In Situ Formation of Zwitterionic Ligands: Changing the Passivation Paradigms of CsPbBr3 Nanocrystals.

CsPbBr3 nanocrystals (NCs) passivated by conventional lipophilic capping ligands suffer from colloidal and optical instability under ambient conditions, commonly due to the surface rearrangements induced by the polar solvents used for the NC purification steps. To avoid onerous postsynthetic approaches, ascertained as the only viable stability-improvement strategy, the surface passivation paradigms of as-prepared CsPbBr3 NCs should be revisited. In this work, the addition of an extra halide source (8-bromooctanoic acid) to the typical CsPbBr3 synthesis precursors and surfactants leads to the in situ formation of a zwitterionic ligand already before cesium injection. As a result, CsPbBr3 NCs become insoluble in nonpolar hexane, with which they can be washed and purified, and form stable colloidal solutions in a relatively polar medium (dichloromethane), even when longly exposed to ambient conditions. The improved NC stability stems from the effective bidentate adsorption of the zwitterionic ligand on the perovskite surfaces, as supported by theoretical investigations. Furthermore, the bidentate functionalization of the zwitterionic ligand enables the obtainment of blue-emitting perovskite NCs with high PLQYs by UV-irradiation in dichloromethane, functioning as the photoinduced chlorine source.

Phytoremediation and detoxification of xenobiotics in plants: herbicide-safeners as a tool to improve plant efficiency in the remediation of polluted environments. A mini-review.

Phytoremediation is a widely studied and applied technology, based on the use of plants and their associated microorganisms to decontaminate polluted sites. In recent years, different strategies have been investigated to improve the phytoremediation efficiency of the selected plants. In this context, some studies have shown that herbicide-safeners, chemicals applied to crops to enhance their tolerance to herbicides, can increase the phytoremediation of soils and water polluted by organic and inorganic contaminants. Safeners, by inducing the xenobiotic detoxification and the antioxidant metabolism in plants, can enhance their removal potential in the cleaning process. In this review, after a short survey of phytoremediation technologies and the biochemical mechanisms activated by plants to tolerate and detoxify heavy metals and herbicides, the use of herbicide-safeners as a tool to increase the phytoremediation performance is reviewed and discussed.

Recent advances in analysis of trace elements in environmental samples by X-ray based techniques (IUPAC Technical Report).

Trace elements analysis is a fundamental challenge in environmental sciences. Scientists measure trace elements in environmental media in order to assess the quality and safety of ecosystems and to quantify the burden of anthropogenic pollution. Among the available analytical techniques, X-ray based methods are particularly powerful, as they can quantify trace elements in situ. Chemical extraction is not required, as is the case for many other analytical techniques. In the last few years, the potential for X-ray techniques to be applied in the environmental sciences has dramatically increased due to developments in laboratory instruments and synchrotron radiation facilities with improved sensitivity and spatial resolution. In this report, we summarize the principles of the X-ray based analytical techniques most frequently employed to study trace elements in environmental samples. We report on the most recent developments in laboratory and synchrotron techniques, as well as advances in instrumentation, with a special attention on X-ray sources, detectors, and optics. Lastly, we inform readers on recent applications of X-ray based analysis to different environmental matrices, such as soil, sediments, waters, wastes, living organisms, geological samples, and atmospheric particulate, and we report examples of sample preparation.

Correlations between As in Earthworms' Coelomic Fluid and As Bioavailability in Highly Polluted Soils as Revealed by Combined Laboratory X-ray Techniques.

Combined X-ray-based spectroscopy techniques were applied to investigate arsenic (As) bioaccumulation in earthworms (Eisenia andrei) exposed to six field-collected polluted soils (58-13 330 mg As kg-1). After 14 days of exposure to the arsenious soils, the As distribution in earthworms was examined by micro-X-ray fluorescence spectroscopy (µXRF), after epoxy resin embedding and preparing thin sections. Similar to µXRF data, XRF-computed tomography (XRF-CT) confirmed As accumulation in the coelom of intact earthworms. Therefore, total-reflection XRF was used to determine total As within both the whole earthworm's body (AsE) and coelomic fluid extracts (AsF). Bioaccumulation data (AsE and AsF) were thereafter evaluated in relation to total As concentration in soils (AsT) and to As mobile fraction in soils. A significant linear correlation (R2 = 0.97) was found between AsE and AsF, indicating that the As sequestrated into the coelomic fluid may reflect the total body concentration. Therefore, we may conclude that the As concentration in the coelomic fluid can be used as an index of As availability. This paper demonstrates that by combining different laboratory X-ray analytical techniques, compartmentalization and bioavailability of potentially toxic elements can be visualized and quantified within indicator-living organisms, thus contributing to an improved risk assessment for contaminated soils.

