Tannin-immobilized mesoporous silica bead (BT–SiO2) as an effective adsorbent of Cr(III) in aqueous solutions

This study describes a new approach for the preparation of tannin-immobilized adsorbent by using mesoporous silica bead as the supporting matrix. Bayberry tannin-immobilized mesoporous silica bead (BT–SiO₂) was characterized by powder X-ray diffraction to verify the crystallinity, field-emission scanning electron microscopy to observe the surface morphology, and surface area and porosity analyzer to measure the mesoporous porous structure. Subsequently, the adsorption experiments to Cr(III) were applied to evaluate the adsorption performances of BT–SiO₂. It was found that the adsorption of Cr(III) onto BT–SiO₂ was pH-dependent, and the maximum adsorption capacity was obtained in the pH range of 5.0–5.5. The adsorption capacity was 1.30 mmol g^?1 at 303 K and pH 5.5 when the initial concentration of Cr(III) was 2.0 mmol L^?1. Based on proton nuclear magnetic resonance (HNMR) analyses, the adsorption mechanism of Cr(III) on BT–SiO₂ was proved to be a chelating interaction. The adsorption kinetic data can be well described using pseudo-first-order model and the equilibrium data can be well fitted by the Langmuir isothermal model. Importantly, no bayberry tannin was leached out during the adsorption process and BT–SiO₂ can simultaneously remove coexisting metal ions from aqueous solutions. In conclusion, this study provides a new strategy for the preparation of tannin-immobilized adsorbents that are highly effective in removal of heavy metals from aqueous solutions.     

As(V) removal from aqueous media using α-MnO2 nanorods-impregnated laterite composite adsorbents

We present a novel way of enhancing the utility of low cost readily available laterite by impregnating it with the α-MnO₂ nanorods, thus making a composite material suitable for the removal of As(V) from aqueous media. The composites were synthesized by two methods: (i) ball-milling of a physical blend of laterite with pre-synthesized MnO₂; and (ii) in situ formation of MnO₂ in the presence of laterite. The BET surface area of composites prepared by both methods was markedly higher compared to un-modified laterite, and the presence of MnO₂ in the composite was also confirmed by XRD analysis and TEM microscopy. The adsorption capacity for As(V) was found to be highly pH dependent and the adsorption kinetics followed a pseudo second-order kinetic model. The Langmuir adsorption isotherm was found to be the best model to describe the adsorption equilibrium of As(V) onto un-modified laterite as well both ball-milled and in situ formed composite. The adsorption capacities at room temperature and pH 7.0 were found to be 1.50 mg g^?1, 8.93 mg g^?1 and 9.70 mg g^?1, for un-modified laterite, ball-milled and in situ formed composite, respectively.     

Equilibrium and kinetics of cadmium adsorption from aqueous solutions using untreated Pinus halepensis sawdust

Untreated Pinus halepensis sawdust has been investigated as an adsorbent for the removal of cadmium from aqueous solutions. Batch experiments were carried out to investigate the effect of pH, adsorbent dose, contact time, and metal concentration on sorption efficiency. The favorable pH for maximum cadmium adsorption was at 9.0. For the investigated cadmium concentrations (1–50 mg/L), maximum adsorption rates were achieved almost in the 10–20 min of contact. An adsorbent dose of 10 g/L was optimum for almost complete cadmium removal within 30 min from a 5 mg/L cadmium solution. For all contact times, an increase in cadmium concentration resulted in decrease in the percent cadmium removal (100–87%), and an increase in adsorption capacity (0.11–5.36 mg/g). The equilibrium adsorption data were best fitted with the Freundlich isotherm (R² = 0.960). The kinetics of cadmium adsorption was very well described by the pseudo-second-order kinetic model (R² > 0.999).     

Thermodynamic and kinetic studies for the adsorption of Hg(II) by nano-TiO2 from aqueous solution

Titanium dioxide nanocrystals were employed, for the first time, for the sorption of Hg(II) ions from aqueous solutions. The effects of varying parameters such as pH, temperature, initial metal concentration, and contact time on the adsorption process were examined. Adsorption equilibrium was established in 420 min and the maximum adsorption of Hg(II) on the TiO₂ was observed to occur at pH 8.0. The adsorption data correlated with Freundlich, Langmuir, Dubinin–Radushkevich (D–R), and Temkin isotherms. The Freundlich isotherm showed the best fit to the equilibrium data. The Pseudo-first order and pseudo-second-order kinetic models were studied to analyze the kinetic data. A second-order kinetic model fit the data with the (k₂ = 2.8126 × 10^?3 g mg^?1min^?1, 303 K). The intraparticle diffusion models were applied to ascertain the rate-controlling step. The thermodynamic parameters (ΔG°, ΔH°, and ΔS°) were calculated which showed an endothermic adsorption process. The equilibrium parameter (R_L) indicated that TiO₂ nanocrystals are useful for Hg(II) removal from aqueous solutions.     

