Trace and rare earth elements in phytoplankton from the Tyrrhenian Sea (Italy).

Plankton plays a very crucial role in bioaccumulation and transfer of metals in the marine food web and represents a suitable bioindicator of the occurrence of trace and rare earth elements in the ecosystem. Trace elements and REEs were analyzed by ICP-MS in phytoplankton samples from the northwestern Mediterranean Sea. Metal concentrations in phytoplankton were found strongly influenced by seasons and depth of collection (- 30 m, - 50 m). Principal component analysis (PCA) has shown that Al, As, Cr, Cu, Ga, and Sn concentrations were related to summer and autumn in samples collected at 30 m depth, while Fe, Mn, Ni, V, and Zn levels related strongly with summer and spring at 50 m depth. Fe, Al, and Zn were the most represented elements in all samples (mean values respectively in the ranges 4.2-8.2, 9.6-13, and 1.0-4.4 mg kg-1) according to their widespread presence in the environment and in the earth crust. Principal component analysis (PCA) performed on REEs showed that mostly all lanthanides' concentrations strongly correlate with summer and autumn seasons (- 30 m depth); the highest ∑REE concentration (75 µg kg-1) was found in winter. Phytoplankton REE normalized profile was comparable to those of other marine biota collected in the same area according to the suitability of lanthanides as geological tracers.

Precision Engineering of 2D Protein Layers as Chelating Biogenic Scaffolds for Selective Recovery of Rare-Earth Elements.

Rare-earth elements, which include the lanthanide series, are key components of many clean energy technologies, including wind turbines and photovoltaics. Because most of these 4f metals are at high risk of supply chain disruption, the development of new recovery technologies is necessary to avoid future shortages, which may impact renewable energy production. This paper reports the synthesis of a non-natural biogenic material as a potential platform for bioinspired lanthanide extraction. The biogenic material takes advantage of the atomically precise structure of a 2D crystalline protein lattice with the high lanthanide binding affinity of hydroxypyridinonate chelators. Luminescence titration data demonstrated that the engineered protein layers have affinities for all tested lanthanides in the micromolar-range (dissociation constants) and a higher binding affinity for the lanthanide ions with a smaller ionic radius. Furthermore, competitive titrations confirmed the higher selectivity (up to several orders of magnitude) of the biogenic material for lanthanides compared to other cations commonly found in f-element sources. Lastly, the functionalized protein layers could be reused in several cycles by desorbing the bound metal with citrate solutions. Taken together, these results highlight biogenic materials as promising bioadsorption platforms for the selective binding of lanthanides, with potential applications in the recovery of these critical elements from waste.

Biological, biomolecular, and bio-inspired strategies for detection, extraction, and separations of lanthanides and actinides.

Lanthanides and actinides are elements of ever-increasing technological importance in the modern world. However, the similar chemical and physical properties within these groups make purification of individual elements a challenge. Current industrial standards for the extraction, separation, and purification of these metals from natural sources, recycled materials, and industrial waste are inefficient, relying upon harsh conditions, repetitive steps, and ligands with only modest selectivity. Biological, biomolecular, and bio-inspired strategies towards improving these separations and making them more environmentally sustainable have been researched for many years; however, these methods often have insufficient selectivity for practical application. Recent developments in the understanding of how lanthanides are selectively acquired and used by certain bacteria offer the opportunity for a newer, more efficient take on these designs, as well as the possibility for fundamentally new designs and strategies. Herein, we review current cell-based and biomolecular (primarily small-molecule and protein-based) methods for detection, extraction, and separations of f-block elements. We discuss how the increasing knowledge regarding the selective recognition, uptake, trafficking, and storage of these elements in biological systems has informed and will continue to promote development of novel approaches to achieve these ends.

Lanthanide rarity in natural waters: implications for microbial C1 metabolism.

