Valorization of keratin biofibers for removing heavy metals from aqueous solutions

Four common waste keratin biofibers (human hair, dog hair, chicken feathers, and degreased wool) have been used as biosorbents for the removal of heavy metal ions from aqueous solutions. Different parameters of the biosorption processes were optimized in batch systems. For multiple-metal systems, consisting of a mixture of eight metal ions [Cr(III), Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II)], the total metal biosorption increased in the order: degreased wool¿>¿chicken feathers¿>¿human hair¿>¿dog hair. From the kinetic models tested, the pseudo-second-order model provided better results. Furthermore, biosorption isotherms of Pb(II) with the different keratin biofibers fitted the Langmuir model. Surface morphology of the biosorbents were analyzed before and after the sorption using Fourier transform infrared spectroscopy and scanning electron microscopy. The keratin biofibers tested are potentially good sorbents of metal ions, with degreased wool and chicken feathers being the more efficient onesPostprint (author's final draft

Agro-Industrial Waste as Potential Heavy Metal Adsorbents and Subsequent Safe Disposal of Spent Adsorbents

Water pollution is an environmental problem that affects the ecosystem and living beings. Adsorption is one of the best technologies for the removal of heavy metals. Since waste recovery is the basis of the Circular Economy, agro-industrial waste is emerging as low-cost adsorbents for these pollutants from wastewater. Residues of pine sawdust, sunflower seed hulls and corn residues mix were evaluated as adsorbents of synthetic aqueous solutions of Ni(II), Zn(II) and Cd(II). These residues were characterized to determine their structure and composition, and to understand the adsorption mechanism. Adsorption efficiencies and capacities for the adsorbents and adsorbates were determined and compared. From the obtained results, it is possible to affirm that all biomasses used are good alternatives to the synthetic materials, with adsorption efficiencies greater than 50%. The order of adsorption was Cd > Zn > Ni. At the concentration range checked, adsorption efficiencies decreased in sawdust when a mixture of all metals together was considered (as present in real sewage). Finally, the heavy metals were immobilized, with efficiencies over 88.5%, in clay ceramics (as brick's precursors). This procedure would help to minimize the contamination that could be generated by the disposal of spent adsorbents, rarely explored in the literature

Use of chemically treated human hair wastes for the removal of heavy metal ions from water

Human hair is considered a ubiquitous waste product and its accumulation can cause environmental problems. Hence, the search for alternatives that take advantage of this waste as a new raw material is of interest, and contributes to the idea of the circular economy. In this study, chemically modified human hair was used as a low cost biosorbent for the removal of heavy metal ions from aqueous solutions. The effect of the contact time, the pH, and the biosorbent concentration on the biosorption process were investigated. Kinetic modeling indicated that the pseudo-second order kinetic equation fitted well with R2> 0.999. Furthermore, the equilibrium data fitted the Langmuir adsorption isotherm at 295 K resulting insaturation concentrations of9.47×10-5, 5.57×10-5, 3.77×10-5,and3.61×10-5mol/g for the sorption of Cr(III), Cu(II), Cd(II), and Pb(II), respectively. The biosorption process did not change the chemical structure and morphology of the hair, which was shown by FTIR and SEM. In addition, desorption experiments prove that 0.1 mol/L EDTA solution is an efficient eluent for the recovery of Pb(II) from the treated human hair. To summarize, treated human hair showed satisfactory biosorption capacity and can be considered as an effective biosorbent for the treatment of waterwith a low concentration of heavy metal ionsPostprint (published version

Composite Electrodes Based on Carbon Materials Decorated with Hg Nanoparticles for the Simultaneous Detection of Cd(II), Pb(II) and Cu(II)

