Biorecovery of cobalt and nickel using biomass-free culture supernatants from Aspergillus niger.

In this research, the capabilities of culture supernatants generated by the oxalate-producing fungus Aspergillus niger for the bioprecipitation and biorecovery of cobalt and nickel were investigated, as was the influence of extracellular polymeric substances (EPS) on these processes. The removal of cobalt from solution was >90% for all tested Co concentrations: maximal nickel recovery was >80%. Energy-dispersive X-ray analysis (EDXA) and X-ray diffraction (XRD) confirmed the formation of cobalt and nickel oxalate. In a mixture of cobalt and nickel, cobalt oxalate appeared to predominate precipitation and was dependent on the mixture ratios of the two metals. The presence of EPS together with oxalate in solution decreased the recovery of nickel but did not influence the recovery of cobalt. Concentrations of extracellular protein showed a significant decrease after precipitation while no significant difference was found for extracellular polysaccharide concentrations before and after oxalate precipitation. These results showed that extracellular protein rather than extracellular polysaccharide played a more important role in influencing the biorecovery of metal oxalates from solution. Excitation-emission matrix (EEM) fluorescence spectroscopy showed that aromatic protein-like and hydrophobic acid-like substances from the EPS complexed with cobalt but did not for nickel. The humic acid-like substances from the EPS showed a higher affinity for cobalt than for nickel.

Subcritical Water Extraction of Valuable Metals from Spent Lithium-Ion Batteries.

The leaching of valuable metals (Co, Li, and Mn) from spent lithium-ion batteries (LIBs) was studied using subcritical water extraction (SWE). Two types of leaching agents, hydrochloric acid (HCl) and ascorbic acid, were used, and the effects of acid concentration and temperature were investigated. Leaching efficiency of metals increased with increasing acid concentration and temperature. Ascorbic acid performed better than HCl, which was attributed to ascorbic acid's dual functions as an acidic leaching agent and a reducing agent that facilitates leaching reactions, while HCl mainly provides acidity. The chemical analysis of leaching residue by X-ray photoelectron spectroscopy (XPS) revealed that Co(III) oxide could be totally leached out in ascorbic acid but not in HCl. More than 95% of Co, Li, and Mn were leached out from spent LIBs' cathode powder by SWE using 0.2 M of ascorbic acid within 30 min at 100 °C, initial pressure of 10 bar, and solid-to-liquid ratio of 10 g/L. The application of SWE with a mild concentration of ascorbic acid at 100 °C could be an alternative process for the recovery of valuable metal in spent LIBs. The process has the advantages of rapid reaction rate and energy efficiency that may benefit development of a circular economy.

Superior removal of Co2+, Cu2+ and Zn2+ contaminants from water utilizing spongy Ni/Fe carbonate-fluorapatite; preparation, application and mechanism.

Spongy Ni/Fe carbonate - fluorapatite was synthesized from natural phosphorite enriched with iron impurities. The morphological, chemical and structural features of the product were estimated using several techniques as XRD, SEM, EDX, and FT-IR. It exhibits spongy structure of nano and micro-pores. The average crystallite size is about 8.27 nm. The suitability of the product for considerable decontamination of Zn2+, Co2+, and Cu2+, ions from water was studied based on several reacting parameters. The equilibrium was attained after 240 min for Zn2+ and Co2+ ions while the adsorption equilibrium of Cu2+ reached after 120 min. The adsorption data for the selected metals was represented well by a pseudo-second-order model which revealed chemisorption uptake. The equilibrium studies were appraised based on traditional models and two advanced models were designed according to the statistical physical theories. The adsorption results highly fitted with Langmuir model followed rather than the other models. This indicated a monolayer adsorption for the metal ions by spongy Ni/Fe carbonate - fluorapatite. The estimated qmax values are 149.25 mg/g, 106.4 mg/g and 147.5 mg/g for the uptake of Zn2+, Co2+, and Cu2+, respectively. Based on monolayer models of one energy and two energies, the number of receptor adsorption sites, number of adsorbed metal ions per active site, the average number of sites which occupied by ions, mono layer adsorption quantity and the adsorption quantity after total saturation were calculated for the first time for such materials.

