identify possible remobilization processes in several soil types and land uses. For soil samples, the δ66/64Zn values ranged from 0.12 ± 0.05‰ to 0.28 ± 0.05‰ in Avilés (Spain) and from - 0.09 ± 0.05‰ to - 0.21 ± 0.05‰ in Príbram (Czech Republic), and the δ114/110Cd ranged from - 0.13 ± 0.05‰ to 0.01 ± 0.04‰ in Avilés and from - 0.86 ± 0.27‰ to - 0.24 ± 0.05‰ in Príbram. The metal fractions extracted using chemical extractions were always enriched in heavier Cd isotopes whilst Zn isotope systematics exhibited light or heavy enrichment according to the soil type and land uses. Coupling Zn and Cd systematics provided a tool for deciphering the mechanisms behind the remobilization processes: leaching of the anthropogenic materials and/or metal redistribution within the soil components prior to remobilization.

Zero valent iron nanoparticles and organic fertilizer assisted phytoremediation in a mining soil: Arsenic and mercury accumulation and effects on the antioxidative system of Medicago sativa L.

Zero valent iron nanoparticles (nZVI) attract interest given their effectiveness in soil remediation. However, little attention has been given to their impacts on plants. Likewise, although fertilizers are commonly used to enhance phytoremediation, their effects on As mobilization, resulting in potential toxic effects, require further study. In this context, we examined the impact of As and Hg accumulation on the antioxidative system of Medicago sativa grown in a soil amended with organic fertilizer and/or nZVI. The experiment consisted of 60 pots. Plants were pre-grown and transferred to pots, which were withdrawn along time for monitoring purposes. As and Hg were monitored in the soil-plant system, and parameters related to oxidative stress, photosynthetic pigments, and non-protein thiol compounds (NPTs) were measured. In general, the application of nZVI immobilized As in soil and increased Hg accumulation in the plant, although it surprisingly decreased oxidative stress. Plants in nZVI-treated soil also showed an increase in NPT content in roots. In contrast, the application of the fertilizer mobilized As, thereby improving bioaccumulation factors. However, when combining fertilizer with nZVI, the As accumulation is mitigated. This observation reveals that simultaneous amendments are a promising approach for soil stabilization and the phytomanagement of As/Hg-polluted soils.

Goethite-based carbon foam nanocomposites for concurrently immobilizing arsenic and metals in polluted soils.

Although different amendments have been used for the immobilization of metals and metalloids in contaminated soils, in most of them there are still important challenges that need to be faced in order to achieve an optimal result. In this work, a new material based on a carbon foam impregnated with goethite nanoneedles has been developed with the aim of evaluating its effect on the mobility and availability of As, Cd, Cu, Pb and Zn in an industrial soil. For this purpose, leaching, sequential extraction and phytotoxicity studies have been carried out. The results were compared with the same carbon foam without goethite impregnation. When the soil was treated with goethite-based carbon foam nanocomposite, the mobility of metal(loid)s was markedly reduced, with the exception of Zn, which showed moderate immobilization. The presence of acid groups on the surface of the carbon foam, together with a high surface area, led to a strong immobilization of pollutants. Moreover, the modification of the foams using goethite nanoneedles, imply that the novel nanocomposite obtained is effective to remediate simultaneously metal and metalloid-polluted soils, without any relevant effect on soil toxicity.

Multiple pollution sources unravelled by environmental forensics techniques and multivariate statistics.

Industrial sites affected by anthropogenic contamination, both past and present-day, commonly have intricate pollutant patterns, and source discrimination can be thus highly challenging. To this goal, this paper presents a novel approach combining multivariate statistics and environmental forensic techniques. The efficiency of this methodology was exemplified in a severely polluted estuarine area (Avilés, Spain), where factor analysis and clustering were performed to identify sub-areas with distinct geochemical behaviour. Once six clusters were defined and a pollution index applied, forensic tools revealed that the As speciation, Pb isotopes, and PAHs molecular ratios were useful to categorise the cluster groups on the basis of distinct pollution sources: Zn-smelting, coaly particles and waste disposal. Overall, this methodology offers valuable insight into pollution sources identification, which can be extended to comparable scenarios of complexly polluted environmental compartments. The information gathered using this approach is also important for the planning of risk assessment procedures and potential remediation strategies.

Bioremediation of a polymetallic, arsenic-dominated reverse osmosis reject stream.

The treatment of metal-laden industrial effluents by reverse osmosis is gaining in popularity worldwide due to its high performance. However, this process generates a polymetallic concentrate (retentate) stream in need of efficient post-treatment prior to environmental discharge. This paper presents results on the bioremediation (in batch mode) of a metal-laden, arsenic-dominated retentate using Shewanella sp. O23S as inoculum. The incubation of the retentate for 14 days under anoxic conditions resulted in the following removal yields: As (8%), Co (11%), Mo (3%), Se (62%), Sb (30%) and Zn (40%). The addition of 1 mmol l-1 cysteine increased the removal rate as follows: As (27%), Co (80%), Mo (78%), Se (88%), Sb (83%) and Zn (90%). The contribution of cysteine as a source of H2 S to enhancing the removal yield was confirmed by its addition after 7 days of incubations initially lacking it. Additionally, the cysteine-sourced H2 S was confirmed by its capture onto headspace-mounted Pb-acetate test strips that were analysed by X-ray diffraction. We show that real metal-laden industrial effluents can be treated to medium-to-high efficiency using a biological system (naturally sourced inocula) and inexpensive reagents (yeast extract, lactate and cysteine).

