Recovery of Lanthanum(III) and Nickel(II) Ions from Acidic Solutions by the Highly Effective Ion Exchanger.

The recovery of La(III) and Ni(II) ions by a macroporous cation exchanger in sodium form (Lewatit Monoplus SP112) has been studied in batch experiments under varying HNO3 concentrations (0.2-2.0 mol/dm3), La(III) and Ni(II) concentrations (25-200 mg/dm3), phase contact time (1-360 min), temperature (293-333 K), and resin mass (0.1-0.5 g). The experimental data revealed that the sorption process was dependent on all parameters used. The maximum sorption capacities were found at CHNO3 = 0.2 mol/dm3, m = 0.1 g, and T = 333 K. The kinetic data indicate that the sorption followed the pseudo-second order and film diffusion models. The sorption equilibrium time was reached at approximately 30 and 60 min for La(III) and Ni(II) ions, respectively. The equilibrium isotherm data were best fitted with the Langmuir model. The maximum monolayer capacities of Lewatit Monoplus SP112 were equal to 95.34 and 60.81 mg/g for La(III) and Ni(II) ions, respectively. The thermodynamic parameters showed that the sorption process was endothermic and spontaneous. Moreover, dynamic experiments were performed using the columns set. The resin regeneration was made using HCl and HNO3 solutions, and the desorption results exhibited effective regeneration. The ATR/FT-IR and XPS spectroscopy results indicated that the La(III) and Ni(II) ions were coordinated with the sulfonate groups.

Recovery of Rare Earth Elements from Wastewater Towards a Circular Economy.

The use of rare earth elements is a growing trend in diverse industrial activities, leading to the need for eco-friendly approaches to their efficient recovery and reuse. The aim of this work is the development of an environmentally friendly and competitive technology for the recovery of those elements from wastewater. Kinetic and equilibria batch assays were performed with zeolite, with and without bacterial biofilm, to entrap rare earth ions from aqueous solution. Continuous assays were also performed in column setups. Over 90% removal of lanthanum and cerium was achieved using zeolite as sorbent, with and without biofilm, decreasing to 70% and 80%, respectively, when suspended Bacillus cereus was used. Desorption from the zeolite reached over 60%, regardless of the tested conditions. When in continuous flow in columns, the removal yield was similar for all of the rare earth elements tested. Lanthanum and cerium were the elements most easily removed by all tested sorbents when tested in single- or multi-solute solutions, in batch and column assays. Rare earth removal from wastewater in open setups is possible, as well as their recovery by desorption processes, allowing a continuous mode of operation.

Biotransformation of lanthanum by Aspergillus niger.

Lanthanum is an important rare earth element and has many applications in modern electronics and catalyst manufacturing. However, there exist several obstacles in the recovery and cycling of this element due to a low average grade in exploitable deposits and low recovery rates by energy-intensive extraction procedures. In this work, a novel method to transform and recover La has been proposed using the geoactive properties of Aspergillus niger. La-containing crystals were formed and collected after A. niger was grown on Czapek-Dox agar medium amended with LaCl3. Energy-dispersive X-ray analysis (EDXA) showed the crystals contained C, O, and La; scanning electron microscopy revealed that the crystals were of a tabular structure with terraced surfaces. X-ray diffraction identified the mineral phase of the sample as La2(C2O4)3·10H2O. Thermogravimetric analysis transformed the oxalate crystals into La2O3 with the kinetics of thermal decomposition corresponding well with theoretical calculations. Geochemical modelling further confirmed that the crystals were lanthanum decahydrate and identified optimal conditions for their precipitation. To quantify crystal production, biomass-free fungal culture supernatants were used to precipitate La. The results showed that the precipitated lanthanum decahydrate achieved optimal yields when the concentration of La was above 15 mM and that 100% La was removed from the system at 5 mM La. Our findings provide a new aspect in the biotransformation and biorecovery of rare earth elements from solution using biomass-free fungal culture systems.

Understanding the factors affecting the adsorption of Lanthanum using different adsorbents: A critical review.

