This study describes the development of a sequential extraction procedure for the evaluation of metal nanoparticle mobility and bioaccessibility in soils. The procedure, that was developed using gold nanoparticles (AuNPs) as model species, relies on the fractionation of nanoparticles by sequentially dissolving soil matrix components (carbonates, metal oxides, organic matter and mineral phases) in order to release the entrapped nanoparticle species in the extract solution. By summing up the concentration of AuNPs recovered in each fraction it was found that 93.5% of the spiked AuNP concentration could be recovered which satisfactorily represents the nominal AuNP concentration in the soil. The efficiency of the procedure was found to depend on several procedural artifacts related to the separation of AuNPs from soil colloids and the reactivity of the extraction reagents with AuNPs and their precursor metal ions. Based on the results obtained a protocol for the speciation of the AuNPs and Au ions in the soil sample was also developed. The results of the study show that both AuNPs and Au ions are mainly associated with soil organic matter, which significantly reduces their mobility, while a small amount (<10%) is associated with metal oxides which are more mobile and potentially bioaccessible. The developed procedure provides a springboard for further development of sequential extraction procedures of metal nanoparticles in soils that could be used to assess both the exposure and release of metal nanoparticles and their precursor metal ions in the environment (as total extractable concentration) as well as provide evidence regarding their bioaccessibility and potential bioavailability by determining the concentration of nanoparticles in each specific soil fraction.

Soils from Aveiro, Glasgow, Ljubljana, Sevilla and Torino have been investigated in view of their potential for translocation of potentially toxic elements (PTE) to the atmosphere. Soils were partitioned into five size fractions and Cr, Cu, Ni, Pb and Zn were measured in the fractions and the whole soil. All PTE concentrated in the <10 μm fraction. Cr and Ni concentrated also in the coarse fraction, indicating a lithogenic contribution. An accumulation factor (AF) was calculated for the <2 and <10 μm fraction. The AF values indicate that the accumulation in the finer fractions is higher where the overall contamination is lower. AF for Cr and Ni are particularly low in Glasgow and Torino. An inverse relationship was found between the AF of some metals and the percentage of <10 μm particles that could be of use in risk assessment or remediation practices.

Chemically oxidative removal of polycyclic aromatic hydrocarbons (PAHs) in soil is related to their occurrence state. Whether the heterogeneity of natural organic matter has an effect on the occurrence of PAHs in soil and, if there is an effect, on the oxidative removal efficiency of PAHs remains unknown. In this study, the removal efficiencies of 16 priority PAHs aged in humic acids (HAs) of different soil aggregate fractions by various oxidants were investigated by combining soil fractionation and microreaction experiments. Results showed that the accumulations of PAHs in particulate HA (P-HA) and microaggregate occluded HA (MO-HA) mainly occurred in the early period of the aging time frame. In contrast, PAH accumulation in non-aggregated silt and clay associated HA (NASCA-HA) was relatively slow and tended to saturate in the late period of the aging time frame. The cumulative contents of PAHs throughout the entire aging period in MO-HA and NASCA-HA were significantly greater than that in P-HA. The aged PAHs in P-HA and NASCA-HA exhibited the highest and lowest removal efficiencies, respectively. This ranking was mainly governed by the molecular size and polarity of HAs. Sodium persulfate and potassium permanganate had the highest removal efficiencies in total PAHs in HAs, with average efficiencies of 85.8% and 79.1%, respectively, in P-HA. Hydrogen peroxide had the lowest degradation efficiency in PAHs. In particular, the degradation efficiency of total PAHs in NASCA-HA was lowered to 31.0%. PAH congeners in HAs showed a large difference in oxidative removal efficiency. Low-ring PAH was more easily degraded than medium- and high-ring PAHs, and in most treatments, fluoranthene and pyrene in the medium ring and benzo[a]pyrene in the high ring demonstrated higher efficiencies than other PAHs with the same number of rings. Our findings are useful in promoting the accurate and green remediation of PAH-contaminated soils.

Since the introduction of standardized nematode toxicity assays by the American Society for Testing and Materials (ASTM) and International Organization for Standardization (ISO), many studies have reported their use. Given that the currently used standardized nematode toxicity assays have certain limitations, in this study, we examined the use of a novel nematode offspring counting assay for evaluating soil ecotoxicity based on a previous soil-agar isolation method used to recover live adult nematodes. In this new assay, adult Caenorhabditis elegans were exposed to soil using a standardized toxicity assay procedure, and the resulting offspring in test soils attracted by a microbial food source in agar plates were counted. This method differs from previously used assays in terms of its endpoint, namely, the number of nematode offspring. The applicability of the bioassay was demonstrated using metal-spiked soils, which revealed metal concentration-dependent responses, and with 36 field soil samples characterized by different physicochemical properties and containing various metals. Principal component analysis revealed that texture fraction (clay, sand, and silt) and electrical conductivity values were the main factors influencing the nematode offspring counting assay, and these findings warrant further investigation. The nematode offspring counting assay is a rapid and simple process that can provide multi-directional toxicity assessment when used in conjunction with other standard methods.