Metal concentrations in hair of patients with various head and neck cancers as a diagnostic aid.

Head and neck cancers are one of the most frequent cancers worldwide. This paper attempts to evaluate disturbances of homeostasis of the necessary elements (calcium, magnesium, zinc, copper, iron, manganese) and changes in the levels of toxic metals (lead, cadmium, cobalt, chromium VI) in hair of patients with head and neck cancers, as well as people without a diagnosed neoplastic disease. In order to quantify the necessary elements and toxic metals, a method using ICP-MS and ICP-OES techniques had been developed and validated. The studies have shown that patients with head and neck cancer used to drink alcohol and smoked much more frequently than healthy individuals, both in the past and presently. Statistically significant differences in concentrations of average metal content in the group of patients with head and neck cancers compared to the control group were confirmed. Significant differences in metal content between the group of patients with head and neck cancers and healthy individuals were found which enabled distinguishing between the study groups. To this end, a more advanced statistical tool, i.e. chemometrics, was used. The conducted research analyses and the use of advanced statistical techniques confirm the benefits of using alternative material to distinguish the patients with head and neck cancers from the healthy individuals.

Removal of Selected Metals from Wastewater Using a Constructed Wetland.

Removal of selected metals from municipal wastewater using a constructed wetland with a horizontal subsurface flow was studied. The objective of the work was to determine the efficiency of Cu, Zn, Ni, Co, Sr, Li, and Rb removal, and to describe the main removal mechanisms. The highest removal efficiencies were attained for zinc and copper (89.8 and 81.5%, respectively). It is apparently due to the precipitation of insoluble sulfides (ZnS, CuS) in the vegetation bed where the sulfate reduction takes place. Significantly lower removal efficiencies (43.9, 27.7, and 21.5%) were observed for Li, Sr, and Rb, respectively. Rather, low removal efficiencies were also attained for Ni and Co (39.8 and 20.9%). However, the concentrations of these metals in treated water were significantly lower compared to Cu and Zn (e.g., 2.8 ± 0.5 and 1.7 ± 0.3 µg/l for Ni at the inflow and outflow from the wetland compared to 27.6 ± 12.0 and 5.1 ± 4.7 µg/l obtained for Cu, respectively). The main perspective of the constructed wetland is the removal of toxic heavy metals forming insoluble compounds depositing in the wetland bed. Metal uptake occurs preferentially in wetland sediments and is closely associated with the chemism of sulfur and iron.

Copper and cobalt recovery from pyrite ashes of a sulphuric acid plant.

The pyrite ashes formed as waste material during the calcination of concentrated pyrite ore used for producing sulphuric acid not only has a high iron content but also contains economically valuable metals. These wastes, which are currently landfilled or dumped into the sea, cause serious land and environmental pollution problems owing to the release of acids and toxic substances. In this study, physical (sulphation roasting) and hydrometallurgical methods were evaluated for their efficacy to recover non-iron metals with a high content in the pyrite ashes and to prevent pollution thereby. The preliminary enrichment tests performed via sulphation roasting were conducted at different roasting temperatures and with different acid amounts. The leaching tests investigated the impact of the variables, including different solvents, acid concentrations and leach temperatures on the copper and cobalt leaching efficiency. The experimental studies indicated that the pre-enrichment via sulphation roasting method has an effect on the leaching efficiencies of copper and cobalt, and that approximate recoveries of 80% copper and 70% cobalt were achieved in the H2O2-added H2SO4 leaching tests.

A sustainable process for the recovery of valuable metals from spent lithium-ion batteries.