Over the past few decades, removal and recovery of Lanthanum (La) have received great attention due to its significance in different industrial processes. In this review, the application of various adsorbents viz. biosorbents, commercial and hybrid materials, nanoparticles, nanocomposites etc. have been summarized in terms of the removal and recovery of La. The influence of various operating parameters including pH, dosage, contact time, temperature, coexisting ions, adsorption kinetics, isotherm and thermodynamics were investigated. Statistical analysis of the obtained data revealed that 60% and 70% of the authors reported an optimum pH of 4-6 and a dose of 1-2 g/L, respectively. It can be concluded on the basis of an extensive literature survey that the adsorbent materials (especially hybrids nanocomposites) containing carboxyl, hydroxyl and amine groups offered efficient La removal over a wide range of pH with higher adsorption capacity as compared to other adsorbents (e.g., biosorbents and magnetic adsorbents). Also, in most cases, equilibrium and kinetics were followed by Langmuir and pseudo second-order model and adsorption was endothermic in nature. To evaluate the adsorption efficiency of several adsorbents towards La, desorption and regeneration of adsorbents should be given due consideration. The main objective of the review is to provide an insight into the important factors that may affect the recovery of La using various adsorbents.

Lanthanum Deposition in the Stomach in the Absence of Helicobacter pylori Infection.

In this case report, we describe two patients who showed a diffusely whitish mucosa in the posterior wall and the lesser curvature of the gastric body. The patients were serologically- and histopathologically-negative for Helicobacter pylori. Random biopsy specimens from the stomach revealed no regenerative changes, intestinal metaplasia, and/or foveolar hyperplasia in either of the patients. Although lanthanum deposition in the gastric mucosa has been reported to occur in close association with H. pylori-associated gastritis, our patients tested negative for H. pylori. These cases suggest that lanthanum deposition presents as whitish lesions in the gastric body in H. pylori-negative patients.

Immobilization of chitosan nanolayers on the surface of nano-titanium oxide as a novel nanocomposite for efficient removal of La(III) from water.

A novel nanocomposite has been designed and synthesized via surface crosslinking of chitosan nanolayers (NChit) with titanium oxide nanoparticles (NTiO2) using glutaraldehyde (Glu) as the crosslinking agent. A simple and green surface chemical reaction was accomplished by the aid of microwave heating process to enforce surface encapsulation and functionalization for the production of the aimed NTiO2-Glu-NChit nanocomposite. The average particles size of nanocomposite was characterized in the range of 52-58nm using SEM and confirmed by the HR-TEM. The XRD, TGA and FTIR were also employed to assure the immobilization and crosslinking processes. NTiO2-Glu-NChit was studied to estimate the sorption efficiency towards La(III) from aqueous solution by the batch technique under different experimental controlling physicochemical parameters such as, initial pH of metal ion solution, contact time, nanocomposite dosage and initial metal ion concentration. The optimum sorption condition for La(III) as the target metal ion was identified at pH=1.0, 3.0 and 6.0. The adsorption process of La(III) was characterized to follow the postulates of Langmuir and Freundlich isotherm models and the adsorption mechanisms were identified to obey the pseudo-second order kinetic model based on the best compatible results with the experimental data.

Recovery of valuable metals from electronic scraps by clays and organo-clays: Study on bi-ionic model solutions.

The demand of valuable metals, as precious metals and rare earths, is constantly increasing in the global market, as many and different technological applications exploit these materials because of their unique properties. Since natural resources are located just in focused areas, an interesting possibility could be the recovery of metals from Waste Electrical and Electronic Equipment (WEEE). The aim of this work is to evaluate the recovery potentialities of clays and organo-clay based systems towards the metals contained in the solutions of electronic scraps dissolved in strong acid, by preliminary tests on bi-ionic model solutions. Lanthanum has been chosen as representative of the rare earths while copper has been considered since it is by far the most used metal in electric and electronic equipment. The considered sorbents are a montmorillonitic clay and two polyamine based organo-clays. Uptake and release processes have been carried out in order to assess the performances of these solids and to evaluate the uptake and release mechanisms. The results showed that the cationic exchange is the prevailing mechanism in the case of pristine clay, while both coordinating effect due to amino groups and cationic exchange occur in the case of modified clays, respectively accounting for copper and lanthanum uptake. Furthermore the pH was found having a great influence in both the adsorption and desorption phenomena.

Identification of lanthanum-specific peptides for future recycling of rare earth elements from compact fluorescent lamps.