Glutamic acid containing supermacroporous poly(hydroxyethyl methacrylate) cryogel disks for UO22+ removal

Supermacroporous cryogel with an average pore size of 10–200 μm in diameter was prepared by cryopolymerization of N-methacryloyl-(l)-glutamic acid (MAGA) and 2-hydroxyethyl methacrylate (HEMA). The poly(HEMA–MAGA) cryogel was characterized by surface area measurements, FTIR, swelling studies, elemental analysis and SEM. The poly(HEMA–MAGA) cryogel had a specific surface area of 23.2 m²/g. The equilibrium swelling ratio of the cryogel is 9.68 g H₂O/g for poly(HEMA–MAGA) and 8.56 g H₂O/g cryogel for PHEMA. The poly(HEMA–MAGA) cryogel disks with a pore volume of 71.6% containing 878 μmol MAGA/g were used in the removal of UO₂²⁺ from aqueous solutions. Adsorption equilibrium of UO₂²⁺ was obtained in about 30 min. The adsorption of UO₂²⁺ ions onto the PHEMA cryogel disks was negligible (0.78 mg/g). The MAGA incorporation significantly increased the UO₂²⁺ adsorption capacity (92.5 mg/g). The adsorption process is found to be a function of pH of the UO₂²⁺ solution, with the optimum value being pH 6.0. Adsorption capacity of MAGA contained PHEMA based cryogel disks increased significantly with pH and then reached the maximum at pH 6.0. Consecutive adsorption and elution cycles showed the feasibility of repeated use for poly(HEMA–MAGA) cryogel disks.     

Synthesis of interstratified graphene/montmorillonite composite material through organics-pillared,delamination and co-stacking and its application in hexavalent chromium removal from aqueous solution

Layers from two different delaminated dispersions of 3-aminopropyltriethoxysilane (APTES)-intercalated montmorillonite (Mts) and octylamine (OA)-intercalated graphene oxide (GO) could be co-stacked to obtain APTES-intercalated Mts (Mts-APTES)/OA-intercalated GO (GO-OA) interstratified composites (MAGO). The synthesized composites were characterized by XRD, FTIR, BET, TGA, TEM and XPS, which showed that MAGO had been prepared successfully. The optimal concentration of APTES was 8% in anhydrous toluene which avoided self-polymerization of APTES while facilitating the nucleophilic attack of APTES amine groups and the protic character of ethanol to compete with silane for the intimal hydroxyl groups by H-bonding. The MAGO demonstrated an extremely fast Cr(VI) removal from aqueous solution with a high removal efficiency at low pH. Data from batch studies of the adsorption process followed pseudo-second-order kinetics. The results fit a Langmuir model of adsorption, with maximum adsorption capacities of MAGO composites at pH 3.0 being 44.25 mg g^?1, 47.46 mg g^?1, 49.58 mg g^?1 under 30 °C, 40 °C, 50 °C, respectively, which were much higher than capacities of some conventional adsorbents. The reusability of the MAGO composite was also determined through adsorption-desorption studies, providing evidence for the potential use of MAGO composite in the removal of Cr(VI) from acidic wastewater.     

Detection of growth factor binding to gelatin and heparin using a photonic crystal optical biosensor

Drug–carrier interactions are important to protein controlled release systems to protect the protein from denaturation and ensure properly timed release. A novel photonic crystal biosensor was used to investigate a gelatin–protein controlled release system to determine the amount of protein bound to the carrier at physiological conditions. The Biomolecular Interaction Detection (BIND) system reflects a narrow band of wavelengths when white light is shone incident to the grating. As mass is deposited onto the surface, the peak wavelength value is shifted due to changes in the optical density of the biosensor. The BIND system was used to detect the binding of growth factors onto acidic gelatin, basic gelatin, and heparin on the sensor surface. Through a series of experiments, including functionalizing the sensor, adjusting the ionic strength of the solution, adjusting the substrate concentration, and minimizing non-specific signal, the adsorption of the gelatins and heparin on the sensor was enhanced. The binding interaction of recombinant human transforming growth factor (rhTGF)-β1 and bone morphogenetic protein (rhBMP)-2 with the two types of gelatin and heparin were investigated. The strength of the interaction between rhTGF-β1 and the substrates is in the following order: heparin > acidic gelatin > basic gelatin. RhBMP-2 bound to the substrates but with less intensity than TGF-β1: heparin > basic gelatin > acidic gelatin. This work provides support for the controlled release mechanism through degradation of the gelatin carrier.     