In this work, an eco-friendly and hydrometallurgical process for the recovery of cobalt and lithium from spent lithium-ion batteries has been proposed, which includes pretreatment, citric acid leaching, selective chemical precipitation and circulatory leaching. After pretreatment (manual dismantling, N-methyl pyrrolidone immersion and calcination), Cu and Al foils are recycled directly and the cathode active materials are separated from the cathode efficiently. Then, the obtained cathode active materials (waste LiCoO2) was firstly leached with 1.25 mol l(-1) citric acid and 1 vol.% H2O2 solution. Then cobalt was precipitated using oxalic acid (H2C2O4) under a molar ratio of 1:1.05 (H2C2O4: Co(2+)). After filtration, the filtrate (containing Li(+)) and H2O2 was employed as a leaching agent and the optimum conditions are studied in detail. The leaching efficiencies can reach as high as 98% for Li and 90.2% for Co, respectively, using filter liquor as leaching reagent under conditions of leaching temperature of 90°C, 0.9 vol.% H2O2 and a solid-to-liquid ratio of 60 ml g(-1) for 35 min. After three bouts of circulatory leaching, more than 90% Li and 80% Co can be leached under the same leaching conditions. In this way, Li and Co can be recovered efficiently and waste liquor re-utilization is achievable with this hydrometallurgical process, which may promise both economic and environmental benefits.

Recovery of Nickel and Cobalt from Laterite Tailings by Reductive Dissolution under Aerobic Conditions Using Acidithiobacillus Species.

Biomining of sulfidic ores has been applied for almost five decades. However, the bioprocessing of oxide ores such as laterites lags commercially behind. Recently, the Ferredox process was proposed to treat limonitic laterite ores by means of anaerobic reductive dissolution (AnRD), which was found to be more effective than aerobic bioleaching by fungi and other bacteria. We show here that the ferric iron reduction mediated by Acidithiobacillus thiooxidans can be applied to an aerobic reductive dissolution (AeRD) of nickel laterite tailings. AeRD using a consortium of Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans extracted similar amounts of nickel (53-57%) and cobalt (55-60%) in only 7 days as AnRD using Acidithiobacillus ferrooxidans. The economic and environmental advantages of AeRD for processing of laterite tailings comprise no requirement for an anoxic atmosphere, 1.8-fold less acid consumption than for AnRD, as well as nickel and cobalt recovered in a ferrous-based pregnant leach solution (PLS), facilitating the subsequent metal recovery. In addition, an aerobic acid regeneration stage is proposed. Therefore, AeRD process development can be considered as environmentally friendly for treating laterites with low operational costs and as an attractive alternative to AnRD.

Removal of cobalt(II) ion from aqueous solution by chitosan-montmorillonite.

Montmorillonite (MMT) modified with chitosan (CTS, molecular weight=5×10(4)) was applied to remove heavy metal cations by using Co(2+) as a model ion. An increase in MMT interlayer distance observed from X-ray diffraction indicates the intercalation of CTS into MMT. Together with the results of scanning electron microscopy and Fourier transform infrared spectroscopy, it was concluded that the composite material of CTS and MMT (CTS-MMT) was prepared successfully. The mass ratio of CTS to MMT had a strong influence on the adsorption performance of CTS-MMT. The highest adsorption value of 150mg/g was obtained over the composite material with CTS to MMT mass ratio of 0.25, which is much higher than those reported in other studies. The adsorption isotherms and kinetic results indicated that Co(2+) was adsorbed over CTS-MMT in a multilayer model, and the chemical sorption of Co(2+) was determined to be the rate-limiting step.

Lithium and cobalt extraction from LiCoO2 assisted by p(VBPDA-co-FDA) copolymers in supercritical CO2.