Iron allocation in leaves of Fe-deficient cucumber plants fed with natural Fe complexes.

Iron (Fe) sources available for plants in the rhizospheric solution are mainly a mixture of complexes between Fe and organic ligands, including phytosiderophores (PS) and water-extractable humic substances (WEHS). In comparison with the other Fe sources, Fe-WEHS are more efficiently used by plants, and experimental evidences show that Fe translocation contributes to this better response. On the other hand, very little is known on the mechanisms involved in Fe allocation in leaves. In this work, physiological and molecular processes involved in Fe distribution in leaves of Fe-deficient Cucumis sativus supplied with Fe-PS or Fe-WEHS up to 5 days were studied combining different techniques, such as radiochemical experiments, synchrotron micro X-ray fluorescence, real-time reverse transcription polymerase chain reaction and in situ hybridization. In Fe-WEHS-fed plants, Fe was rapidly (1 day) allocated into the leaf veins, and after 5 days, Fe was completely transferred into interveinal cells; moreover, the amount of accumulated Fe was much higher than with Fe-PS. This redistribution in Fe-WEHS plants was associated with an upregulation of genes encoding a ferric(III) -chelate reductase (FRO), a Fe(2+) transporter (IRT1) and a natural resistance-associated macrophage protein (NRAMP). The localization of FRO and IRT1 transcripts next to the midveins, beside that of NRAMP in the interveinal area, may suggest a rapid and efficient response induced by the presence of Fe-WEHS in the extra-radical solution for the allocation in leaves of high amounts of Fe. In conclusion, Fe is more efficiently used when chelated to WEHS than PS and seems to involve Fe distribution and gene regulation of Fe acquisition mechanisms operating in leaves.

Spatially resolved (semi)quantitative determination of iron (Fe) in plants by means of synchrotron micro X-ray fluorescence.

Iron (Fe) is an essential element for plant growth and development; hence determining Fe distribution and concentration inside plant organs at the microscopic level is of great relevance to better understand its metabolism and bioavailability through the food chain. Among the available microanalytical techniques, synchrotron µ-XRF methods can provide a powerful and versatile array of analytical tools to study Fe distribution within plant samples. In the last years, the implementation of new algorithms and detection technologies has opened the way to more accurate (semi)quantitative analyses of complex matrices like plant materials. In this paper, for the first time the distribution of Fe within tomato roots has been imaged and quantified by means of confocal µ-XRF and exploiting a recently developed fundamental parameter-based algorithm. With this approach, Fe concentrations ranging from few hundreds of ppb to several hundreds of ppm can be determined at the microscopic level without cutting sections. Furthermore, Fe (semi)quantitative distribution maps were obtained for the first time by using two opposing detectors to collect simultaneously the XRF radiation emerging from both sides of an intact cucumber leaf.

Iron (Fe) speciation in xylem sap by XANES at a high brilliant synchrotron X-ray source: opportunities and limitations.

The development of highly brilliant synchrotron facilities all around the world is opening the way to new research in biological sciences including speciation studies of trace elements in plants. In this paper, for the first time, iron (Fe) speciation in xylem sap has been assessed by X-ray absorption near-edge structure (XANES) spectroscopy at the highly brilliant synchrotron PETRA III, beamline P06. Both standard organic Fe-complexes and xylem sap samples of Fe-deficient tomato plants were analyzed. The high photon flux provided by this X-ray synchrotron source allows on one side to obtain good XANES spectra in a reasonable amount of time (approx. 15 min for 200 eV scan) at low Fe concentrations (sub parts-per-million), while on the other hand may cause radiation damage to the sample, despite the sample being cooled by a stream of liquid nitrogen vapor. Standard Fe-complexes such as Fe(III)-succinate, Fe(III)-α-ketoglutarate, and Fe(III)-nicotianamine are somehow degraded when irradiated with synchrotron X-rays and Fe(III) can undergo photoreduction. Degradation of the organic molecules was assessed by HPLC-UV/Vis analyses on the same samples investigated by X-ray absorption spectroscopy (XAS). Fe speciation in xylem sap samples revealed Fe(III) to be complexed by citrate and acetate. Nevertheless, artifacts created by radiation damage cannot be excluded. The use of highly brilliant synchrotrons as X-ray sources for XAS analyses can dramatically increase the sensitivity of the technique for trace elements thus allowing their speciation in xylem sap. However, great attention must be paid to radiation damage, which can lead to biased results.