Fabrication and characterization of a zirconia/multi-walled carbon nanotube mesoporous composite

A zirconia/multi-walled carbon nanotube (ZrO₂/MWCNT) mesoporous composite was fabricated via a simple method using a hydrothermal process with the aid of the cationic surfactant cetyltrimethylammonium bromide (CTAB). Transmission electron microscopy (TEM), N₂ adsorption–desorption, Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD) techniques were used to characterize the as-made samples. The cubic ZrO₂ nanocrystallites were observed to overlay the surface of MWCNTs, which resulted in the formation of a novel mesoporous–nanotube composite. On the basis of a TEM analysis of the products from controlled experiment, the role of the acid-treated MWCNTs and CTAB was proposed to explain the formation of the mesoporous–nanotube structure. The as-made composite possessed novel properties, such as a high surface area (312 m² · g^? 1) and a bimodal mesoporous structure (3.18 nm and 12.4 nm). It was concluded that this composite has important application value due to its one-dimensional hollow structure, excellent electric conductivity and large surface area.     

Removal of Pb(II) ions from aqueous solution by adsorption using bael leaves (Aegle marmelos)

Biosorption of Pb(II) on bael leaves (Aegle marmelos) was investigated for the removal of Pb(II) from aqueous solution using different doses of adsorbent, initial pH, and contact time. The maximum Pb loading capacity of the bael leaves was 104 mg g^?1 at 50 mg L^?1 initial Pb(II) concentration at pH 5.1. SEM and FT-IR studies indicated that the adsorption of Pb(II) occurs inside the wall of the hollow tubes present in the bael leaves and carboxylic acid, thioester and sulphonamide groups are involved in the process. The sorption process was best described by pseudo second order kinetics. Among Freundlich and Langmuir isotherms, the latter had a better fit with the experimental data. The activation energy E_a confirmed that the nature of adsorption was physisorption. Bael leaves can selectively remove Pb(II) in the presence of other metal ions. This was demonstrated by removing Pb from the effluent of exhausted batteries.     

Synthesis of new silicas with high stable and large mesopores and macropores for biocatalysis applications

Monomodal or bimodal porous silicas with large mesopores, constituted by particles or having a monolithic (block type) morphology, respectively, are synthesized using sodium silicate as siliceous species source, cetyltrimethylammonium bromide (CTAB) as pore template and ethyl acetate (EtAc) as pH modifier. The monomodal porosity is represented by 20–30 nm pores and the bimodal one by these pores and also macropores. These characteristics are modulated in function of the CTAB and EtAc concentrations as well as the pH and hydrothermal treatment. The role of these reagents upon the porosity is rationalized. The presence of high CTAB concentration and a rather low pH decreasing rate (function of EtAc concentration and hydrothermal treatment) are essential for having the already known bimodal mesoporous silicas (BMS). On the contrary a rather high pH decreasing rate promotes the formation of the new bimodal mesoporous–macroporous silicas (BMMS) synthesized in this work, where the EtAc also plays the role of emulsion forming agent. The hydrolytic stability of the synthesized silica under aqueous conditions, at different pH values, makes these silicas good candidates for application in different areas of catalysis, especially in the enzymatic one.     

Effect of grinding conditions on mechanochemical grafting of poly(1-vinyl-2-pyrrolidone) onto quartz particles