Supercritical CO2 (scCO2) extraction assisted by complexing copolymers is a promising process to recover valuable metals from lithium-ion batteries (LIBs). CO2, in addition to being non-toxic, abundant and non-flammable, allows an easy separation of metal-complexes from the extraction medium by depressurization, limiting the wastewater production. In this study, CO2-philic gradient copolymers bearing phosphonic diacid complexing groups (poly(vinylbenzylphosphonic diacid-co-1,1,2,2-tetrahydroperfluorodecylacrylate), p(VBPDA-co-FDA)) were synthesized for the extraction of lithium and cobalt from LiCoO2 cathode material. Notably, the copolymer was able to play the triple role of leaching agent, complexing agent and surfactant. The proof of concept for leaching, complexation and extraction was achieved, using two different extraction systems. A first extraction system used aqueous hydrogen peroxide as reducing agent while it was replaced by ethanol in the second extraction system. The scCO2 extraction conditions such as extraction time, temperature, functional copolymer concentration, and the presence of additives were optimized to improve the metals extraction from LiCoO2 cathode material, leading to an extraction efficiency of Li and Co up to ca. 75 % at 60 °C and 250 bar.

Nickel-manganese-cobalt tetragonal spinel ternary oxide nanocomposite as an effective adsorbent for dispersive solid phase micro-extraction of cadmium in food and water samples.

Nickel-manganese-cobalt tetragonal spinel ternary oxide nanocomposite (NMC-TSO) was synthesized. It was utilized as an efficient sorbent for the dispersive solid phase microextraction (D-SPµE) without vortexing of cadmium. The analysis of the cadmium was carried out by FAAS. The effective analytical parameters including pH (6) contact times (no vortexing), sample volume (70 mL), eluent volume (3 mL of 2 mol L-1 HCl), linear dynamic ranges (1.07-85.7 µg L-1), and re-useability (33) on the D-SPµE efficiency were investigated. The PF, RSD% and LOD of the D-SPµE for cadmium were 23.3, ≤ 2.8% and 0.49 µg L-1, respectively. The tolerable concentrations of Ca2+, Mg2+, K+ and Na+ on Cd(II) were 50,000 mg L-1, 50,000 mg L-1, 25,000 mg L-1 and 7500 mg L-1, respectively. The method was accurated by analysis of food and water certificate reference materials (NW-TMDA-54.6 Lake water, SPS-WW1 121 Batch wastewater, 1573a Tomato Leaves and TORT-3 Lobster Hepatopancreas) and - recovery experiments. The D-SPµE-FAAS method was applied for the cadmium determination in dam water, wastewater, river water, well water, sea water, tea, cacao, nut, bitter chocolate, rice, leek, cinnamon and parsley.

Removal of Cr, Mn, and Co from textile wastewater by horizontal rotating tubular bioreactor.

Environmental pollution by industrial wastewaters polluted with toxic heavy metals is of great concern. Various guidelines regulate the quality of water released from industrial plants and of surface waters. In wastewater treatment, bioreactors with microbial biofilms are widely used. A horizontal rotating tubular bioreactor (HRTB) is a combination of a thin layer and a biodisc reactor with an interior divided by O-ring shaped partition walls as carriers for microbial biomass. Using a biofilm of heavy metal resistant bacteria in combination with this special design provides various advantages for wastewater treatment proven in a pilot study. In the presented study, the applicability of HRTB for removing metals commonly present in textile wastewaters (chromium, manganese, cobalt) was investigated. Artificial wastewaters with a load of 125 mg/L of each metal underwent the bioreactor treatment. Different process parameters (inflow rate, rotation speed) were applied for optimizing the removal efficiency. Samples were drawn along the bioreactor length for monitoring the metal contents on site by UV-vis spectrometry. The metal uptake of the biomass was determined by ICP-MS after acidic microwave assisted digestion. The maximum removal rates obtained for chromium, manganese, and cobalt were: 100%, 94%, and 69%, respectively.

A novel micellar electrokinetic chromatographic method for separation of metal-DDTC complexes.

