Rare earth elements (REEs) are typically present as mixtures in the environment, but a quantitative understanding of mixture toxicity and interactions of REEs is still lacking. Here, we examined the toxicity to wheat (Triticum aestivum L.) of Y, La, and Ce when applied individually and in combination. Both concentration addition (CA) and independent action (IA) reference models were used for mixture toxicity analysis because the toxicity mechanisms of REEs remain obscure. Upon single exposure, the EC50s of Y, La, and Ce, expressed as dissolved concentrations, were 1.73 ± 0.24 μM, 2.59 ± 0.23 μM, and 1.50 ± 0.22 μM, respectively. The toxicity measured with relative root elongation followed La < Y ≈ Ce, irrespective of the dose descriptors. The use of CA and IA provided similar estimates of REE mixture interactions and toxicity. When expressed as dissolved metal concentrations, nearly additive effects were observed in Y-La and La-Ce mixtures, while antagonistic interactions were seen in Y-Ce mixtures. When expressed as free metal activities, antagonistic interactions were found for all three binary mixtures. This can be explained by a competitive effect of REEs ions for binding to the active sites of plant roots. The application of a more elaborate MIXTOX model in conjunction with the free ion activities, which incorporates the non-additive interactions and bioavailability-modifying factors, well predicted the mixture toxicity (with >92% of toxicity variations explained). Our results highlighted the importance of considering mixture interactions and subsequent bioavailability in assessing the joint toxicity of REEs.

Waste water of the Kettara village, as well as the abandoned tailings, constitute a potential environmental issue with direct consequences on air, soil, water resources qualities and, on human health. In this paper, experimental investigations examine the environmental impact which is induced by the wastewater, mine tailings and the lithological factors of rocks. This multidisciplinary research allows to i) understand the transfer of the Metallic Trace Elements (selenium, arsenic, nickel and zinc) and sulfate ions in the fractured shales media, ii) to assess the water potability by using the microbiological analysis. The microbiological results reveal the domestic impact by the presence of several kinds of bacteria in the groundwater resources: E. coli, Fecal coliforms, Total coliforms, Enterococci, Mesophilic Aerobic Flora, Sulphite-reducing bacteria and Salmonella.Selenium, arsenic and the bacteriological contamination of the groundwater could be explained by five kinds of factors: i) the geological formations and the nature of the hydrogeological system (unconfined layer), ii) the groundwater flow, the hydraulic relation between the hydrogeological wells and, the fractures network in the shale aquifer. The piezometric map allows to highlight the groundwater flow from the North-East to North-West and to the South-West, the drainage axis towards the P21 well and the presence of the dividing axis in the contaminated zone by the arsenic, iii) the absence of the unhealthy habitats with permeable traditional septic tanks in the village; iv) the transfer of the spreading animal excrements from the soil to groundwater and, v) the migration of the wastewater towards downstream of the groundwater flow. The presence of the reed beds could explain the reduction of bacteria in the hydrogeological wells of the study area.

In order to exhaustively investigate the physical and chemical mechanisms of heavy metal immobilization in sludge incineration residue (SIR)-based magnesium potassium phosphate cement (MKPC), this work investigated the influence of Pb²⁺ and Zn²⁺ on the compressive strength and microstructure of SIR-based MKPC, and the efficiency of Pb and Zn immobilization. Taking the difference of Ksp (solubility product) of different heavy metal compounds as the entry point, the physical and chemical mechanisms of Pb and Zn immobilization, and the competitive mechanism between coexisting ions, were comprehensively analyzed. It was discovered that Pb²⁺ is in the form Pb₃(PO₄)₂, and Zn²⁺ is immobilized in the form Zn₂(OH)PO₄ [Zn₃(PO₄)₂ is preferentially formed, when the pH > 7, Zn₃(PO₄)₂ is converted to Zn₂(OH)PO₄]. The low solubility of heavy metal phosphates is the main reason that Pb²⁺ and Zn²⁺ are well immobilized. The preferential formation of Pb₃(PO₄)₂ (Kₛₚ = 8 × 10⁻⁴³) and Zn₃(PO₄)₂ (Kₛₚ = 9.0 × 10⁻³³) reduced the amount of MgKPO₄·6H₂O (Kₛₚ = 2.4 × 10⁻¹¹), resulting in a decrease in compressive strength. Besides, coexisting Pb²⁺ and Zn²⁺ has a competitive effect: Pb²⁺ will weaken the immobilization efficiency of Zn²⁺. The new exploration of these mechanisms provide a theoretical basis for rationally adjusting the Magnesia/Phosphate ratio to enhance the compressive strength and improve the efficiency of heavy metals immobilization.