Presence of microorganisms in soils strongly affects mobility of metals. This fact is often excluded when mobile metal fraction in soil is studied using extraction procedures. Thus, the first objective of this paper was to evaluate strain Aspergillus niger’s exometabolites contribution on aluminium mobilization. Fungal exudates collected in various time intervals during cultivation were analyzed and used for two-step bio-assisted extraction of alumina and gibbsite. Oxalic, citric and gluconic acids were identified in collected culture media with concentrations up to 68.4, 2.0 and 16.5 mmol L−1, respectively. These exometabolites proved to be the most efficient agents in mobile aluminium fraction extraction with aluminium extraction efficiency reaching almost 2.2%. However, fungal cultivation is time demanding process. Therefore, the second objective was to simplify acquisition of equally efficient extracting agent by chemically mimicking composition of main organic acid components of fungal exudates. This was successfully achieved with organic acids mixture prepared according to medium composition collected on the 12th day of Aspergillus niger cultivation. This mixture extracted similar amounts of aluminium from alumina compared to culture medium. The aluminium extraction efficiency from gibbsite by organic acids mixture was lesser than 0.09% which is most likely because of more rigid mineral structure of gibbsite compared to alumina. The prepared organic acid mixture was then successfully applied for aluminium extraction from soil samples and compared to standard single step extraction techniques. This showed there is at least 2.9 times higher content of mobile aluminium fraction in soils than it was previously considered, if contribution of microbial metabolites is considered in extraction procedures. Thus, our contribution highlights the significance of fungal metabolites in aluminium extraction from environmental samples, but it also simplifies the extraction procedure inspired by bio-assisted extraction of aluminium by common soil fungus A. niger.

Soils containing high concentrations of metals were treated using a soil washing process. The hypothesis was that metals could be concentrated in a single or small number of fine fractions which could be removed and disposed of to treat the contaminated soil. Lead and zinc were shown to be distributed over the > 4000, 2000–4000, 600–2000, 180–600, 38–180, 38–23, and < 9 µm soil size fractions. The study demonstrated that only one of four of the composites tested, generated a metal-rich fraction as a result of washing and soil fractionation. Using a scaling approach, with a laboratory prototype, this study demonstrates that lead and zinc contamination across the site were not able to be concentrated into any size fraction. Further, the metals could not be concentrated to any commercially viable extent to enable the development of a remediation strategy. The approach illustrated how costs can be contained in developing full-scale remediation processes through using a staged process based on the principles of prototyping and scaling.

For remediating polluted soils, phytoextraction of metals received considerable attention in recent years, although slow removal of metals remained a major constraint in this approach. We, therefore, studied the effect of selected organic and inorganic amendments on the solubility of zinc (Zn), cadmium (Cd), and lead (Pb) in polluted soil and enhancing the efficacy of phytoextraction of these metals by Indian mustard (Brassica juncea cv. Pusa Vijay). For this purpose, a greenhouse experiment was conducted using a metal-polluted soil to evaluate the effect of amendments, viz. green manure (T2), EDTA (T3), sulfur (S)+S oxidizing bacteria (Thiobacillus spp.) (T4), metal-solubilizing bacteria (Pseudomonas spp.) (T5), and green manure + metal-solubilizing bacteria (T6), on solubility and bioavailability of Zn, Cd, and Pb. Distribution of metals in different soil fractions revealed that Cd content in water soluble + exchangeable fraction increased to the extent of 34.1, 523, 133, 123, and 75.8% in T2, T3, T4, T5, and T6 treatments, respectively, over control (T1). Cadmium concentrations in soil solution as extracted by Rhizon sampler were recorded as 3.78, 88.1, 11.2, 6.29, and 4.27 μg L⁻¹in T2, T3, T4, T5, and T6, respectively, whereas soil solution concentration of Cd in T1 was 0.99 μg L⁻¹. Activities of Cd (pCd²⁺) in Baker soil extract were 12.2, 10.9, 6.72, 7.74, 7.67, and 7.05 for T1, T2, T3, T4, T5, and T6, respectively. Cadmium contents in shoot were recorded as 2.74, 3.12, 4.03, 4.55, 4.68, and 4.63 mg kg⁻¹ in T1, T2, T3, T4, T5, and T6 treatments, respectively. Similar trend in Zn and Pb content with different magnitude was also observed across the different amendments. Cadmium uptake by shoot of mustard was enhanced to the extent of 125, 62.5, 175, 175, and 212% grown on T2-, T3-, T4-, T5-, and T6-treated soil, respectively, over T1. By and large, free ion activity of metals as measured by Baker soil test proved to be the most effective index for predicting Zn, Cd, and Pb content in shoot of mustard, followed by EDTA and DTPA. Among the metal fractions, only water soluble + exchangeable metal contributed positively towards plant uptake, which explained the variation in shoot Zn, Cd, and Pb content to the extent of 74, 81, and 87%, respectively, along with other soil metal fractions. Risk to human health for intake of metals through the consumption of leafy vegetable (mustard) grown on polluted soil in terms of hazard quotient (HQ) ranged from 0.64 to 1.10 for Cd and 0.11 to 0.34 for Pb, thus rendering mustard unfit for the human consumption. Novelty of the study mainly consisted of the use of natural means and microorganisms for enhancing solubility of metals in soil with the ultimate aim of hastening the phytoremediation.