As components of electronic scrap, rare earth minerals are an interesting but little used source of raw materials that are highly important for the recycling industry. Currently, there exists no cost-efficient technology to separate rare earth minerals from an electronic scrap mixture. In this study, phage surface display has been used as a key method to develop peptides with high specificity for particular inorganic targets in electronic scrap. Lanthanum phosphate doped with cerium and terbium as part of the fluorescent phosphors of spent compact fluorescent lamps (CFL) was used as a target material of economic interest to test the suitability of the phage display method to the separation of rare earth minerals. One random pVIII phage library was screened for peptide sequences that bind specifically to the fluorescent phosphor LaPO4 :Ce3+ ,Tb3+ (LAP). The library contained at least 100 binding pVIII peptides per phage particle with a diversity of 1 × 109 different phage per library. After three rounds of enrichment, a phage clone containing the surface peptide loop RCQYPLCS was found to bind specifically to LAP. Specificity and affinity of the identified phage bound peptide was confirmed by using binding and competition assays, immunofluorescence assays, and zeta potential measurements. Binding and immunofluorescence assays identified the peptide's affinity for the fluorescent phosphor components CAT (CeMgAl11 O19 :Tb3+ ) and BAM (BaMgAl10 O17 :Eu2+ ). No affinity was found for other fluorescent phosphor components such as YOX (Y2 O3 :Eu3+ ). The binding specificity of the RCQYPLCS peptide loop was improved 3-51-fold by using alanine scanning mutagenesis. The identification of peptides with high specificity and affinity for special components in the fluorescent phosphor in CFLs provides a potentially new strategic approach to rare earth recycling. Biotechnol. Bioeng. 2017;114: 1016-1024. © 2016 Wiley Periodicals, Inc.

Monte Carlo Simulations for the Detection of Buried Objects Using Single Sided Backscattered Radiation.

BACKGROUND: Detection of buried improvised explosive devices (IEDs) is a delicate task, leading to a need to develop sensitive stand-off detection technology. The shape, composition and size of the IEDs can be expected to be revised over time in an effort to overcome increasingly sophisticated detection methods. As an example, for the most part, landmines are found through metal detection which has led to increasing use of non-ferrous materials such as wood or plastic containers for chemical based explosives being developed. METHODOLOGY: Monte Carlo simulations have been undertaken considering three different commercially available detector materials (hyperpure-Ge (HPGe), lanthanum(III) bromide (LaBr) and thallium activated sodium iodide (NaI(Tl)), applied at a stand-off distance of 50 cm from the surface and burial depths of 0, 5 and 10 cm, with sand as the obfuscating medium. Target materials representing medium density wood and mild steel have been considered. Each detector has been modelled as a 10 cm thick cylinder with a 20 cm diameter. PRINCIPAL FINDINGS: It appears that HPGe represents the most promising detector for this application. Although it was not the highest density material studied, its excellent energy resolving capability leads to the highest quality spectra from which detection decisions can be inferred. CONCLUSIONS: The simulation work undertaken here suggests that a vehicle-born threat detection system could be envisaged using a single betatron and a series of detectors operating in parallel observing the space directly in front of the vehicle path. Furthermore, results show that non-ferrous materials such as wood can be effectively discerned in such remote-operated detection system, with the potential to apply a signature analysis template matching technique for real-time analysis of such data.

[Leaching of Rare Earth Elements from Coal Ashes Using Acidophilic Chemolithotrophic Microbial Communities].

A method for leaching rare earth elements from coal ash in the presence of elemental sulfur using communities of acidophilic chemolithotrophic microorganisms was proposed. The optimal parameters determined for rare element leaching in reactors were as follows: temperature, 45 degrees C; initial pH, 2.0; pulp density, 10%; and the coal ash to elemental sulfur ratio, 10 : 1. After ten days of leaching, 52.0, 52.6, and 59.5% of scandium, yttrium, and lanthanum, respectively, were recovered.

Selective Dissolution of A-Site Cations in ABO3 Perovskites: A New Path to High-Performance Catalysts.

Selective dissolution is a common corrosion process in dealloying in which an alloy is immersed in acid to remove the active element, leaving behind an inert constituent. We introduce this technique into the treatment of oxide catalysts. A three-dimensionally ordered macroporous LaMnO3 perovskite has been prepared and treated with diluted HNO3 to selectively remove La cations, acquiring a novel γ-MnO2-like material. LaMnO3 is not a satisfactory catalyst on CO oxidation. Upon the removal of La cations, the obtained sample showed a significantly higher CO oxidation catalytic activity (T50=89 °C) than the initial precursor LaMnO3 (T50=237 °C) and ordinary γ-MnO2 (T50=148 °C). A large surface area, a high degree of mesoporosity, excellent low-temperature reducibility, and especially improved surface oxygen species are deduced to be responsible for CO oxidation at lower temperatures.

Decontamination of protective clothing against radioactive contamination.