Grinding of quartz in an aqueous solution of 1-vinyl-2-pyrrolidone (VP) in a stirred media mill results in grafting of poly(1-vinyl-2-pyrrolidone) (PVP) onto the quartz particles as proven by FTIR-spectroscopy. The grinding kinetics, the particle size of the final product and the amount of PVP grafted onto the silica particles depend on grinding conditions like VP and quartz concentration, pH and size of grinding media. The grinding kinetics becomes slower in the presence of VP due to the damping effect of the forming PVP chains. The final particle size, however, is almost independent on VP concentration. The amount of PVP grafted onto the silica particles ground for 12 h increases with growing VP concentration because the amount of adsorbed VP and the polymerization rate increase with growing VP concentration.The primary particle size and the kinetics of particle breakage do not depend on the pH-value of the dispersing medium, whereas the degree of agglomeration of the particles decreases with increasing pH-value of the medium. Under alkaline conditions, however, less PVP is grafted onto the quartz particles than under neutral or strong acidic conditions. The reasons for these effects are pH-dependent interactions between the grafted PVP chains and the surface hydroxyl groups on the quartz particles. If the quartz concentration in the suspension decreases the grinding kinetics becomes much faster because the specific energy input increases with decreasing particle concentration if the other process parameters are kept constant. For a very low quartz concentration (1 wt.%), however, after 7 h of grinding the particle size measured by dynamic light scattering starts to increase with grinding time. SEM investigations reveal that grinding of 1 wt.% quartz in aqueous VP solution for longer than 7 h results in the formation of plate-like particles.     

One-step synthesis of hydrophobic mesoporous silica ellipsoidal particles with a bimodal mesopore system

Highly CH₃-functionalized mesoporous silica ellipsoidal particles with bimodal mesopore structure were prepared via a one-step route using polymethylhydrosiloxane (PMHS) and tetraethoxysilane (TEOS) with triblock copolymer P123 as template under acidic conditions. N₂ adsorption–desorption, XRD, HRTEM, SEM and ²⁹Si MAS NMR were used to characterize the obtained material. The introduction of PMHS into the synthetic system led to the formation of a bimodal mesopore system consisting of framework mesopores of ∼7.2 nm and textural mesopores of ∼29.4 nm. The two scale pores were directly observed in HRTEM images and indirectly proved by the two-step increase in N₂ adsorption–desorption isotherm. Also, PMHS played an important role in morphology controlling and organic functionalization, ensuring monodisperse ellipsoidal particle morphology and high CH₃ functionalization degree of the mesoporous silica product. Subjected to removing highly diluted nonylphenol from aqueous solution, the hydrophobic bimodal mesoporous silica ellipsoidal particles showed high adsorption performance.     

Purification of yeast alcohol dehydrogenase by using immobilized metal affinity cryogels

In this study, poly(2-hydroxyethyl methacrylate–glycidylmethacrylate) [poly(HEMA–GMA)] cryogels were prepared by radical cryocopolymerization of HEMA with GMA as a functional comonomer and N,N′-methylene-bisacrylamide (MBAAm) as a crosslinker. Iminodiacetic acid (IDA) functional groups were attached via ring opening of the epoxy group on the poly(HEMA–GMA) cryogels and then Zn(II) ions were chelated with these structures. Characterization of cryogels was performed by FTIR, SEM, EDX and swelling studies. These cryogels have interconnected pores of 30–50 μm size. The equilibrium swelling degree of Zn(II) chelated poly(HEMA–GMA)-IDA cryogels was approximately 600%. Zn(II) chelated poly(HEMA–GMA)-IDA cryogels were used in the adsorption of alcohol dehydrogenase from aqueous solutions and adsorption was performed in continuous system. The effects of pH, alcohol dehydrogenase concentration, temperature, and flow rate on adsorption were investigated. The maximum amount of alcohol dehydrogenase adsorption was determined to be 9.94 mg/g cryogel at 1.0 mg/mL alcohol dehydrogenase concentration and in acetate buffer at pH 5.0 with a flow rate of 0.5 mL/min. Desorption of adsorbed alcohol dehydrogenase was carried out by using 1.0 M NaCI at pH 8.0 phosphate buffer and desorption yield was found to be 93.5%. Additionally, these cryogels were used for purification of alcohol dehydrogenase from yeast with a single-step. The purity of desorbed alcohol dehydrogenase was shown by silver-stained SDS–PAGE. This purification process can successfully be used for the purification of alcohol dehydrogenase from unclarified yeast homogenates and this work is the first report about the usage of the cryogels for purification of alcohol dehydrogenase.     

An eco-friendly process: Predictive modelling of copper adsorption from aqueous solution on Spirulina platensis

The adsorption of copper ions on Spirulina platensis was studied as a function of contact time, initial metal ion concentration, and initial pH regimes. Characterization of this adsorbent was confirmed by FTIR spectrum. Modified Gompertz and Logistic models have not been previously applied for the adsorption of copper. Logistic was the best model to describe experimental kinetic data. This adsorption could be explained by the intra-particle diffusion, which was composed of more than one sorption processes. Langmuir, Freundlich, and Redlich–Peterson were fitted to equilibrium data models. According to values of error functions and correlation coefficient, the Langmuir and Redlich–Peterson models were more appropriate to describe the adsorption of copper ions on S. platensis. The monolayer maximum adsorption capacity of copper ions was determined as 67.93 mg g^?1. Results indicated that this adsorbent had a great potential for removing of copper as an eco-friendly process.     