Monitoring water quality has become a goal to prevent issues related to human health and environmental conditions. In this sense, the concentration of metal ions in water sources is screened, as these are considered persistent contaminants. In this work, we describe the implementation of customized graphite electrodes decorated with two types of Hg nanoparticles (Hg-NPs), optimized toward the electrochemical detection of Cd, Pb and Cu. Here, we combine Hg, a well-known property to form alloys with other metals, with the nanoscale features of Hg-NPs, resulting in improved electrochemical sensors towards these analytes with a substantial reduction in the used Hg amount. Hg-NPs were synthesized using poly(diallyldimethylammonium) chloride (PDDA) in a combined role as a reducing and stabilizing agent, and then appropriately characterized by means of Transmission Electron Microscopy (TEM) and Zeta Potential. The surface of composite electrodes with optimized graphite content was modified by the drop-casting of the prepared Hg-NPs. The obtained nanocomposite electrodes were morphologically characterized by Scanning Electron Microscopy (SEM), and electrochemically by Cyclic Voltammetry (CV) and Electrochemical Impedance Spectroscopy (EIS). The results show that the Hg-NP-modified electrodes present better responses towards Cd(II), Pb(II) and Cu(II) detection in comparison with the bare graphite electrode. Analytical performance of sensors was evaluated by square-wave anodic stripping voltammetry (SWASV), obtaining a linear range of 0.005-0.5 mg·L−1 for Cd2+, of 0.028-0.37 mg·L−1 for Pb2+ and of 0.057-1.1 mg·L−1 for Cu2+. Real samples were analyzed using SWASV, showing good agreement with the recovery values of inductively coupled plasma-mass spectrometry (ICP-MS) measurement

Customized in situ functionalization of nanodiamonds with nanoparticles for composite carbon-paste electrodes

The incorporation of nanomaterials on (bio)sensors based on composite materials has led to important advances in the analytical chemistry field due to the extraordinary properties that these materials offer. Nanodiamonds (NDs) are a novel type of material that has raised much attention, as they have the possibility of being produced on a large scale by relatively inexpensive synthetic methodologies. Moreover, NDs can present some other interesting features, such as fluorescence, due to surface functionalization and proved biocompatibility, which makes them suitable for biomedical applications. In addition, NDs can be customized with metallic nanoparticles (NPs), such as silver or gold, in order to combine the features of both. Raw NDs were used as modifiers of sensors due to the electrocatalytic effect of the sp2 and oxygenated species present on their surface. The aim of this research work is evaluating the applicability of NDs modified with silver (Ag@NDs) and gold (Au@NDs) nanoparticles for the development of a suitable (bio)sensing platform. A complete morphological and electrochemical characterization as a function of the prepared nanocomposite composition was performed in order to improve the electroanalytical properties of the developed (bio)sensors. In the present work, the optimal composition for Au@NDs present on the nanocomposite matrix is 3.5% and the one for Ag@NDs is 1%. Good results were obtained in the evaluation of the optimal composition towards hydrogen peroxide and glucose as a model analyte using a (bio)sensor based on graphite-epoxy-Ag@NDs (17:82:1)

Insights of microorganisms role in rice and rapeseed wastes as potential sorbents for metal removal

Altres ajuts: acord transformatiu CRUE-CSICRice and rapeseed agricultural wastes, as nonliving biomass, are proposed for heavy metal remediation in polluted effluents (chromium, cadmium, copper and lead). The physicochemical characterization of these biomasses shows that the surface of both sorbents is negatively charged (zeta potential), the surface area of sorbents is 4.39 and 40.7 (Brunauer-Emmett-Teller), and the main functional groups are carboxylic and hydroxyl (attenuated total reflection Fourier-transform infrared spectroscopy). The main purpose of this work is to evaluate the insights of microorganisms associated with these nonliving biomasses in the removal of heavy metals from synthetic aqueous solutions, adjusted at pH 4.0 (as the best acidic condition for the sorption process). The isolates (Bacillus genus in rice and Escherichia, Micrococcus and Staphylococcus genus in rapeseed) remove heavy metals from mentioned solutions, mainly in consortia, with contribution percentage over than 80% of total metals. In addition, when they are present in biomass, they provide an additional metal removal effect, especially in rapeseed biomass system and with multiple heavy metals aqueous solutions: i.e. Cr(III) removal, at 4 mmol/L, increases from 70 to 100%. This knowledge makes possible the use of the nonliving biomasses with no need for any special pretreatment against the microorganisms, prior to their use as metal sorbents that implies their good feasibility for application from an economical point of view

Enhanced terahertz sensitivity for glucose detection with a hydrogel platform embedded with Au nanoparticles

