Exploiting the biological response of two Serratia fonticola strains to the critical metals, gallium and indium.

The use of microorganisms that allows the recovery of critical high-tech elements such as gallium (Ga) and indium (In) has been considered an excellent eco-strategy. In this perspective, it is relevant to understand the strategies of Ga and In resistant strains to cope with these critical metals. This study aimed to explore the effect of these metals on two Ga/In resistant strains and to scrutinize the biological processes behind the oxidative stress in response to exposure to these critical metals. Two strains of Serratia fonticola, A3242 and B2A1Ga1, with high resistance to Ga and In, were submitted to metal stress and their protein profiles showed an overexpressed Superoxide Dismutase (SOD) in presence of In. Results of inhibitor-protein native gel incubations identified the overexpressed enzyme as a Fe-SOD. Both strains exhibited a huge increase of oxidative stress when exposed to indium, visible by an extreme high amount of reactive oxygen species (ROS) production. The toxicity induced by indium triggered biological mechanisms of stress control namely, the decrease in reduced glutathione/total glutathione levels and an increase in the SOD activity. The effect of gallium in cells was not so boisterous, visible only by the decrease of reduced glutathione levels. Analysis of the cellular metabolic viability revealed that each strain was affected differently by the critical metals, which could be related to the distinct metal uptakes. Strain A3242 accumulated more Ga and In in comparison to strain B2A1Ga1, and showed lower metabolic activity. Understanding the biological response of the two metal resistant strains of S. fonticola to stress induced by Ga and In will tackle the current gap of information related with bacteria-critical metals interactions.

Adsorption of indium by waste biomass of brown alga Ascophyllum nodosum.

The biosorption capacities of dried meal and a waste product from the processing for biostimulant extract of Ascophyllum nodosum were evaluated as candidates for low-cost, effective biomaterials for the recovery of indium(III). The use of indium has significantly grown in the last decade, because of its utilization in hi-tech. Two formats were evaluated as biosorbents: waste-biomass, a residue derived from the alkaline extraction of a commercial, biostimulant product, and natural-biomass which was harvested, dried and milled as a commercial, "kelp meal" product. Two systems have been evaluated: ideal system with indium only, and double metal-system with indium and iron, where two different levels of iron were investigated. For both systems, the indium biosorption by the brown algal biomass was found to be pH-dependent, with an optimum at pH3. In the ideal system, indium adsorption was higher (maximum adsorptions of 48 mg/g for the processed, waste biomass and 63 mg/g for the natural biomass), than in the double metal-system where the maximum adsorption was with iron at 0.07 g/L. Good values of indium adsorption were demonstrated in both the ideal and double systems: there was competition between the iron and indium ions for the binding sites available in the A. nodosum-derived materials. Data suggested that the processed, waste biomass of the algae, could be a good biosorbent for its indium absorption properties. This had the double advantages of both recovery of indium (high economic importance), and also definition of a virtuous circular economic innovative strategy, whereby a waste becomes a valuable resource.

S-layer protein-AuNP systems for the colorimetric detection of metal and metalloid ions in water.

Bacterial surface layer proteins (S-layer) possess unique binding properties for metal ions. By combining the binding capability of S-layer proteins with the optical properties of gold nanoparticles (AuNP), namely plasmonic resonance, a colorimetric detection system for metal and metalloid ions in water was developed. Eight S-layer proteins from different bacteria species were used for the functionalization of AuNP. The thus developed biohybrid systems, AuNP functionalized with S-layer proteins, were tested with different metal salt solutions, e.g. Indium(III)-chloride, Yttrium(III)-chloride or Nickel(II)-chloride, to determine their selective and sensitive binding to ionic analytes. All tested S-layer proteins displayed unique binding affinities for the different metal ions. For each S-layer and metal ion combination markedly different reaction patterns and differences in concentration range and absorption spectra were detected by UV/vis spectroscopy. In this way, the selective detection of tested metal ions was achieved by differentiated analysis of a colorimetric screening assay of these biohybrid systems. A highly selective and sensitive detection of yttrium ions down to a concentration of 1.67 × 10-5 mol/l was achieved with S-layer protein SslA functionalized AuNP. The presented biohybrid systems can thus be used as a sensitive and fast sensor system for metal and metalloid ions in aqueous systems.

Separation and recovery of glass, plastic and indium from spent LCD panels.