The aim of this study is to describe the experimental results of external surface mechanical decontamination of the studied materials forming selected suits. Seven types of personal protective suits declaring protection against radioactive aerosol contamination in different price ranges were selected for decontamination experiments. The outcome of this study is to compare the efficiency of a double-step decontamination process on various personal protective suits against radioactive contamination. A comparison of the decontamination effectiveness for the same type of suit, but for the different chemical mixtures ((140)La in a water-soluble or in a water-insoluble compound), was performed.

The kinetics of uptake and recovery of lanthanum using freshwater algae as biosorbents: comparative analysis.

In this study, the adsorption and desorption kinetics of lanthanum (La) on micro algal cells was investigated. The internal transcribed spacer (ITS) and 18S ribosomal RNA gene (rRNA) were used for molecular identification of the species. The algal species were found to have 95-98% identities to Desmodesmus multivariabilis, Scenedesmus acuminutus, Chloroidium saccharophilum and Stichococcus bacillaris. The species were cultured and tested independently. D. multivariabilis was found to be the most efficient at adsorbing lanthanum with a maximum sorption capacity (qmax) of 100 mg/g and a high affinity (b) of 4.55 L/g. Desorption of La was also highest in D. multivariabilis with recovery up to 99.63% at initial concentration as high as 100 mg/L. Desorption data fitted best to the modified pseudo second-order with a better correlation coefficient (R(2)) of ⩽0.98 than first order model. The results showed feasibility of lanthanum recovery using algal sorbents, a cost effective method.

Capillary microextraction combined with fluorinating assisted electrothermal vaporization inductively coupled plasma optical emission spectrometry for the determination of trace lanthanum, europium, dysprosium and yttrium in human hair.

In this work, a congo red modified single wall carbon nanotubes (CR-SWCNTs) coated fused-silica capillary was prepared and used for capillary microextraction (CME) of trace amounts of lanthanum (La), europium (Eu), dysprosium (Dy) and yttrium (Y) in human hair followed by fluorinating assisted electrothermal vaporization-inductively coupled plasma-optical emission spectrometry (FETV-ICP-OES) determination. The adsorption properties and stability of the prepared CR-SWCNTs coated capillary along with the various factors affecting the separation/preconcentration of La, Eu, Dy and Y by CME were investigated in detail. Under the optimized conditions, with a consumption of 2 mL sample solution, a theoretical enrichment factor of 50 and a detection limit (3σ) of 0.12 ng mL(-1) for La, 0.03 ng mL(-1) for Eu, 0.11 ng mL(-1) for Dy and 0.03 ng mL(-1) for Y were obtained, respectively. The preparation reproducibility of the CR-SWCNTs coated capillary was investigated and the relative standard deviations (RSDs) were ranging from 4.1% (Eu) to 4.4% (La) (CLa, Dy=1.4 ng mL(-1); CY, Eu=0.25 ng mL(-1), n=7) in one batch, and from 5.7% (Eu) to 6.1% (Y) (CLa, Dy=1.4 ng mL(-1); CY, Eu=0.25 ng mL(-1), n=5) among different batches. The proposed method was applied to the analysis of real-world human hair sample and the recoveries for the spiked sample were in the range of 93-105%. The method was also applied to the determination of La, Eu, Dy and Y in Certified Reference Material of GBW07601 human hair, and the determined values were in good agreement with the certified values.

Biosorption and desorption of lanthanum(III) and neodymium(III) in fixed-bed columns with Sargassum sp.: perspectives for separation of rare earth metals.

Rare earth (RE) metals are essentials for the manufacturing of high-technology products. The separation of RE is complex and expensive; biosorption is an alternative to conventional processes. This work focuses on the biosorption of monocomponent and bicomponent solutions of lanthanum(III) and neodymium(III) in fixed-bed columns using Sargassum sp. biomass. The desorption of metals with HCl 0.10 mol L(-1) from loaded biomass is also carried out with the objective of increasing the efficiency of metal separation. Simple models have been successfully used to model breakthrough curves (i.e., Thomas, Bohart-Adams, and Yoon-Nelson equations) for the biosorption of monocomponent solutions. From biosorption and desorption experiments in both monocomponent and bicomponent solutions, a slight selectivity of the biomass for Nd(III) over La(III) is observed. The experiments did not find an effective separation of the RE studied, but their results indicate a possible partition between the metals, which is the fundamental condition for separation perspectives.

Several factors influencing the stability of extracted species in synergistic extraction of lanthanide(III) with pivaloyltrifluoroacetone and 2,2'-bipyridyl.