The objective of this study was to evaluate the influence of the soil parameters (particle size, initial contamination level, etc.) on the performances of an attrition process to remove As, Cr, Cu, pentachlorophenol (PCP) and dioxins and furans (PCDD/F). Five different contaminated soils were wet-sieved to isolate five soil fractions (< 0.250, 0.250–1, 1–4, 4–12 and > 12 mm). Five attrition steps of 20 min each, carried out in the presence of a biodegradable surfactant ([BW] = 2%, w w⁻¹) at room temperature with a pulp density fixed at 40% (w w⁻¹), were applied to the coarse soil fractions (> 0.250 mm) of different soils. The results showed good performances of the attrition process to simultaneously remove PCP and PCDD/F from contaminated soil fractions initially containing between 1.1 and 13 mg of PCP kg⁻¹ (dry basis) and between 1795 and 5720 ng TEQ of PCDD/F kg⁻¹. It appeared that the amounts of contaminants removed were significantly correlated (p value < 0.05, R ² = 0.96) with the initial amounts of PCP and PCDD/F, regardless of the particle size of the soils studied. The nature of the soil (granulometric distribution, pH, total organic carbon (TOC) (organic matter) and diverse industrial origin) slightly and negatively influenced the efficiency of organic contaminants removals using attrition. However, the attrition treatment allowed an efficient removal of both PCP and PCDD/F from the coarse fraction of contaminated soil, despite the nature of the soil.

This study investigated the effect of selenate and selenite application on the distribution, transformation of selenium (Se) fractions in soil, as well as the accumulation and availability of Se in each part of wheat plants. A pot experiment was conducted using different concentrations of exogenous selenite or selenate (0.5, 1, 2.5, 5, and 10 mg Se kg⁻¹ soil). Sequential extraction was used to determine the Se fractions in soil, and different models were used to study the behavior of Se in soil and its availability to wheat. Results showed that the distribution and availability of Se in soil and its accumulation in wheat affected both by Se concentrations and forms of exogenous Se. In selenite-treated soil, the proportion of exchangeable and carbonate-bound Se (EXC–Se) (21–42%) fraction increased compared to that in control (12%), while organic matter-bound Se (OM–Se) (23–33%) and Fe–Mn oxide-bound Se (FMO–Se) (11–15%) fractions decreased compare with those in control (37 and 32%, respectively). In selenate-treated soil, soluble-Se (SOL–Se) fraction (30–54%) increased and the OM–Se (9.8–20%) and FMO–Se (4.7–14.2%) fractions decreased compared with those in control. Residual Se (RES–Se) fraction was increased for selenite (7.4–13.4%) and selenate (12–20%) treatments compared with that in control (6.5%). In comparison with control, the available Se (SOL−Se + EXC−Se) fraction increased for both selenite (32–47%) or selenate (54–72%) treatments. Moreover, at the same rate of Se application, Se availability was higher in wheat grown in selenate-treated soils than that in selenite-treated soils. The redistribution index (U ₜₛ) of Se increased from 1 (in control) to 1.2–1.9 and 1.5–2 for selenite and selenate treatments, respectively; additionally, the mobility factor (MF) in selenate-treated soil was 40–90% higher than that in selenite-treated soil. Furthermore, relative bonding intensity (I R) for both selenite (0.38–0.45) and selenate treatment (0.33–0.41) decreased compared with that in control (0.55). These differences indicated that selenite and selenate varied in terms of fixation capacities in soil, in transformation and distribution of Se in soil fractions, and in their availability to plants. The results of Michaelis–Menten equation demonstrated the high affinity of leaf to selenate, and the high affinity of roots and grains to selenite. Selenate was dominant in nearly all parts of wheat plants and in each application level. However, the affinity of selenite to wheat grains suggests that selenite is a useful Se fertilizer that must be considered in biofortification programs. In-depth studies at the pot and field scales by using different wheat varieties and application methods of Se in different ecological zones must be conducted to elucidate the mechanism and biochemical properties of Se in soil-plant system and ultimately produce Se-rich staple foods.