The present paper deals with physico-mechanical pre-treatments for dismantling of spent liquid crystal displays (LCDs) and further recovery of valuable fractions like plastic, glass and indium. After a wide experimental campaign, two processes were designed, tested and optimized. In the wet process, 20%, 15% and 40% by weight of the feeding panels are recovered as plastic, glass and indium concentrate, respectively. Instead, in the dry process, only two fractions were separated: around 11% and 85% by weight are recovered as plastic and glass/indium mixture. Indium, that concentrated in the -212µm fraction, was completely dissolved by sulphuric acid leaching (0.75molL-1 H2SO4 solution, 80°C, 10%vol H2O2, pulp density 10%wt/vol, leaching time 3h). 100% of indium can be extracted from the pregnant solution with 5%wt/vol Amberlite™ resin, at room temperature and pH 3 in 24h. Indium was thus re-extracted from the resin by means of a 2molL-1 H2SO4 solution, at room temperature and S/L of 40%wt/vol.

Beneficiation and recovery of indium from liquid-crystal-display glass by hydrometallurgy.

Considering indium scarcity, the end-of-life (EOL) LCD, which accounts for up to 90% of market share can be a feasible secondary resource upon successful recycling. In the preferred hydrometallurgical process of such critical metals, leaching is the essential primary and essential phase has been investigated. In this process, LCD was mechanically separated along with other parts from EOL TVs through a smartly engineered process developed at our institute, Institute for Advanced Engineering (IAE), the Republic of Korea. After removing plastics and metals from the LCD, it was mechanically shredded for size reduction. The mechanically shredded LCD waste was leached with HCl for recovery of indium. Possible leaching parameters such as; effect of acid concentration, pulp density, temperature and effect of oxidant H2O2 concentration were investigated to identify the best conditions for indium extraction. Indium (76.16×10-3g/L) and tin (10.24×10-3g/L) leaching was achieved at their optimum condition, i.e. lixiviant of 5M HCl, a pulp density of 500g/L, temperature 75°C, agitation speed of 400rpm and time for 120min. At optimum condition the glass, plastic and the valuable metal indium have completely been separated. From indium enriched leach liquor, indium can be purified and recovered through hydrometallurgy.

Adsorption of indium(III) ions from aqueous solution using chitosan-coated bentonite beads.

Batch adsorption study was utilized in evaluating the potential suitability of chitosan-coated bentonite (CCB) as an adsorbent in the removal of indium ions from aqueous solution. The percentage (%) removal and adsorption capacity of indium(III) were examined as a function of solution pH, initial concentration, adsorbent dosage and temperature. The experimental data were fitted with several isotherm models, where the equilibrium data was best described by Langmuir isotherm. The mean energy (E) value was found in the range of 1-8kJ/mol, indicating that the governing type of adsorption of indium(III) onto CCB is essentially physical. Thermodynamic parameters, including Gibbs free energy, enthalpy, and entropy indicated that the indium(III) ions adsorption onto CCB was feasible, spontaneous and endothermic in the temperature range of 278-318K. The kinetics was evaluated utilizing the pseudo-first order and pseudo-second order model. The adsorption kinetics of indium(III) best fits the pseudo-second order (R(2)>0.99), which implies that chemical sorption as the rate-limiting step.

Recycling indium from waste liquid crystal display panel by vacuum carbon-reduction.

This study investigated the recovery of indium from waste liquid crystal display (LCD) panel using vacuum carbon-reduction. First of all, high purity In2O3 was investigated. The results indicated that indium can be reclaimed from In2O3 using vacuum carbon-reduction in thermodynamics and dynamics. The conditions of 1223K, 50wt% carbon addition, 30min, and 1Pa were confirmed as the optimal conditions for pure In2O3 and high purity indium could be selectively recovered on condensing zone. Based on this, the experiment of the recovery of indium from waste LCD power was performed. The best parameters were confirmed as 1223K and 1Pa with 30wt% carbon addition for 30min. The recovery rate of indium from LCD powder could reach to 90wt%. No hazardous materials produced in this process. Therefore, this technique provides the possibility of reutilization of LCD in an environmentally friendly way.

Recovery of indium from used LCD panel by a time efficient and environmentally sound method assisted HEBM.