The stability constants and the hydration number of a complex between tris(pivaloyltrifluoroacetonato)lanthanide(III) (LnA(3)) and 2,2'-bipyridyl (B), LnA(3)B, and the complexation heat were determined across the Ln series by a solvent-extraction technique, Karl Fischer coulometry, and calorimetry, successively. The number of water molecules released from LnA(3) upon the complexation with B as well as the values of the stability constant increased along with increasing Ln atomic number to around Dy(III); via a maximum, it decreased. It is concluded that the largest stability constant of the complex of Ho(III) or this vicinity is derived from the strongest bond energy, due to the fitness between LnA(3) and B. This conclusion was supported by the trend of the variation of the entropy change as well as that of the hydration number across the Ln series.

Reversibility of La and Lu sorption onto smectites: implications for the design of engineered barriers in deep geological repositories.

The sorption reversibility of La and Lu (considered as actinide analogues) onto a set of smectites (bentonite FEBEX; hectorite, HEC; MX80; saponite, SAP; Otay montmorillonite, SCa-3; and Texas montmorillonite, STx-1) was studied to estimate actinide retention by smectites that are candidates for use as engineered barriers in deep geological repositories. The sorption distribution coefficients (K(d)) and the reversibility parameters (desorption distribution coefficients (K(d,des)), adjusted distribution coefficients (K(d,adj)), and desorption rates (R(des))) were determined from batch tests in two ionic media: deionized water and Ca 0.02 mol L(-1). The latter simulates possible conditions due to the presence of concrete leachates. The results varied greatly depending on the ionic medium, the lanthanide concentration and the clay structure. The high values of K(d,des) obtained (up to 1.1 x 10(5) and 9.2 x 10(4) L kg(-1) for La and Lu in water, and 2.8 x 10(4) and 4.1 x 10(4)L kg(-1) for La and Lu in the Ca medium) indicate the suitability of the tested smectites for lanthanide (and therefore, actinide) retention. Based on all the data, SCa-3, HEC and FEBEX clays are considered the best choices for water environments, whereas in Ca environments the suitable clays depended on the lanthanide considered.

Recovery of rare metal compounds from nickel-metal hydride battery waste and their application to CH4 dry reforming catalyst.

The recovery of valuable components such as nickel from nickel-metal hydride (Ni-MH) battery waste by chemical processes and their applications to CH(4) dry reforming catalysts were investigated. Three types of compound, identified by XRD analysis as NiO, CeO(2) and LaCoO(3) phases, were successfully separated from the waste by a series of chemical processes at room temperature using aqueous solutions of HCl, NaOH and NH(3), and Ni component of approximately 70% in Ni-MH battery waste was recovered. The separated NiO, CeO(2) and LaCoO(3) showed catalytic activities for CH(4) dry reforming. In particular, the separated NiO easily reduced to Ni(0) at an initial stage, and exhibited excellent catalytic activity in terms of CH(4) conversion and stability. Furthermore, it was found that the resulting Ni from separated NiO exhibited an anomalous catalysis from the comparison with that from regent NiO.

Studies on the adsorption behavior of trace amounts of 90Sr2+, 140La3+, 60Co2+, Ni2+ and Zr4+ cations on synthesized inorganic ion exchangers.

Three inorganic ion exchangers namely potassium zinc hexacyanoferrate(II) (PZF), magnesium oxide-polyacrylonitrile composite (MgO-PAN) and ammonium molybdophosphate (AMP) were synthesized. The physicochemical properties of these ion exchangers were determined using different techniques including inductively coupled plasma (ICP), CHNSO elemental analysis, infrared spectroscopy (IR), X-ray diffraction (XRD), thermogravimetric (TGA) and pH - titration curve analysis. The solubility of the synthesized ion exchangers in different acidic and alkaline media, their thermal stability and the effect of gamma irradiation were investigated. It was observed that the exchange capacity of the ion exchangers depend upon the pH value of the solution used. Furthermore, the adsorption of (90)Sr(2+), (140)La(3+), (60)Co(2+) and the distribution coefficient of these ion exchangers for Ni(2+)and Zr(4+) were studied. The effect of parameters such as pH and contact time on the adsorption was also investigated and the optimum conditions for separation of these ions were determined.

Development of soft-based double-stranded peptide chelators which selectively separate europium and lanthanum ions based on the hardness concept.

New double-stranded peptide chelators (1) conjugated Cat (2,3-dihydroxybenzoic acid) were synthesized and formed a molecular complex 1-Eu(3+) (or 1-Lu(3+)) with Eu(3+) and Lu(3+) but not La(3+). The double-stranded peptide chelator may prove to be useful tools for studying the selective separation of lanthanide ions.