Research in the last decade has illuminated the important role that lanthanides play in microbial carbon metabolism, particularly methylotrophy. Environmental omics studies have revealed that lanthoenzymes are dominant in some environments, and laboratory studies have shown that lanthoenzymes are favored over their calcium-containing counterparts even when calcium is far more abundant. Lanthanide elements are common in rocks but occur at exceedingly low levels in most natural waters (picomolar to nanomolar range) with the exception of volcanic hot springs, which can reach micromolar concentrations. Calcium is orders of magnitude higher in abundance than lanthanide elements across natural settings. Bacteria that use lanthanides for growth on simple carbon compounds (e.g. methanol and ethanol) grow optimally at micromolar concentrations. It is highly likely that bacteria in the environment have evolved specialized lanthanide sequestration and high-affinity uptake systems to overcome lanthanide deprivation. Indeed, we identified genes in soil metagenomes encoding the lanthanide-binding protein lanmodulin, which may be important for cellular differentiation between calcium and lanthanides. More research is needed on microbial adaptations to lanthanide scarcity.

Colorimetric identification of lanthanide ions based on two carboxylic acids as an artificial tongue.

We report a colorimetric array, which consists of two carboxylic acids (quinolinic acid (QA), tannic acid (TCA)) as the sensor element and Eriochrome Black T (EBT) as the colorimetric signal readout. The assay is based on coordination binding between lanthanide ions and EBT, and between lanthanide ions and the carboxylic acids. The competitive binding of lanthanide ions with the carboxylic acids and EBT leads to the change in absorbance and color of the solutions. To test the efficacy of our sensor array, the sensor array was exposed to five target lanthanide ions (La3+, Sm3+, Eu3+, Gd3+ and Yb3+) with diverse concentrations (10, 50, 100, 200, 300, 400, and 500 nM). Linear discriminant analysis (LDA) results show that the sensor array can identify the five lanthanide ions, with a low discrimination limit of 10 nM. More importantly, the sensor array realizes fast discrimination of lanthanide ions in river samples, showing potential in environmental monitoring.

Determination of the lanthanides, uranium and plutonium by means of on-line high-pressure ion chromatography coupled with sector field inductively coupled plasma-mass spectrometry to characterize nuclear samples.

High-pressure ion chromatography (HPIC) was coupled with sector field inductively coupled plasma-mass spectrometry (SF-ICP-MS) to separate plutonium (Pu), uranium (U), neodymium (Nd) and gadolinium (Gd) nuclides from isobaric nuclides and to quantify them with high sensitivity. In this study, mixed bed ion exchange columns CG5A and CS5A were used, from which Pu and U were eluted first using 1 M nitric acid. The lanthanides were then separated using a gradient of 0.1-0.15 M oxalic acid with the pH adjusted to 4.5. The HPIC-SF-ICP-MS method was validated using different sample matrices, i.e. spent nuclear fuel and soil. The method was found to be repeatable and gave rise to transient signals suitable for quantification of nuclide-specific concentrations using external calibration. In terms of accuracy, the HPIC-SF-ICP-MS measurement results were in good agreement with those obtained using thermal ionization mass spectrometry (TIMS). Finally, the method provides an improvement in sample throughput (≤60 minutes per sample) and reduces exposure of the operator to radiation compared to off-line gravitational chromatography followed by TIMS.

Mechanistic study of colorimetric and absorbance sensor developed for trivalent yttrium (Y3+) using chlortetracycline-functionalized silver nanoparticles.