Micellar electrokinetic chromatography (MEKC) was examined for the separation and determination of Mo(VI), Cr(VI), Ni(II), Pd(II), and Co(III) as diethyl dithiocarbamate (DDTC) chelates. The separation was achieved from fused silica capillary (52 cm × 75 µm id) with effective length 40 cm, background electrolyte (BGE) borate buffer pH 9.1 (25 mM), CTAB 30% (100 mM), and 1% butanol in methanol (70 : 30 : 5 v/v/v) with applied voltage of -10 kV using reverse polarity. The photodiode array detection was achieved at 225 nm. The linear calibration for each of the element was obtained within 0.16-10 µg/mL with a limit of detection (LOD) 0.005-0.0167 µg/mL. The separation and determination was repeatable with relative standard deviation (RSD) within 2.4-3.3% (n = 4) in terms of migration time and peak height/peak area. The method was applied for the determination of Mo(VI) from potatoes and almond, Ni(II) from hydrogenated vegetable oil, and Co(III) from pharmaceutical preparations with RSD within 3.9%. The results obtained were checked by standard addition and rechecked by atomic absorption spectrometry.

Feasibility of reduced iron species for promoting Li and Co recovery from spent LiCoO2 batteries using a mixed-culture bioleaching process.

The recovery of metals from spent LiCoO2 batteries (SLBs) is essential to avoid resource wastage and the production of hazardous waste. However, the major challenge in regard to recovering metals from SLBs using traditional bioleaching is the low Co yield. To overcome this issue, a mixed culture of Acidithiobacillus caldus and Sulfobacillus thermosulfidooxidans was designed for use in SLBs leaching in this study. With the assistance of Fe2+ as a reductant, 99% of Co and 100% of Li were leached using the above mixed-culture bioleaching (MCB) process, thus solving the problem of low metal leaching efficiency from SLBs. Analysis of the underlying mechanism revealed that the effective extraction of metals from SLBs by the Fe2+-MCB process relied on Fe2+-releasing electrons to reduce refractory Co(III) to Co(II) that can be easily bioleached. Finally, the hazardous SLBs was transformed into a non-toxic material after treatment utilizing the Fe2+-MCB process. However, effective SLBs leaching was not achieved by the addition of Fe0 to the MCB system. Only 25% Co and 31% Li yields were obtained, as the addition of Fe0 caused acid consumption and bacterial apoptosis. Overall, this study revealed that reductants that cause acid consumption and harm bacteria should be ruled out for use in reductant-assisted bioleaching processes for extracting metals from SLBs.

Chemo-enzymatic functionalized sustainable cellulosic membranes: Impact of regional selectivity on ions capture and antifouling behavior.

Most of the polymeric membranes synthesized for decentralization of polluted water use fossil-based components. Thus, there is an urgent need to create robust and tunable nano/micro materials for confidently designing efficient and selective polymeric water filters with guaranteed sustainability. We have chosen a robust high-grade microfibrillated cellulose (MFC) as the functional material and selectively tuned it via enzymatic catalysis, which led to the attachment of phosphate group at the C6 position, followed by esterification (fatty acid attachment at C2 and C3 carbon), which led to the increase in its antifouling properties. We have demonstrated the robustness of the functionalization by measuring the separation of various metal ions, and the antifouling properties by adding foulants, such as Bovine Serum Albumin (BSA) and cancerous cells to the test solutions. These prototype affinity MFC membranes represent the most promising type of next-generation high-performance filtration devices for a more sustainable society.

Synthesis and characterization of titania hollow fiber and its application to the microextraction of trace metals.

A titania hollow fiber membrane was successfully synthesized in a macro range via a template method coupled with a sol-gel process. Thermal gravimetric and differential thermal analysis (TG-DTA) was employed to study the effect of heat treatment on the synthesized hollow fiber, and the crystal forms of the titania hollow fiber membranes at different temperatures were studied by X-ray diffraction (XRD). The pore structure of the prepared titania hollow fiber was characterized by scanning electron micrograph (SEM) and nitrogen adsorption/desorption measurements. The prepared titania hollow fiber membrane was explored as a new adsorption material for trace metals for the first time and a new method of titania hollow fiber membrane solid phase microextraction (MSPME) online coupled to inductively coupled plasma mass spectrometry (ICP-MS) was developed for the determination of trace amount of Cd, Co, V and Ni in human serum samples. In order to validate the developed method, two certified reference materials of NIES.No.10-b rice flour and BCR No.184 bovine muscle were analyzed and the determined values were in good agreement with the certified values.

