A high-resolution soil sampling has been applied to two forest podzols (ACB-I and ACB-II) from SW Europe in order to investigate the soil components and processes influencing the content, accumulation and vertical distribution of Hg. Total Hg contents (THg) were 28.0 and 23.6 μg kg⁻¹ in A horizons of ACB-I and ACB-II, then they strongly decreased in the E horizons and peaked in the Bhs horizons of both soils (55.3 and 63.0 μg kg⁻¹). THg decreased again in BwC horizons to 17.0 and 39.8 μg kg⁻¹. The Bhs horizons accounted for 46 and 38% of the total Hg stored (ACB-I and ACB-II, respectively). Principal component analysis (PCA) and principal components regression (PCR), i.e. using the extracted components as predictors, allowed to distinguish the soil components that accounted for Hg accumulation in each horizon. The obtained model accurately predicted accumulated Hg (R² = 0.845) through four principal components (PCs). In A horizons, Hg distribution was controlled by fresh soil organic matter (PC4), whereas in E horizons the negative values of all PCs were consistent with the absence of components able to retain Hg and the corresponding very low THg concentrations. Maximum THg contents in Bhs horizons coincided with the highest peaks of reactive Fe and Al compounds (PC1 and PC2) and secondary crystalline minerals (PC3) in both soils. The THg distribution in the deepest horizons (Bw and BwC) seemed to be influenced by other pedogenetic processes than those operating in the upper part of the profile (A, E and Bhs horizons). Our findings confirm the importance of soils in the global Hg cycling, as they exhibit significant Hg pools in horizons below the uppermost O and A horizons, preventing its mobilization to other environmental compartments.

The sorption behaviour of three perfluoroalkyl substances (PFASs), namely perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorohexane sulfonic acid (PFHxS), was determined on 28 tropical soils. Tropical soils are often highly weathered, richer in sesquioxides than temperate soils and may contain variable charge minerals. There are little data on sorption of PFASs in tropical soils. The highest Kd values were found for PFOS with mean values ranging from 0 to 31.6 L/kg. The Kd values for PFOA and PFHxS ranged from 0 to 4.9 L/kg and from 0 to 5.6 L/kg, respectively. While these values are in the range of literature sorption data, the average Kd values for PFOS and PFOA from the literature were 3.7 times and 3.6 times higher, respectively, than those measured in this study. Stepwise regression analysis did explain some of the variance, but with different explanatory variables for the different PFASs. The main soil properties explaining sorption for PFOS and PFOA were oxalate-extractable Al and pH, and for PFHxS was pH.

In this study, comparative effects of foliar application of ceria nanoparticles (NPs) and Ce3+ ions on common bean plants were investigated. Soil grown bean seedlings were exposed to ceria NPs and Ce3+ ions at 0, 40, 80, and 160 mg Ce·L−1 every other day at the vegetative growth stage for 17 d. The plants were harvested 47 d after the last treatment. Performed analyses involved growth, physiological and biochemical parameters of the plants and nutritional quality of the pods. Ceria NPs at 40 mg Ce·L−1 increased dry weight of the plants by 51.8% over the control. Neither ceria NPs nor Ce3+ ions significantly affected other vegetative growth parameters. Pod yields and nutrient contents except for several mineral elements were also not significantly different among groups. Compared to control, pods from ceria NPs at 80 mg Ce·L−1 had significantly less S and Mn. At 40 and 80 mg Ce·L−1, ceria NPs reduced pod Mo by 27% and 21%, while Ce3+ ions elevated Mo contents by 20% and 18%, respectively, compared with control. Ce3+ ions at 80 and 160 mg Ce·L−1 significantly increased pod Zn by 25% and 120%, respectively, compared with control. At the end of the experiment, Ce3+ ions at 40, 80, and 160 mg Ce·L−1 increased contents of malondialdehyde (MDA) by 46%, 65%, and 82% respectively as compared with control. While ceria NPs led to a significant increase of MDA level only at the highest concentration. X-ray absorption near edge structure (XANES) analysis of the leaf samples revealed that both ceria NPs and Ce3+ ions kept their original chemical species after foliar applications, suggesting the observed effects of ceria NPs and Ce3+ ions on the plants were probably due to their nano-specific properties and ionic properties respectively.

Electron transfer capacities (ETC) of humic-like acids (HLA) and their effects on dechlorination are dependent on their redox-active properties. Aging and minerals can affect the chemical compositions and structures of HLA. However, the underlying mechanism and the impacts on the dechlorination capacities of HLA are poorly understood. We investigated how redox properties change in association with the intrinsic chemical natures and exterior minerals of the HLA extracted from landfilled solid wastes. Furthermore, the ETC of the landfill-derived HLA could be strengthened by increasing landfill age and demineralization, thereby facilitating the dechlorination of pentachlorophenol (PCP). The HLA molecules started to polymerize aromatic macromolecules during landfilling, leading to an increase in ETC and dechlorination capacities. Macromolecular HLA were dissociated to smaller molecules and exposed more aromatic and carboxyl groups when separated from minerals, which enhanced the ETC and the dechlorination abilities of the HLA. Microbial-mediated dechlorination was an effective way to degrade PCP, and almost 80% of the PCP was transformed after 40 days of demineralized HLA and Shewanella oneidensis MR-1 incubation. The demineralization and aging further facilitated the microbial-mediated PCP dechlorination. The findings provide a scientific base for improving in-situ bioremediation of chlorinated compound-contaminated soils using freshly synthesized HLA.