The presence of hazardous, radioactive, and rare earth metal such as yttrium (Y3+) in water poses a serious health concern to the public health, thus, exploring novel Y3+-binding molecules and colorimetric indicators are desired. Chlortetracycline (CTC)-functionalized silver nanoparticles (AgNPs-CTC) were synthesized, purified by centrifugation and then characterized by UV-vis spectroscopy, XPS, XRD, and HR-TEM. Functionalization of AgNPs with CTC molecules enabled the rapid and sensitive detection of trivalent yttrium ion (Y3+). A decrease in the intensity of the original surface plasmon resonance peak at 420 nm was observed within the fraction of a min, with the simultaneous appearance of a new peak at a longer wavelength (540 nm); thus, a novel colorimetric and ratiometric absorbance probe was achieved. The free-O-containing moieties of CTC on the AgNPs surface coordinate with Y3+. Thus, CTC molecules led to the bridging of the AgNPs and subsequent aggregation. A good linear relationship (R2 = 0.933) in the range of 18 to 243 nM for Y3+ was observed, and the limit of detection (LOD) for ratiometric results was approximately 57.7 nM. The AgNPs-CTC sensor exhibited better colorimetric performance in terms of excellent sensitivity, LOD, and rapid formation of the AgNPs-CTC complex towards Y3+. The Y3+ spiked water samples from different sources and fetal bovine serum suggest that the developed method is practically useful and essentially portable for on-site monitoring. The AgNPs-CTC sensor can be also applied as a common colorimetric indicator for the detection of trace levels of Y3+ and lanthanides.

A preliminary study on the authentication and traceability of extra virgin olive oil made from Taggiasca olives by means of trace and ultra-trace elements distribution.

Extra virgin olive oil (EVO) is among the most counterfeit foodstuffs in the present market. The Italian production is with no doubt one of the most valuable and therefore mostly counterfeit, due to the difficulty in checking the geographic provenance of olives. In order to provide a way for verifying the provenance of EVO, the role of microelements and, in particular, of lanthanides in the oil production chain has been studied. The distribution of lanthanides as determined by means of ICP-MS analysis appeared to provide a good tool for tracing the EVO production chain. Lanthanides and other microelements were then used for distinguishing a particularly prised EVO production from Liguria (northwestern Italy) made from Taggiasca olive variety, verifying that this production can be easily authenticated on the base of these chemical descriptors.

Design and optimization of a fused-silica microfluidic device for separation of trivalent lanthanides by isotachophoresis.

Elemental analysis of rare earth elements is essential in a variety of fields including environmental monitoring and nuclear safeguards; however, current techniques are often labor intensive, time consuming, and/or costly to perform. The difficulty arises in preparing samples, which requires separating the chemically and physically similar lanthanides. However, by transitioning these separations to the microscale, the speed, cost, and simplicity of sample preparation can be drastically improved. Here, all fourteen non-radioactive lanthanides (lanthanum through lutetium minus promethium) are separated by ITP for the first time in a serpentine fused-silica microchannel (70 µm wide × 70 µm tall × 33 cm long) in <10 min at voltages ≤8 kV with limits of detection on the order of picomoles. This time includes the 2 min electrokinetic injection time at 2 kV to load sample into the microchannel. The final leading electrolyte consisted of 10 mM ammonium acetate, 7 mM α-hydroxyisobutyric acid, 1% polyvinylpyrrolidone, and the final terminating electrolyte consisted of 10 mM acetic acid, 7 mM α-hydroxyisobutyric acid, and 1% polyvinylpyrrolidone. Electrophoretic electrodes are embedded in the microchip reservoirs so that voltages can be quickly applied and switched during operation. The limits of detection are quantified using a commercial capacitively coupled contactless conductivity detector (C4 D) to calculate ITP zone lengths in combination with ITP theory. Optimization of experimental procedures and reproducibility based on statistical analysis of subsequent experimental results are addressed. Percent error values in band length and conductivity are ≤8.1 and 0.37%, respectively.

Quantitative Measurement of Cell-Nanoparticle Interactions Using Mass Cytometry.

Mass cytometry is a technique that uses inductively coupled plasma mass spectrometry (ICP-MS) to quantify the isotopic composition of cells in suspension. Traditionally it has been used in conjunction with antibodies labeled with stable lanthanide isotopes to investigate cellular heterogeneity. Here we describe its use to quantify uptake of metal nanoparticles by cells in suspension.

Scandium, yttrium, and lanthanide contents in soil from Serbia and their accumulation in the mushroom Macrolepiota procera (Scop.) Singer.