TXRF spectral information enhanced by multivariate analysis: A new strategy for food fingerprint.

The increased costumers' request of safe and high-quality food products makes food traceability a priority for frauds identification and quality certification. Elemental profiling is one of the strategies used for food traceability, and TXRF spectroscopy is widely used in food analysis even if its potentialities have not been fully investigated. In this work, a new method for food traceability using directly TXRF spectra coupled with multivariate analyses, was tested. Twenty-four different beans' genotypes (Phaseolus vulgaris L.) grown onto two different sites have been studied. After the development of the method for beans' analysis, TXRF spectra were collected and processed with PCA combined with SNV and GLSW filter obtaining a perfect clustering of the seeds according to their geographical origin. Finally, using PLS-DA, beans were correctly classified demonstrating that TXRF spectra can be successfully used as fingerprint for food/seed traceability and that elemental quantification procedure is not necessary to this aim.

Fire-induced effects on the bioavailability of potentially toxic elements in a polluted agricultural soil: implications for Cr uptake by durum wheat plants.

Fire events can modify the distribution and speciation of potentially toxic elements (PTEs) in soil, especially if they are associated to organic matter (OM). In fact, OM can undergo substantial structural modifications at high temperatures, up to the complete mineralization. The present study aims to investigate the changes of PTEs' bioavailability to durum wheat (Triticum durum Desf.) plants after simulating fire events (up to 300 °C and 500 °C) in an agricultural soil polluted by Cr, Zn, Cu, and Pb. The PTEs' uptake and allocation in plant tissues were assessed using the RHIZOtest system. After the fire simulations, no evident risk of accumulation and translocation in plants was observed for Zn, Pb, and Cu. Conversely, a high accumulation in roots and a significant translocation to shoots were observed for Cr, which reached concentrations of 829 mg kg-1 in roots and 52 mg kg-1 in shoots at 500 °C. Additional experimental evidence suggested that Cr was taken up by plants grown on heated soils as Cr(VI). Once acquired by roots, only a small part of Cr (up to 6%) was translocated to shoots where it was likely present as mobile forms, as evidenced by micro X-ray fluorescence (µ-XRF) analyses. Overall, the results obtained provide evidence that the high temperatures occurring during fire events can increase the mobility and bioavailability of certain PTEs transforming apparently safe environments into potentially dangerous sources of pollution. These processes can ultimately affect the human health through the food chain transfer of PTEs or their migration into surface water and groundwater.

Combining micro- and portable-XRF as a tool for fast identification of virus infections in plants: The case study of ASa-Virus in Fraxinus ornus L.

Plant viruses can affect micro- and macro-nutrients homeostasis in woody plants, with fluctuation in the concentration of some elements at the leaf level due to the pathogen activity and/or the plant physiological response to the infection.Leaves of Fraxinus ornus L. (flowering ash) were sampled for three consecutive years in the city of Hamburg (Germany), from both trees showing the typical symptoms of the ash shoestring associated virus infection (ASaV+) and healthy trees (ASaV-). Such leaves were analyzed by µ-XRF, using both laboratory and synchrotron X-ray sources, and large differences between symptomatic and not symptomatic leaves were observed: ASaV+ samples showed uneven element distribution and regions of the lamina with severe depletions of P, S, and Ca. Differently, K appeared more concentrated. Thus, 139 leaflets sampled from various healthy and infected ash trees over the three-year period were analyzed for K and Ca concentration with a portable XRF instrument. We found that the K:Ca concentration ratio was always significantly higher in ASaV+ samples, and this trend was verified for all the samplings over the tree years. We conclude that the K:Ca ratio parameter has potential in the frame of trendsetting diagnostics and could be used, together with visual symptoms, for a rapid, non-destructive, on-site and cheap indirect ASaV detection.