While determining the uranium concentration in the rock (background level) and soils on the Iberian Massif of western Spain, several geochemical anomalies were observed. The uranium concentration was much higher than the geochemical levels at these locations, and several uranium minerals were detected. The proposed uranium background levels for natural soils in the west of Salamanca Province (Spain) are 29.8 mg kg−1 in granitic rock and 71.2 mg kg−1 in slate. However, the soil near the tailings of abandoned mines exhibited much higher concentrations, between 207.2 and 542.4 mg kg−1.The calculation of different pollution indexes (Pollution Factor and Geo-accumulation Index), which reveal the conditions in the superficial horizons of the natural soils, indicated that a good percentage of the studied samples (16.7–56.5%) are moderately contaminated. The spatial distribution of the uranium content in natural soils was analysed by applying the inverse distance weighted method.The distribution of uranium through the horizons of the soils shows a tendency to accumulate in the horizons with the highest clay content. The leaching of uranium from the upper horizons and accumulation in the lower horizons of the soil could be considered a process for natural attenuation of the surface impacts of this radiogenic element in the environment. Environmental restoration is proposed in the areas close to the abandoned mining facilities of this region, given the high concentration of uranium. First, all the tailings and other mining waste would be covered with a layer of impermeable material to prevent leaching by runoff. Then, a layer of topsoil with organic amendments would be added, followed by revegetation with herbaceous plants to prevent surface erosion.

Mining and metallurgy generate residues that may contain thallium (Tl), a highly toxic metal, for which it is currently not feasible to determine its geochemical speciation through X-ray absorption spectroscopy due to a combination of very low contents and the interference of accompanying high arsenic contents. Therefore, fractionation studies in residues and soils are required to analyze the mobility and bioavailability of this metal, which in turn provide information to infer its speciation. For this purpose, in this work a modification of the BCR procedure was applied to residues and contaminated soils from three mining zones of Mexico and two mining zones of Spain, spanning samples with acidic to alkaline pH values.The Tl extraction procedure consisted of the following fractions: (1) water-extractable, (2) easily exchangeable and associated to carbonates, associated to (3) poorly-crystalline and (4) crystalline Fe and Mn oxyhydroxides, and (5) associated to organic matter and sulfides; and finally a residual fraction as associated to refractory primary and other secondary minerals. The extracted contents were analyzed by Inductively-Coupled Plasma with Mass Spectrometry.Surprisingly, water-soluble, in Tl(I) oxidation state, was detected in most areas, regardless of the pH, a fact that has not been reported before in these environments, and alerts to potential health risks not previously identified. Most of the samples from a metallurgy area showed high levels of Tl in non-residual fractions and a strong correlation was obtained between extracted Mn and Tl in the third fraction, suggesting its association to poorly crystalline manganese oxides. In the majority of samples from purely mining environments, most of the Tl was found in the residual fraction, most probably bound to alumino-silicate minerals. The remaining Tl fractions were extracted mainly associated to the reducible mineral fractions, and in one case also in the oxidizable fraction (presumably associated to sulfides).Capsule: Soluble Tl(I) was found in all soil samples contaminated with either mining or metallurgical wastes. Additionally, in those affected by metallurgical wastes a very strong Tl-Mn correlation was found.

Emission of hazardous trace elements (HTEs) from energy production is receiving much attention due to concerns about the toxicity to the ecosystem and human health. This study presented new field measurement data on the HTEs partitioning behavior and size-segregated elemental compositions of gaseous particular matter (PM) generated from a commercial circulating fluidized bed (CFB) power plant. Mineralogical and morphological characteristics of combustion ash and PM2.5 (particle diameter less than 2.5 μm) were determined by X-ray diffractometer (XRD) and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS). Functional groups alteration during CFB combustion was characterized by Fourier transform infrared spectroscopy (FTIR). The presence of aliphatic hydrogen at 2910 cm−1 and 2847 cm−1 in the PM2.5 suggested that the aliphatic carbon-rich volatiles were absorbed on the fine particles with large surface area. Fine fly ash (PM2.5) occurred as irregular glass particles or/and as unburned carbon. The typical irregular particles were mainly composed of Al-Si-Ca or Al-Si-Fe phases. The enrichment behavior of HTEs was determined for the airborne size-segregated particular matter. Elemental occurrences, combustion temperature, unburnt carbon, and limestone additives during CFB combustion were critical in the transformation behavior of HTEs. The total potentially mobile pollutants that exit the CFB power plant every year were estimated as follows: 0.22 tons of Cr, 0.12 tons of Co, 0.73 tons of Ni, 0.04 tons of As, 0.07 tons of Se, 3.95 kg of Cd, and 3.34 kg of Sb.

The alteration behavior of minerals and hazardous elements during simulated combustion (100–1200 °C) of a raw coal collected from a power plant were studied. Thermogravimetric analysis indicated that there were mainly four alteration stages during coal combustion. The transformation behavior of mineral phases of raw coal, which were detected by X-ray polycrystalline diffraction (XRD) technique, mainly relied on the combustion temperature. A series of changes were derived from the intensities of mineral (e.g. clays) diffraction peaks when temperature surpassed 600 °C. Mineral phases tended to be simple and collapsed to amorphous glass when temperature reached up to 1200 °C. The characteristics of functional groups for raw coal and high-temperature (1200 °C) ash studied by Fourier transform infrared spectroscopy (FTIR) were in accordance with the result obtained from XRD analysis. The volatilization ratios of Co, Cr, Ni and V increased consistently with the increase of combustion temperature, suggesting these elements were gradually released from the organic matter and inorganic minerals of coal.