The mobility (fractionation) of rare earth elements (REEs) and their possible impacts on ecosystems are still relatively unknown. Soil samples were collected from two sites in central Serbia, an unpolluted mountain region (site 1) and a forest near a city (site 2). In order to investigate REE fractions (acid-soluble/exchangeable, reducible, oxidizable, and residual) in soils, BCR sequential extraction was performed. Additionally, the content of REEs was also determined in stipes and caps of the mushroom Macrolepiota procera, growing in the observed sites. Sc, Y, and lanthanide contents were determined by inductively coupled plasma mass spectrometry (ICP-MS), and results were subjected to multivariate data analysis. Application of pattern recognition technique revealed the existence of two distinguished clusters belonging to different geographical sites and determined by greater levels of Sc, Y, and lanthanides in Goc soil compared to Trstenik soil. Additionally, PCA analysis showed that REEs in soil were concentrated in two groups: the first consisted of elements belonging to light REEs and the second contained heavy REEs. These results suggest that the distribution of REEs in soils could indicate the geographical origin and type of soil. The bioconcentration factors and translocation factors for each REE were also calculated. This study provides baseline data on the rare earth element levels in the wild edible mushroom M. procera, growing in Serbia. In terms of bioconcentration and bioexclusion concept, Sc, Y, and REEs were bioexcluded in M. procera for both studied sites.

Development of a fast and efficient analytical technique for the isotopic analysis of fission and actinide elements in environmental matrices.

An automated separation-direct analysis scheme has been developed to determine both the concentration and isotopic composition of a suite of elements down to the low picogram level in a complex silicon-based matrix. With the ultimate goal of performing rapid analysis of materials with non-natural isotopic compositions, RAPID (Rapid Analysis of Post-Irradiation Debris) consists of a high-pressure ion chromatography system directly coupled to an inductively coupled plasma mass spectrometer. The RAPID method achieves matrix exclusion and direct online analysis of the elementally separated components, yielding precise isotopic compositions for up to 40 elements in less than one hour per sample. When combined with isotope dilution, this approach shows the potential to yield elemental concentrations with low uncertainties, providing a rapid analytical method that encompasses group I and II metals, transition metals, refractory metals, platinum group metals, lanthanides, and actinides. The method development, robustness, sensitivity, uncertainties, and potential applications in nuclear and environmental measurements will be discussed in this paper.

A Minimalist Approach for Distinguishing Individual Lanthanide Ions Using Multivariate Pattern Analysis.

To discriminate among the 14 trivalent lanthanide ions, curcumin, a naturally occurring, nontoxic, off-the-shelf, commercially available compound containing a single fluorophore, was chosen as a probe in the water media at pH 6.8 and pH 8.2. By measuring the emission and absorption spectra of the probe, under the different pH conditions, and by performing linear discriminant analysis on the data, 14 Ln3+ ions were discriminated. Additionally, an easy tool for the nonspecialists was developed with easily available household substances, using a smartphone app, which added an extra advantage to this single probe. This probe possesses advantageous features in terms of low-cost and instant on-site detection of the lanthanide ions.

Inhalation exposure and potential health risk estimation of lanthanides elements in PM2.5 associated with rare earth mining areas: a case of Baotou city, northern China.

Particulate pollution, especially PM2.5 (particles with an aerodynamic equivalent diameter of 2.5 µm or less), has received increased attention in China recently. In this study, PM2.5 samples were collected in August 2013 and April 2014 from different regions of Baotou, the largest rare earth elements (REEs) processing city in northern China. The concentrations and distribution patterns of REEs in PM2.5 were analyzed, and the inhalation exposure to REEs associated with PM2.5 was assessed. The results showed that the REEs levels were 56.9 and 15.3 ng m-3 in August 2013 and April 2014, respectively. These values are much higher than those in non-REEs mining areas. The distribution patterns of REEs exhibited LREE enrichment. The Eu and Ce anomalies displayed slightly positive and negative values, respectively, which were in accordance with the background soil and ore. The average daily intake amounts of REEs for population through inhalation exposure of PM2.5 in Baotou were in the range of 5.09 × 10-7 to 2.25 × 10-5 mg kg-1 day-1.