The effect of process parameters on kinetics and mechanisms of Co2+ removal by bone char.

Bone char powder, composed mainly of poorly crystalline hydroxyapatite (Ca(10)(PO(4))(6)(OH)(2)), carbon and CaCO(3), has potential applicability in the removal of Co(2+) ions from contaminated effluents. In the present study, the influence of process parameters: particle size, agitation speed, initial pH and initial sorbate concentration, onto kinetics and mechanism of Co(2+)sorption was studied and discussed. In order to describe and compare time evolution of the process under different conditions, the experimental data were analyzed using pseudo-first, pseudo-second and Vermeulen's kinetic models. Generally, experimental results were best fitted with the pseudo-second-order model, which accurately predicted the equilibrium sorbed amounts. The pseudo-second-order rate constant was the most influenced by variations in initial metal concentration and pH, in the investigated ranges. The conclusions about sorption mechanism were derived based on Co(2+) amounts sorbed during time, as well as considering solution pH changes, changes of Ca(2+) amounts released into liquid phase and Ca(2+)/Co(2+) molar ratios. It was concluded that rapid sorption stage was governed by surface complexation reactions, whereas the contribution of the ion-exchange mechanism increased with time and became more significant in the second, slower phase. Experimentally determined maximum sorption capacity towards Co(2+), under optimal conditions, was found to be 0.38 mmol/g. The results show that bone char represents cost-effective alternative to synthetic hydroxyapatite sorbent.

A basic and effective liquid phase microextraction with a novel automated mixing system for the determination of cobalt in quince samples by flame atomic absorption spectrometry.

A new, green, and simple liquid-phase microextraction method namely sieve conducted two syringe-based pressurized liquid-phase microextraction methods was combined with flame atomic absorption spectrometry for the preconcentration and determination of cobalt. For this aim, a novel automated syringe mixing system was developed to be used in the developed extraction procedure. Two syringes were connected to each other by an apparatus having six holes to produce efficient dispersion of the extractant. The pressure created between the two syringes by the forward and backward movements of the syringe plungers created an efficient dispersion of the extractant. In the present study, ligand as complexing agent was synthesized in our laboratory. Limits of detection and quantification were determined to be 1.8 and 6.0 µg L-1, respectively. A 33.7-fold enhancement in detection power was obtained with the developed method. Method was effectively applied for the determination of cobalt in quince samples.

Removal of heavy metal ion cobalt (II) from wastewater via adsorption method using microcrystalline cellulose-magnesium hydroxide.

Microcrystalline cellulose (MCC), magnesium sulfate hexahydrate, and trisodium citrate were reacted in ammonia bath in an aqueous solution to prepare a MCC-magnesium hydroxide (MH) composite adsorbent, which was used to adsorb heavy metal Co(II) ion. The method of using MCC-MH to adsorb and remove Co(II) was studied under different pH values, adsorbent dosages, contact times, initial Co(II) ion concentrations, and temperatures. The optimal process parameters include an MCC-MH dosage of 2.5 mg/mL, a contact reaction equilibrium time of 50 min, a Co(II) solution pH of 6.0-8.0, an initial Co(II) concentration of 300 mg/L, and a temperature of 303 K. The removal rate of Co(II) solution by MCC-MH was as high as 97.67%, and the maximum adsorption capacity of MCC-MH reached 153.84 mg/g under these optimal conditions. The adsorption isotherm of Co(II) conformed to the Langmuir model, the kinetic data of Co(II) conformed to the pseudo-second-order kinetic model, and the adsorption of Co(II) by MCC-MH was a spontaneous endothermic reaction under the optimized conditions. Analytical studies showed that Co(II) adsorption on MCC-MH composites is affected by chemical adsorption and involves the influence of intraparticle diffusion to a certain extent.