Benzo[a]pyrene sourcing and abundance in a coal region in transition reveals historical pollution, rendering soil screening levels impractical.

Benzo[a]pyrene (BaP) is a hazardous compound for human health and for environmental compartments. Its transfer and deposition through the atmosphere affects soil quality. In this context, we quantified the content of BaP and other Polycyclic Aromatic Hydrocarbons (PAHs) in the soils of a prominent Coal Region in Transition to test whether the soil screening levels in force are realistic and whether they reflect the complexity of regions closely linked to heavy industries and mining. In this regard, soil screening levels are thresholds often established without considering historical anthropogenic activities that affect soil (diffuse pollution). The 150 soil samples studied showed a notable content of high molecular weight PAHs, and BaP surpassed the threshold levels in practically the entire area. PAH-parent diagrams revealed a relatively homogenous fingerprint of four clusters obtained in a multivariate statistical study. In addition, molecular diagnostic ratios pointed to coal combustion as the main pollution source, whereas only some outliers appeared to be related to specific spills. A BaP threshold was calculated to be 0.24 mg kg-1, over 10 times the limit established in Spain. Finally, a factor analysis revealed a positive correlation of BaP with elements usually emitted in coal combustion processes, such as Tl and V. This observation fosters the hypothesis of a historical and indelible pollution fingerprint in soils whose sources, characteristics and potential environmental and health concerns deserve further attention. All things considered, caution should be taken when using soil screening levels in regions associated with coal exploitation and heavy industry.

Zero valent iron and goethite nanoparticles as new promising remediation techniques for As-polluted soils.

The capacity of two iron-based nanomaterials, namely goethite nanospheres (nGoethite) and zero valent iron nanoparticles (nZVI), to immobilize As in a polluted soil was evaluated and compared. The composition and morphology of the products were studied by energy dispersive X-ray analysis and transmission electron microscopy, while zeta potential and average sizes were determined by dynamic light scattering. To assess As immobilization, soil subsamples were treated with nGoethite or nZVI at a range of Fe doses (0.5%, 2%, 5% and 10%) and then studied by the TCLP test and the Tessier sequential extraction procedure. The influence of both nanoparticles on As speciation was determined, as was impact on soil pH, electrical conductivity, Fe availability and phytotoxicity (watercress germination). For nZVI, notable results were achieved at a dose of 2% (89.5% decrease in As, TCLP test), and no negative effects on soil parameters were detected. Indeed, even soil phytotoxicity was reduced and only at the highest dose was a slight increase in As3+ detected. In contrast, excellent results were obtained for nGoethite at the lowest dose (0.2%) (82.5% decrease in As, TCLP test); however, soil phytotoxicity was increased at higher doses, probably due to a marked enhancement of electrical conductivity. For both types of nanoparticle, slight increases in Fe availability were observed. Thus, our results show that both nZVI and nGoethite have the capacity to effectively immobilize As in this brownfield. The use of lower doses of nGoethite emerges as a promising soil remediation strategy for soils affected by As pollution.

Nanoremediation and long-term monitoring of brownfield soil highly polluted with As and Hg.

In the last decade, several laboratory-scale experiments have shown the use of nanoscale zero-valent iron (nZVI) to be effective in reducing metal(loid) availability in polluted soils. The present study evaluates the capacity of nZVI for reducing the availability of As and Hg in brownfield soils at a pilot scale, and monitors the stability of the immobilization of these contaminants over a 32 month period. To the best of our knowledge, this is the first study to apply nZVI to metal(loid)-polluted soils under field conditions. Two sub-areas (A and B) that differed in pollution load were selected, and a 5 m2 plot was treated with 2.5% nZVI (by weight) in each case (Nanofer 25S, NanoIron). In sub-area A, which had a greater degree of pollution, a second application was performed eight months after the first application. Overall, the treatment significantly reduced the availability of both As and Hg, after only 72 h, although the effectiveness of the treatment was highly dependent on the degree of initial contamination. Sub-area B (with a lower level of pollution) showed the best and most stable immobilization results, with As and Hg in toxicity characteristics leaching procedure (TCLP) extracts decreasing by 70% and 80%, respectively. In comparison, the concentrations of As and Hg in sub-area A decreased by 65% and 50%, respectively. Based on our findings, the use of nZVI at a dose of 2.5% appears to be an effective approach for the remediation of soils at this brownfield site, especially in sub-area B. For sub-area A, a higher dose of nZVI-or its use in combination with other remediation strategies-should be tested.