Predictive Models for HOMO and LUMO Energies of N-Donor Heterocycles as Ligands for Lanthanides Separation.

Quantum chemical calculations combined with QSPR methodology reveal challenging perspectives for the solution of a number of fundamental and applied problems. In this work, we performed the PM7 and DFT calculations and QSPR modeling of HOMO and LUMO energies for polydentate N-heterocyclic ligands promising for the extraction separation of lanthanides because these values are related to the ligands selectivity in the respect to the target cations. Data for QSPR modeling comprised the PM7 calculated HOMO and LUMO energies of N-donor heterocycles, including several types of both known and virtual undescribed polydentate ligands. Ensemble modeling included various molecular fragments as descriptors and different variable selection techniques to build consensus models (CMs) on a training set of 388 ligands using external cross-validation. CMs were then verified to make predictions for two external test sets: 45 ligands (T1) that were similar to the ligands of the training set, and 1546 structures (T2), which were substantially different from the ligands of the training set. The consensus models predict well in 5-fold cross-validation (RMSEHOMO =0.097 eV, RMSELUMO =0.064 eV), and on the external test sets (T1: RMSEHOMO =0.26 eV, RMSELUMO =0.24 eV; T2: RMSEHOMO =0.26 eV, RMSELUMO =0.17 eV). An analysis of the results reveals that substituents in heteroaromatic rings of the ligands and at the amide nitrogens can deeply influence their metal binding properties.

Kinetics-mediate fabrication of multi-model bioimaging lanthanide nanoplates with controllable surface roughness for blood brain barrier transportation.

Effective delivery of imaging agents or therapeutics to the brain has remained elusive due to the poor blood-brain barrier (BBB) permeability, resulting in the apparent risks of inefficient diagnosis and therapeutic agents for brain disease. Herein, we report on the surface roughness mediated BBB transportation for the first time. The lanthanide-based core/shell/shell structured NaYF4:Yb,Er@NaGdF4:Yb@NaNdF4:Yb nanoplates with controllable surface roughness and multi-model bioimaging features were synthesized and used to evaluate the surface roughness dependent BBB permeability without any surface bio-functionalization. By controlling the kinetics of the shell coating process, the hexagon-disc, multi-petals and six-petals nanoplates with different surface roughness can be obtained. Comparing with the NPs with less Ra and receptor-conjugated NPs, the obtained six-petals nanoplates with highest roughness exhibit excellent performance in BBB transportation and tumor targeting, which lay solid foundation for the diagnosis and the therapy of brain tumor.

Role of Lanthanides in the Traceability of the Milk Production Chain.

The traceability and authentication of milk were studied using trace and ultratrace elements as chemical markers. Among these variables, the group of lanthanides resulted in being particularly useful for this purpose as a result of their homogeneous distribution inside milk, which showed on the contrary to be intrinsically inhomogeneous from the elemental point of view. Using in this pilot study milk samples from a factory in Piedmont (Italy), we demonstrated that the distribution of lanthanides can be used as a fingerprint to put into relation the soil of the pasture land on which cows graze and the bottled milk produced in the factory. In fact, the distribution is maintained nearly unaltered along the production chain of milk, apart from the passage into the stomachs of the cows. Using the same variables, it was possible to discriminate between milk produced in the factory and milk samples taken from the large-scale retail trade.

Quantitative characterization of single cells by use of immunocytochemistry combined with multiplex LA-ICP-MS.