In this study, a method which is environmentally sound, time and energy efficient has been used for recovery of indium from used liquid crystal display (LCD) panels. In this method, indium tin oxide (ITO) glass was crushed to micron size particles in seconds via high energy ball milling (HEBM). The parameters affecting the amount of dissolved indium such as milling time, particle size, effect time of acid solution, amount of HCl in the acid solution were tried to be optimized. The results show that by crushing ITO glass to micron size particles by HEBM, it is possible to extract higher amount of indium at room temperature than that by conventional methods using only conventional shredding machines. In this study, 86% of indium which exists in raw materials was recovered about in a very short time.

Extraction of gallium(III) from hydrochloric acid solutions by trioctylammonium-based mixed ionic liquids.

The extractabilities of aluminium(III), gallium(III), and indium(III) from hydrochloric acid solutions were investigated using a mixture of two protic ionic liquids, trioctylammonium bis(trifluoromethanesulfonyl)amide ([TOAH][NTf(2)]) and trioctylammonium nitrate ([TOAH][NO(3)]). At a HCl concentration of 4 mol L(-1) or more, gallium(III) was nearly quantitatively extracted and the extractability order was Ga > Al >> In. The extractability of gallium(III) increased with increasing [TOAH][NO(3)] content in the mixed ionic liquid. The extracted gallium(III) was quantitatively stripped with aqueous nitric acid solutions. The separation and recovery of gallium(III) from hydrochloric acid solutions containing excess indium(III) was demonstrated using the mixed ionic liquid.

Leaching of indium from obsolete liquid crystal displays: comparing grinding with electrical disintegration in context of LCA.

In order to develop an effective recycling system for obsolete Liquid Crystal Displays (LCDs), which would enable both the leaching of indium (In) and the recovery of a pure glass fraction for recycling, an effective liberation or size-reduction method would be an important pre-treatment step. Therefore, in this study, two different types of liberation methods: (1) conventional grinding, and (2) electrical disintegration have been tested and evaluated in the context of Life Cycle Assessment (LCA). In other words, the above-mentioned methods were compared in order to find out the one that ensures the highest leaching capacity for indium, as well as the lowest environmental burden. One of the main findings of this study was that the electrical disintegration was the most effective liberation method, since it fully liberated the indium containing-layer, ensuring a leaching capacity of 968.5mg-In/kg-LCD. In turn, the estimate for the environmental burden was approximately five times smaller when compared with the conventional grinding.

Determination of trace indium in urine after preconcentration with a chelating-resin-packed minicolumn.

A simple and rapid chelating-resin-packed column has been developed for preconcentration of trace indium in biological samples. A large-sized urine sample was pumped through a minicolumn at a flow rate of 1.0 mL/min by using a peristaltic pump, and the eluents were analyzed using graphite furnace atomic absorption spectrometry (GFAAS). Four commercially available chelating resins including Chelex-100, Amberlite IRC-50, Duolite GT-73, and Celite 545-AW were studied for evaluating the indium sorption performance. Several parameters, such as pH, resin amount, eluent volume, eluent flow rate, and the volume of sample, were investigated and optimized. A 100-200 mL of the sample was loaded into a column containing 1.2 g of wet Chelex-100 and subjected to the ion-exchange procedure. The retained analytes were eluted with 5.0 mL of 0.1 M HNO(3) and quantified by GFAAS. The correlation coefficient in the range 10-250 ng/mL was of 0.9994. The limit of detection of the proposed method was 2.75 ng/mL. The method developed was successfully applied to analysis of spiked urine samples with good recoveries of 93-103% (n = 6) and reproducibility (relative standard deviation < 4.9%). The accuracy of procedure was confirmed by indium determination in spiked certified reference materials.

Extraction equilibrium of indium(III) from nitric acid solutions by di(2-ethylhexyl)phosphoric acid dissolved in kerosene.

The extraction equilibrium of indium(III) from a nitric acid solution using di(2-ethylhexyl) phosphoric acid (D2EHPA) as an acidic extractant of organophosphorus compounds dissolved in kerosene was studied. By graphical and numerical analysis, the compositions of indium-D2EHPA complexes in organic phase and stoichiometry of the extraction reaction were examined. Nitric acid solutions with various indium concentrations at 25 °C were used to obtain the equilibrium constant of InR3 in the organic phase. The experimental results showed that the extraction distribution ratios of indium(III) between the organic phase and the aqueous solution increased when either the pH value of the aqueous solution and/or the concentration of the organic phase extractant increased. Finally, the recovery efficiency of indium(III) in nitric acid was measured.