Evidence of hexavalent chromium formation and changes of Cr speciation after laboratory-simulated fires of composted tannery sludges long-term amended agricultural soils.

Controlled or accidental fires can impact agricultural soils amended with composted organic materials since high temperatures cause fast organic matter (OM) mineralization and soil properties modifications. During these events, potentially toxic elements (PTEs) associated with OM can be released and change their distribution and speciation thus becoming a threat to the environment and to crops. In this study, we investigated the changes of distribution and speciation of chromium in soils long-term amended with compost obtained from tannery sludges, after simulating fires of different intensity (300, 400 and 500 °C) likely to occur on agricultural soils. A combination of conventional soil chemical analyses and bulk and (sub)micro X-ray analyses allowed the observation of the formation of hexavalent chromium and changes of chromium speciation. Specifically, a strong decrease of Cr-OM associations was found with increasing temperature in favour of Cr-iron (hydr)oxides interactions and CaCrO4 formation. These data provide first evidence that fires can transform OM-stabilized Cr into more mobile, available and toxic Cr-forms potentially accessible for plant uptake, thus posing a risk for the food chain and the environment.

Overcome the limits of multi-contaminated industrial soils bioremediation: Insights from a multi-disciplinary study.

Phytoremediation can be a promising and sustainable strategy to recovery Potentially Toxic Elements (PTEs) contaminated soils. However, at the field level, this tool can be limited by many issues. Herein, we combined native plant species with different cover type (mono and poly culture) in an in-field mesocosm experiment for the remediation of multi-contaminated soils from Bagnoli brownfield site (Southern Italy). We preliminary gain insights about the physical, chemical and biological features of the soils and subsequently induced a potential variation in the soil microbiome. We found that polyculture better respond both in terms of pollutant phytostabilization efficiency and from a stress tolerance perspective. Among plant species, Festuca achieved the best performance due to the overexpression of metal transporters able in both PTEs influx and sequestration from the cytoplasm. We achieved a site-specific bio-factory, which represents a strategy for the sustainable and relatively fast recovery of large contaminated areas.

Corn salad (Valerianella locusta (L.) Laterr.) growth in a water-saving floating system as affected by iron and sulfate availability.

BACKGROUND: Unbalanced nutrient availability causes disequilibrated plant growth, which can result in a worsening of harvested product quality, such as high nitrate content in edible tissues. To cope with this problem, improved knowledge of the mechanisms involved in nutrient acquisition and regulation is necessary. For this purpose the responses of acquisition mechanisms of N, Fe and S were studied as a function of Fe and S availability using two corn salad cultivars grown hydroponically, considering also aspects related to N metabolism. RESULTS: The results showed that an increase in Fe or S availability enhanced nitrate uptake and assimilation, which in turn increased biomass production of leaves with lower nitrate content. In particular, high S availability exerted a positive effect (gene expression and functionality) both on the uptake and metabolism of N and on Fe acquisition mechanisms. CONCLUSION: The data presented here show close interactions between N, S and Fe, highlighting that relevant improvements in yield and quality from soilless culture might also be obtained through appropriate adjustments of nutrient availability. In this respect, concerning the role of S in the acquisition mechanisms of N and Fe and in N metabolism, its level of availability should be taken into high consideration for equilibrated plant growth.

Antinutritional factors, mineral composition and functional properties of dry fractionated flours as influenced by the type of pulse.

Coarse (CF) and Fine (FF) fractions were obtained by dry fractionation (air classification) of raw micronized flour (RM) of kabuli chickpea, green pea, yellow and red lentil. Pea showed the highest phytate content in RM and CF. Stachyose was the main oligosaccharide in lentils, exceeding 50 mg g-1, whereas raffinose (39.9 mg g-1) was abundant in chickpea. Antinutritional factors were significantly enriched in FF, whereas decreased in CF. Total-reflection X-ray fluorescence identified potassium as the main macronutrient in pulses. Ca was highly variable, ranging from 0.92 to 0.28 g kg-1 in pea and yellow lentil, respectively. A significant shift of minerals was observed in FF, but despite the highest phytate content, phytate:Zn ratio of lentils was lower than RM, indicating that Zn was enriched more than phytates. Yellow lentil and pea FF showed a protein content higher than 55 g 100g-1. Dry fractionation significantly affected the physicochemical properties, indicating different potential use of fractions.