Actual research demonstrates that LA-ICP-MS is capable of being used as an imaging tool with cellular resolution. The aim of this investigation was the method development for LA-ICP-MS to extend the versatility to quantitative and multiplexing imaging of single eukaryotic cells. For visualization of individual cells selected, lanthanide-labeled antibodies were optimized for immuno-imaging of single cells with LA-ICP-MS. The molar content of the artificial introduced labels per cell was quantified using self-made nitrocellulose-coated slides for matrix-matched calibration and calculated amounts were in the range of 3.1 to 17.8 atmol per cell. Furthermore, the quantification strategy allows a conversion of 2D intensity profiles based on counts per second (cps) to quantitative 2D profiles representing the molar amount of the artificial introduced elemental probes per pixel for each individual cell. Graphical abstract ᅟ.

Selective solid phase extraction of lanthanides from tap and river waters with ion imprinted polymers.

For the first time, an ion imprinted polymer (IIP) able to selectively extract simultaneously all the lanthanide ions was successfully synthesized in acetonitrile using Nd3+ as a template ion, methacrylic acid as a complexing monomer, and ethylene glycol dimethacrylate as a cross-linker. A non-imprinted polymer (NIP) was synthesized under the same conditions as those of the IIP, but in the absence of the template ion. After the removal of the template ions, grounding and sieving, the IIP particles were packed in solid phase extraction (SPE) cartridges. The selectivity of the IIP was evaluated by comparing its behavior with the one of the NIP. Each SPE step (percolation, washing, and elution) was optimized in order to find the best compromise between the selectivity and the extraction recoveries. Using the optimized SPE conditions, the extraction recoveries of eight lanthanide ions representative of the lanthanide family were higher than 77% with an average value of 83% with the IIP, whereas, in the case of the NIP, they ranged between 14 and 36% and they were below 3% for the interfering ions from alkali, transition, and post-transition metal families with the IIP. A first evaluation of the reproducibility of the SPE profiles was carried out by performing statistical tests on the data obtained with several cartridges filled with particles obtained from two different IIP and NIP syntheses. Promising results were obtained. The specific capacity, i. e. the adsorption capacity of Nd3+ ions by the specific cavities of the imprinted polymer, was about 9 mg of Nd3+ per gram of IIP (60 µmol g-1), which is more than enough for the extraction of the lanthanide ions at trace levels. The breakthrough volume was about 1 mL per mg of IIP, leading to an enrichment factor of 15, which allows not only to selectively extract the lanthanides but also to concentrate them. Finally, the imprinted polymer was successfully used to selectively extract lanthanides from tap and river waters spiked at 1 µg L-1.

Isobaric dilution analysis as a calibration tool for long lived radionuclides in ICP-MS.

A novel quantification method named isobaric dilution analysis (IBDA) is introduced for internal calibration using inductively coupled plasma mass spectrometry (ICP-MS). Unlike isotope dilution analysis (IDA), where a sample to be analysed for a target analyte element is spiked with an isotopically enriched solution of the same element, IBDA uses the fact that conventional mass analysers cannot distinguish between two isobaric isotopes of different elements. Therefore, in IBDA, the sample with the element of interest is spiked with a solution of a different element, which shares at least one isobaric isotope and shows similar chemical properties resulting in a similar response. This method offers a less expensive alternative to conventional IDA especially for long-lived radionuclides of elements for which a spiking element that fulfils the above mentioned requirements can be provided. In addition, IBDA offers the advantage of making certain metastable, sometimes monoisotopic elements accessible to internal calibration using a strategy analogous to IDA. One of the elements accessible by the new calibration strategy is technetium (Tc), which suffers from a lack of standards due to safety requirements associated with its radioactivity. In this work, the principle of IBDA is first demonstrated for a certified gadolinium standard, which was diluted with a dysprosium spike exhibiting an isobaric isotope with m/z 160. The results obtained by IBDA were compared with those obtained by a conventional IDA. The concept of IBDA was subsequently used for the determination of 99Tc in a contrast agent. Since no certified Tc standards are available, the response of 99Tc was interpolated allowing accurate determinations with an uncertainty of 1%.