Processing of spent platinum-based catalysts via fusion with potassium hydrogenosulfate.

This work describes a route for processing spent platinum-based commercial catalysts (Pt and PtSnIn/Al(2)O(3)) via fusion with potassium hydrogenosulfate (KHSO(4)). Samples were previously ground. The optimized experimental parameters were: temperature, 450°C; time, 3h; sample/flux mass ratio, 1/10. The fused mass was dissolved in water and the elements present were isolated by a multi-step separation procedure. Platinum was recovered as the only water-insoluble residue. About 45 wt% of aluminium was recovered as KAl(SO(4))(2)·12H(2)O (alum), whereas the remaining element was recovered as Al(OH)(3). Tin and indium were recovered together as sulfides at pH 1. About 72 wt% of potassium was recovered as K(2)SO(4) when the final effluent was treated with sulfuric acid (pH 1) and slowly evaporated. Generation of final wastes was greatly reduced. More than 98 wt% of the elements present in the catalysts examined was recovered.

Recovery of indium from etching wastewater using supercritical carbon dioxide extraction.

This study presents supercritical carbon dioxide (scCO(2)) extraction as an inherently safer and cleaner method for the recovery of indium (In) from the real etching wastewater obtained from indium tin oxide (ITO) etching process. Efficient chelation-supercritical fluids extraction (SFE) from etching wastewater was obtained at 80 degrees C, a pressure of 20.7MPa, and with 15 min static extractions followed by 15 min dynamic extraction. The extractions were performed using unmodified scCO(2) in the presence of the fluorinated beta-diketone chelating agent, 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione (HFOD). Percentages of indium recovery from etching wastewater were between 90.8% and 100.3% (n=6) with relative standard deviations of <10%. The accuracy of the procedure was confirmed by determining indium levels in a single element standard solution. The developed method was applied to the analysis of real etching wastewater samples as well as to a commercially available ITO etching reagent (ITO-06SD) with satisfactory results.

Effect of operating parameters on indium (III) ion removal by iron electrocoagulation and evaluation of specific energy consumption.

The aim of this study is to investigate the effects of operating parameters on the specific energy consumption and removal efficiency of synthetic wastewater containing indium (III) ions by electrocoagulation in batch mode using an iron electrode. Several parameters, including different electrode pairs, supporting electrolytes, initial concentration, pH variation, and applied voltage, were investigated. In addition, the effects of applied voltage, supporting electrolyte, and initial concentration on indium (III) ion removal efficiency and specific energy consumption were investigated under the optimum balance of reasonable removal efficiency and relative low energy consumption. Experiment results indicate that a Fe/Al electrode pair is the most efficient choice of the four electrode pairs in terms of energy consumption. The optimum supporting electrolyte concentration, initial concentration, and applied voltage were found to be 100 mg/l NaCl, 20 mg/l, and 20V, respectively. A higher pH at higher applied voltage (20 or 30V) enhanced the precipitation of indium (III) ion as insoluble indium hydroxide, which improved the removal efficiency. Results from the indium (III) ion removal kinetics show that the kinetics data fit the pseudo second-order kinetic model well. Finally, the composition of the sludge produced was characterized with energy dispersion spectra (EDS).

Recovery of valuable materials from waste liquid crystal display panel.

Associated with the rapid development of the information and electronic industry, liquid crystal displays (LCDs) have been increasingly sold as displays. However, during the discarding at their end-of-life stage, significant environmental hazards, impacts on health and a loss of resources may occur, if the scraps are not managed in an appropriate way. In order to improve the efficiency of the recovery of valuable materials from waste LCDs panel in an environmentally sound manner, this study presents a combined recycling technology process on the basis of manual dismantling and chemical treatment of LCDs. Three key processes of this technology have been studied, including the separation of LCD polarizing film by thermal shock method the removal of liquid crystals between the glass substrates by the ultrasonic cleaning, and the recovery of indium metal from glass by dissolution. The results show that valuable materials (e.g. indium) and harmful substances (e.g. liquid crystals) could be efficiently recovered or separated through above-mentioned combined technology. The optimal conditions are: (1) the peak temperature of thermal shock to separate polarizing film, ranges from 230 to 240 degrees C, where pyrolysis could be avoided; (2) the ultrasonic-assisted cleaning was most efficient at a frequency of 40 KHz (P = 40 W) and the exposure of the substrate to industrial detergents for 10 min; and (3) indium separation from glass in a mix of concentrated hydrochloric acid at 38% and nitric acid at 69% (HCl:HNO(3):H(2)O = 45:5:50, volume ratio). The indium separation process was conducted with an exposure time of 30 min at a constant temperature of 60 degrees C.