Combined Effect of Laboratory-Simulated Fire and Chromium Pollution on Microbial Communities in an Agricultural Soil.

Fire events in agricultural soils can modify not only soil properties but also the structure of soil microbial communities, especially in soils containing high concentrations of potentially toxic elements (PTEs). The recolonization of burned soils can in fact favor the proliferation of certain microorganisms, more adaptable to post-fire soil conditions and higher PTE availability, over others. In this study, we simulated with laboratory experiments the microbial recolonization of an agricultural soil containing high Cr concentrations after heating at 500 °C for 30 min, to mimic the burning of crop residues. Changes in soil properties and Cr speciation were assessed, as well as soil microbial structure by means of 16S rRNA gene sequencing. Both altered soil conditions and increased Cr availability, especially Cr(VI), appeared to be responsible for the reduction in species diversity in heated soils and the proliferation of Firmicutes. Indeed, already after 3 days from the heat treatment, Firmicutes increased from 14% to 60% relative abundance. In particular, Paenibacillus was the most abundant genus identified after the simulation, with an average relative abundance of 40%. These bacteria are known to be good fire-responders and Cr-tolerant. These results could be useful to identify bacterial strains to be used as bioindicators of altered environments and for the recovery of fire-impacted polluted sites.

Fire effects on the distribution and bioavailability of potentially toxic elements (PTEs) in agricultural soils.

In the last years, uncontrolled fires are frequently occurring in forest and agricultural areas as an indirect effect of the rising aridity and global warming or caused by intentional illegal burnings. In addition, controlled burning is still largely used by farmers as an agricultural practice in many parts of the world. During fire events, soil can reach very high temperatures at the soil surface, causing dramatic changes of soil properties and elements biogeochemistry. Among soil elements, also potentially toxic elements (PTEs) can be affected by fires, becoming more or less mobile and bioavailable, depending on fire severity and soil characteristics. Such transformations could be particularly relevant in agricultural soils used for crop productions since fire events could modify PTEs speciation and uptake by plants and associated (micro)organisms thus endangering the whole food-chain. In this review, after describing the effects of fire on soil minerals and organic matter, the impact of fires on PTEs distribution and speciation in soils is presented, as well as their influence on soil microorganisms and plants uptake. The most common experimental methods used to simulate fires at the laboratory and field scale are briefly illustrated, and finally the impact that traditional and innovative agricultural practices can have on PTEs availability in burned agricultural soils is discussed in a future research perspective.

Size-tunable and stable cesium lead-bromide perovskite nanocubes with near-unity photoluminescence quantum yield.

Stable cesium lead bromide perovskite nanocrystals (NCs) showing a near-unity photoluminescence quantum yield (PLQY), narrow emission profile, and tunable fluorescence peak in the green region can be considered the ideal class of nanomaterials for optoelectronic applications. However, a general route for ensuring the desired features of the perovskite NCs is still missing. In this paper, we propose a synthetic protocol for obtaining near-unity PLQY perovskite nanocubes, ensuring their size control and, consequently, a narrow and intense emission through the modification of the reaction temperature and the suitable combination ratio of the perovskite constituting elements. The peculiarity of this protocol is represented by the dissolution of the lead precursor (PbBr2) as a consequence of the exclusive complexation with the bromide anions released by the in situ SN2 reaction between oleylamine (the only surfactant introduced in the reaction mixture) and 1-bromohexane. The obtained CsPbBr3 nanocubes exhibit variable size (ranging from 6.7 ± 0.7 nm to 15.2 ± 1.2 nm), PL maxima between 505 and 517 nm, and near-unity PLQY with a narrow emission profile (fwhm of 17-19 nm). Additionally, the NCs synthesized with this approach preserve their high PLQYs even after 90 days of storage under ambient conditions, thus displaying a remarkable optical stability. Through the rationalization of the obtained results, the proposed synthetic protocol provides a new ground for the direct preparation of differently structured perovskite NCs without resorting to any additional post-synthetic treatment for improving their emission efficiency and stability.