A particulate matter (PM) source apportionment study was carried out in one of the most polluted districts of Tuscany (Italy), close to an old waste incinerator plant. Due to the high PM10 levels, an extensive field campaign was supported by the Regional Government to identify the main PM sources and quantify their contributions. PM10 daily samples were collected for one year and analysed by different techniques to obtain a complete chemical characterisation (elements, ions and carbon fractions). Hourly fine (<2.5 μm) and coarse (2.5–10 μm) aerosol samples were collected by a Streaker sampler for a shorter period and hourly elemental concentrations were obtained by PIXE.Positive Matrix Factorization (PMF) analysis of daily and hourly data allowed the identification of 10 main sources: six anthropogenic (Biomass Burning, Traffic, Secondary Nitrates, Secondary Sulphates, Incinerator, Heavy Oil combustion), two natural (Saharan Dust and Fresh Sea Salt) and two mixed sources (Local Dust and Aged Sea Salt). Biomass burning turned out to be the main source of PM, accounting for 30% of the PM10 mass as annual average, followed by Traffic (18%) and Secondary Nitrates (14%). Emissions from the Incinerator turned out to be only 2% of PM10 mass on average.PM10 composition and source apportionment have been assessed in a polluted area near a waste incinerator, by PMF analysis on daily and hourly compositional data sets.

Schwertmannite (SCH) has strong adsorption ability to As(III). However, there are few reports on the stability of SCH load with As(III) (SCH-As(III)). In this study, the effects of tartaric acid (TA), pH and coexisting ions including K+, Ca2+, Al3+ and CO32− on the photoreductive dissolution of SCH- As(III) and the release of the adsorbed As (III) were investigated. The results showed that under UV irradiation TA could greatly enhance the release of total Fe and total As from SCH-As(III). Nevertheless, the total Fe and total As in the solution decreased when TA was consumed up. Compared to SCH, the reductive dissolution of SCH-As(III) was obviously suppressed. In the dark, TA could slowly enhance the dissolution of SCH-As(III), but its effect on the release of adsorbed As(III) was weak. Low pH was conducive to the release of iron and arsenic. Ca2+, K+, and CO32− promoted the decrease of the dissolved total Fe in the later reaction. However, Al3+ inhibited the decrease of the dissolved total Fe and total As. The analyses of FTIR and XRD demonstrated that the mineralogical phase of SCH-As(III) after reaction changed. With light, the dissolved total Fe and total As existed mainly as Fe(II) and As(V), respectively. This is because Fe(II) was generated via ligand to metal charge transfer and As(III) was oxidized to As(V) by ·OH produced during the reaction. Thus, this study provides us with a comprehensive understanding of the stability of SCH-As(III) and the release of adsorbed As(III) in natural environments.

The effects of fulvic acid (FA) and ions on mesophilic pathogenic bacteria survival under freeze-thaw (FT) stress in natural water and its resistant mechanisms are rarely understood. Therefore, survival patterns of Escherichia coli in river water added with various concentrations of FA or FA-ion under FT stress were studied in this work. Meanwhile, cell surface hydrophobicity (CSH), unit activities of superoxide dismutase (SOD) and catalase (CAT) were determined and Escherichia coli morphologies were observed to explore the bacterial resistant mechanisms against FT stress. The results demonstrated that FT cycles significantly reduced bacterial quantities as sampling time, i.e. freeze-thaw cycle time increased. And the biggest reducing rate was observed after the first FT cycle in every system. Ttd values, time needed to reach detection limit under FT stress decreased under FT stress as FA was added into water, while the changes of ttd values were quite complicated when FA and various ions existed together. Generally, the ttd values of FA-cation systems exceeded that of FA system except FA-Ca²⁺ systems, but it was opposite for FA-anion systems. CSH was heightened after FT cycles and reached peak value at last sampling time in every system. Mechanical constraint from extracellular ice crystals and high CSH induced bacterial aggregation, which protect inner cells of aggregation from extracellular ice crystals. And the unit activities of SOD were significantly higher than those of CAT. Unit activities of SOD and CAT in large part of tested systems increased with sampling time under FT stress, which reduced reactive oxygen species produced from repeated FT cycles. Thus, these could improve the resistance of Escherichia coli to freeze-thaw stress and promote their survival. This work explored the survival pattern and strategy of Escherichia coli in natural water under FT stress.