We presented a strategy for enhancing the sensitivity of terahertz glucose sensing with a hydrogel platform pre-embedded with Au nanoparticles. Physiological-level glucose solutions ranging from 0 to 0.8 mg/mL were measured and the extracted absorption coefficients can be clearly distinguished compared to traditional terahertz time domain spectroscopy performed directly on aqueous solutions. Further, Isotherm models were applied to successfully describe the relationship between the absorption coefficient and the glucose concentration (R2 = 0.9977). Finally, the origin of the sensitivity enhancement was investigated and verified to be the pH change induced by the catalysis of Au nanoparticles to glucose oxidation

Comparison of biochars derived from different types of feedstock and their potential for heavy metal removal in multiple-metal solutions

Three different types of feedstocks and their biochars were used to remove Cr(III), Cd(II), Cu(II) and Pb(II) ions from a mixture of multiple heavy metals. The effect of the initial concentration of heavy metals in solution has been analysed, and kinetics modelling and a comparison of the adsorption capacity of such materials have been performed to elucidate the possible adsorption mechanisms. The results show that the adsorption capacity is dependent on the type of feedstock and on the pyrolysis conditions. The adsorption capacity of the biomass types is ranked as follows: FO (from sewage sludge)» LO > ZO (both from agriculture biomass waste)» CO (from wood biomass waste). Biochars, which are the product of the pyrolysis of feedstocks, clearly improve the adsorption efficiency in the case of those derived from wood and agricultural biomasses. Complexation and cation exchange have been found to be the two main adsorption mechanisms in systems containing multiple heavy metals, with cation exchange being the most significant. The pore structure of biomass/biochar cannot be neglected when investigating the adsorption mechanism of each material. All the disposal biomasses presented here are good alternatives for heavy metal removal from wastewaters

Synthesis and adsorption behavior of mesoporous alumina and Fe-doped alumina for the removal of dominant arsenic species in contaminated waters

Ordered mesoporous Al2O3 and Fe-Al2O3 materials were synthesized at room temperature by an easy and environmentally friendly self-assembly sol-gel route, to be tested for arsenic removal. Solid samples were thoroughly characterized by several techniques. Synthetized and commercial alumina samples were evaluated as adsorbents for the removal of dominant arsenic species under a wide pH range (3.6-11.5). The mesoporous alumina showed higher adsorption capacity (90 mg/g As(V), pHeq 4) than commercial alumina (54 mg/g As(V), pHeq 4), due to its amorphous structure, uniform accessible mesopores and higher surface acidity. The Fe bearing material exhibited strong As affinity. As(III) adsorption resulted much lower than for arsenate (maximum uptake of 16 mg/g, at pH 8), since As(III)-adsorbent interaction is only based on weak Van der Waals force. Arsenic isotherms adjusted well to the Freundlich model and more accurately to the three parameters Sip's model. The kinetics results fitted the Elovich model. As pH increased, adsorption capacity decreased due to the reduction of electrostatic interactions. Under alkaline conditions arsenic desorption was achieved, although the stability of the material was compromised. The presence of several interfering ions was evaluated. Phosphate ions showed the highest interference. The use of a tap water matrix increased As(V) adsorption, encouraging the use of these materials in the treatment of real polluted waters

Coffee Husk and Lignin Revalorization: Modification with Ag Nanoparticles for Heavy Metals Removal and Antifungal Assays

This study presents the use of the modified coffee husk and coffee lignin as sorbents in the heavy metal ions sorption of Pb(II), Cd(II), Cr(III), and Cu(II) in an aqueous solution. The modification of sorbents was carried out by the impregnation method, using silver nitrate (AgNO3) and sodium borohydride (NaBH4) as a nanoparticles' (NPs) precursor, and reducing agent, respectively. The obtained nanocomposite material was morphologically characterized by electron microscopy. In addition, an evaluation of metal ions' sorption, pseudo‐first‐order, and pseudo‐second‐order kinetics modeling was performed. Finally, antifungal activity was evaluated on different Candida species. Coffee and lignin modified with AgNPs increased the extraction capacity with the highest sorption for Pb ions with 2.56 mg/g and 1.44 mg/g, respectively