Natural Mn-todorokite as an efficient and green azo dye-degradation catalyst.

A natural Mn mineral, i.e., todorokite [(Ca,Na,K)X(Mn4+,Mn3+)6O12·3.5H2O], has been collected in the Apulia region, south of Italy, and evaluated as an oxidation catalyst for the degradation of methyl orange (MO) dye. This Mn-todorokite mineral has been firstly characterized by X-ray diffraction, wavelength-dispersive X-ray fluorescence, BET, scanning electron microscopy, attenuated total reflectance Fourier transform infrared spectroscopy, and thermogravimetry. Catalytic dye-degradation data show that this Mn-todorokite can operate under strongly oxidizing potentials (Eh > + 400 mV) vs. standard hydrogen electrode performing fast MO degradation (t1/2 < 1 min). A detailed study using electron paramagnetic resonance spectroscopy revealed that, under oxidative conditions (Eh > + 450 mV), the active Mn centers of todorokite evolve rapidly through Mn3+/Mn4+ states and this is correlated with the fast catalytic degradation of MO. These results suggest Mn-todorokite mineral as an efficient, low-cost, and green catalyst which can be used for industrial and environmental purposes.

Assessing chromium pollution and natural stabilization processes in agricultural soils by bulk and micro X-ray analyses.

A combined approach based on multiple X-ray analytical techniques and conventional methods was adopted to investigate the distribution and speciation of Cr in a polluted agricultural soil, from the bulk-scale down to the (sub)micro-level. Soil samples were collected from two different points, together with a control sample taken from a nearby unpolluted site. The bulk characterization revealed that the polluted soils contained much higher concentrations of organic matter (OM) and potentially toxic elements (PTE) than the control. Chromium was the most abundant PTE (up to 5160 g kg-1), and was present only as Cr(III), as its oxidation to Cr(VI) was hindered by the high OM content. According to sequential extractions, Cr was mainly associated to the soil oxidisable fraction (74%) and to the residual fraction (25%). The amount of Cr potentially bioavailable for plant uptake (DTPA-extractable) was negligible. Characterization of soil thin sections by micro X-ray fluorescence (µXRF) and field emission scanning electron microscopy coupled with microanalysis (FEGSEM-EDX) showed that Cr was mainly distributed in aggregates ranging from tens micrometres to few millimetres in size. These aggregates were coated with an aluminosilicate layer and contained, in the inner part, Cr, Ca, Zn, P, S and Fe. Hyperspectral elaboration of µXRF data revealed that polluted soils were characterised by an exogenous organic-rich fraction containing Cr (not present in the control), and an endogenous aluminosilicate fraction (present also in the control), coating the Cr-containing aggregates. Analyses by high-resolution micro X-ray computed tomography (µCT) revealed a different morphology of the soil aggregates in polluted soils compared with the control. The finding of microscopic leather residues, combined with the results of bulk- and micro-characterizations, suggested that Cr pollution was likely ascribable to soil amendment with tannery waste-derived matrices. However, over the years, a natural process of Cr stabilization occurred in the soil thus reducing the environmental risks.

Combined micro X-ray fluorescence and micro computed tomography for the study of extraterrestrial volcanic rocks. The case of North West Africa (NWA) 8657: A shergottite martian meteorite.

The combined potentiality of benchtop micro X-ray fluorescence spectroscopy (µ-XRF) and micro computed tomography (µ-CT) has been applied to describe microstructures, type and distribution of mineralogical phases as well as geological constraints on the history of the North West Africa (NWA) 8657 shergottite Martian meteorite. The 3D rendering of the sample was used to compute its vesiculation, infer the presence of cracks and reveal different shapes in its crystal habits including subhedral pyroxene phases and rounded sulphide and/or sulphates minerals. Phase discrimination was achieved by comparing chemical information about element distribution with mineral classes segmented as a function of their relative density. In particular, the relationships between the plagioclase/maskelynite phase and other minerals such as Ca-phosphates, the chemical zoning of Ca-pyroxenes and maskelynite and the presence of S-bearing phases in the form of K-sulphates and Fe-sulphides were revealed, which allowed reconstructing satisfactorily meteorite history. The successful performance of the combined approach used in this work shows promising for further application to other types of meteorites.