Utility of 1-octanol/octane mixed solvents for the solvent extraction of aluminum(III), gallium(III), and indium(III) with 8-quinolinol.

Using 1-octanol/octane mixed solvents, the extraction of aluminum(III), gallium(III) and indium(III) with 8-quinolinol was carried out at 25 degrees C. The formation constants of the respective metal(III) 8-quinolinolates in the aqueous phase and their partition constants between the mixed solvents and water were determined based on an analysis of the extraction equilibria. The relationship between the partition constants of 8-quinolinol and its complexes was analyzed by the regular solution theory. The molar volumes of aluminum(III), gallium(III) and indium(III) 8-quinolinolates, calculated from the present results, suggest that the electrostriction effect functions in complex forming. It has been found that octane/1-octanol mixed solvents were available not only for the extraction of metal ions, but also for determining the formation constants of these metal 8-quinolinolates in the aqueous phase and their partition constants.

A solid phase extraction procedure for indium prior to its graphite furnace atomic absorption spectrometric determination.

A procedure based on solid phase extraction of indium ions at trace level on Chromosorb 108 resin as bathocuproinedisulfonic acid chelate is presented for its preconcentration. The optimum pH value for quantitative sorption is 8.0-9.0, and desorption can be achieved by using 10.0 ml of 2 M HNO3. The effects of diverse ions on the sorption and recovery of indium have been studied. The capacity of sorbent was 3.78 mg In/g resin. Recoveries for indium from water samples were in the range 95-105%. The accuracy of procedure was confirmed by indium determination in certified reference materials. The method developed was applied with varying results to the analysis of real samples including metallic zinc with satisfactory results.

Characterization and ultrafiltration of semiconductor indium phosphide (InP) wastewater for recycling.

This research work investigated the physical and chemical properties of a new type of wastewater produced from the semiconductor industry. The wastewater generated from indium phosphide (InP) wafer backgrinding and sawing processes was characterized in term of its particle size distribution (PSD), zeta potential, suspended and dissolved solids, total organic carbon, and turbidity. The wastewater contained high concentration of fine InP dusts with a size ranging from 0.07 - 1.44 mm. In spite of its high concentration of suspended solids resulting in high turbidity up to 371 NTU, the wastewater contained very low organic matters (TOC < 2.2 mg l(-1)) and other inorganic impurities (SO4(2-) < 0.21 mg l(-1) and Na+ < 0.16 mg l(-1)). Based on the experimental data collected, the treatment technologies using chemical precipitation and ultrafiltration were applied to the wastewater. Both processes could effectively remove InP particles from the wastewater, however the coagulants in chemical precipitation introduced other ionic contents into the process resulting in difficulties of water recycling in the later stage. In comparison, ultrafiltration was more promising for InP wastewater treatment and recycling. Based on the results of this study, a full-scale UF system was built in a local semiconductor plant and it has successfully reclaimed water from the InP wastes for the past six months without any quality issue being raised.

Simultaneous determination of gallium and indium with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol in cationic micellar medium using derivative spectrophotometry.

A new derivative spectrophotometric method for rapid and selective trace analysis of Ga3+ and In3+ and for their simultaneous determination using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol in a cationic micellar medium is reported. Molar absorptivity and Sandell's sensitivity of 1:1 Ga+ and In3+ complexes at their lambda(max) 553 nm and 558 nm are: 7.22 x 10(4) l mol(-1) cm(-1) and 5.85 x 10(4) l mol(-1) cm(-1), and 0.96 ng cm(-2) and 1.96 ng cm(-2), respectively. Linearity is observed in the concentration range 0.023-0.700 microg ml(-1) for gallium and 0.076-1.52 microg ml(-1) for indium; IUPAC detection limit is 0.012 and 0.035 ng ml(-1), respectively. These metal ions interfere with the determination of each other. However, 0.07-0.70 microg ml(-1) Ga3+ and 0.115-1.150 microg ml(-1) In3+ could be determined simultaneously when present together by the derivative method without any prior separation. The proposed procedures have been successfully applied for the individual and simultaneous determination of gallium and indium in synthetic binary mixtures, standard reference materials and environmental samples.