In this study, reactive pyrite (FeS2) particles were prepared through a modified hydrothermal method and tested for immobilization of Cr(VI) in contaminated soil and synthetic groundwater. The addition of a NaAc buffer in the synthetic process resulted in pyrite particles of greater specific surface area, more uniform size, and more crystalline structure. The particles can effectively immobilize Cr(VI) in both water and a model Chinese loess soil. Over 99.9% of Cr(VI) was rapidly removed from water at pH 6.0 (Initial Cr(VI) = 25 mg/L, FeS2 dosage = 0.48 g/L), and the removal remained high (>82%) even at pH 9.5. Both adsorption and reductive precipitation were found operative in the Cr(VI) immobilization, with ∼66% of Cr immobilized due to reduction. Fe(II) ions associated on the FeS2 surface played a key role in the reduction of Cr(VI) to Cr(III), and S22− also facilitated the reductive removal of Cr(VI). The presence of humic acid enhanced Cr(VI) removal at pH 4.0, but the effect was negligible at pH 6.0. Batch kinetic tests showed that treating a Cr(VI)-laden soil with 0.48 g/L (as Fe) of FeS2 decreased the equilibrium water-leachable Cr(VI) by >99.0% at pH 6.0 and by >70.0% at pH 9.0. The distribution coefficient (Kd) value of the pyrite-amended soil was 1477.8 at pH 6.0, which is 306 times higher than for the untreated soil. Column elution tests showed that installation of a 3-cm reactive layer of FeS2 in a soil column was able to capture the leachable Cr(VI) from the soil, and the retardation factor (Rd) for the 3-cm FeS2 layer sample was 381 times higher than that for the plain soil. The synthetic pyrite particles may serve as an reactive material for effective removal or immobilization of Cr(VI) in contaminated water or soil.

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.

In this work, magnesium ferrite (MgFe₂O₄) nano-platelets with rich defects and abundant surface hydroxyl groups were synthesized, and used for the removal of low concentration As(V) in aqueous solution. Results from scanning electron microscopy (SEM) showed that the as-synthesized MgFe₂O₄ nano-platelets were consisted of many individual nanospheres. Rietveld refinement of X-ray diffraction (XRD) data indicated that the Mg²⁺ ions substituted the Fe³⁺ ions at both the octahedral and the tetrahedral sites of the crystal structure. Batch adsorption experiment showed that the equilibrium concentration of As(V) could be reduced down to 4.9 μg·L⁻¹ when the initial concentration of As(V) is 1 mg·L⁻¹, which complied with the drinking water standard of WHO (10 μg·L⁻¹). The adsorption capacity of synthesized MgFe₂O₄ towards As(V) was higher than commonly used iron oxide adsorbents (Fe₃O₄, γ-Fe₂O₃ and α-Fe₂O₃). Mechanistic studies proved that the superior adsorption capacity was attributed to: (1) increased amount of surface hydroxyl groups that resulted from the surface defects. (2) formation of tridentate hexanuclear surface complexes instead of bidentate binuclear complexes, and (3) formation of excess Mg-OH surface hydroxyl groups and As-Mg monodentate mononuclear surface complexes. This work disclosed the correlation of the superior As(V) adsorption ability with the surface hydroxyl groups in defective MgFe₂O₄, and propose MgFe₂O₄ as a potential candidate for the remediation of As-contaminated water.