Poly(N,N-dimethylaminoethyl methacrylate) modification of activated carbon for copper ions removal

Poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) functionalization of rice husk-based activated carbon was prepared and its application in the removal of copper ions was investigated. The structural properties of the resulting composite material were characterized by means of N₂ adsorption/desorption, Fourier transform infrared (FT-IR) and thermogravimetric analysis (TGA). The obtained composite is observed to hold a relatively large pore diameter of 3.8 nm and high surface area of 789 m² g^?1 with 12 wt% of PDMAEMA coated, which is significant for its use as adsorbent. The ability of the composite material for removing Cu²⁺ from aqueous solution was studied by batch experiments. The adsorption data obeyed the Langmuir isotherms, which revealed that 1 g of the prepared material could adsorb 31.46 mg of Cu²⁺ from its aqueous solution. The PDMAEMA functionalized activated carbon is expected to be used as an efficient adsorbent for removing other heavy metal ions and dyes in water.     

Adsorption kinetics of malachite green onto activated carbon prepared from Tunçbilek lignite

Adsorbent (T₃K618) has been prepared from Tunçbilek lignite by chemical activation with KOH. Pore properties of the activated carbon such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by t-plot based on N₂ adsorption isotherm. The N₂ adsorption isotherm of malachite green on T₃K618 is type I. The BET surface area of the adsorbent which was primarily contributed by micropores was determined 1000 m²/g. T₃K618 was used to adsorb malachite green (MG) from an aqueous solution in a batch reactor. The effects of initial dye concentration, agitation time, initial pH and adsorption temperature have been studied. It was also found that the adsorption isotherm followed both Freundlich and Dubinin–Radushkevich models. However, the Freundlich gave a better fit to all adsorption isotherms than the Dubinin–Radushkevich. The kinetics of adsorption of MG has been tested using pseudo-first-order, pseudo-second-order and intraparticle diffusion models. Results show that the adsorption of MG from aqueous solution onto micropores T₃K618 proceeds according to the pseudo-second-order model. The intraparticle diffusion of MG molecules within the carbon particles was identified to be the rate-limiting step. The adsorption of the MG was endothermic (ΔH° = 6.55–62.37 kJ/mol) and was accompanied by an increase in entropy (ΔS° = 74–223 J/mol K) and a decrease in mean value of Gibbs energy (ΔG° = −6.48 to −10.32 kJ/mol) in the temperature range of 20–50 °C.     

Removal,preconcentration and spectrophotometric determination of picric acid in water samples using modified magnetic iron oxide nanoparticles as an efficient adsorbent

A simple, fast and sensitive spectrophotometric method is developed for removal, preconcentration and determination of trace amounts of picric acid in water samples. Magnetic iron oxide nanoparticles (MIONPs) were synthesized and characterized by transmission electron microscopy (TEM). The magnetic nanoparticles were coated with cetyltrimethylammonium bromide (CTAB) and were applied for fast separation, preconcentration and spectrophotometric determination of picrate anion (the ion of picric acid) in an aqueous solution. The separation, preconcentration procedure is fast and will be completed in 2 min. Methanol is used for desorption of adsorbed picrate anion. The effects of important parameters such as pH of aqueous medium, CTAB dosage, adsorbent amount, temperature, electrolyte concentration, desorbing solvent and interfering ions on the adsorption of picrate anion were investigated. The method showed good linearity for the determination of picric acid in the concentration range of 0.02–1.00 μg mL^? 1 with a regression coefficient of 0.999. The limit of detection (LOD) is obtained to be 0.007 μg mL^? 1. The relative standard deviation (RSD) for 0.03 μg mL^? 1 and 0.8 μg mL^? 1 of picric acid were 3.98% and 1.97% respectively. Picric acid was separated, preconcentrated and determined successfully in spiked samples of Karoon River water.     

Characterization of sodium dodecyl sulfate modified iron pillared montmorillonite and its application for the removal of aqueous Cu(II) and Co(II)

Anionic surfactant modified Fe-pillared montmorillonites were prepared by Fe-hydrate solution and sodium dodecyl sulfate (SDS) solution. These organo–inorgano complex montmorillonites were divided into three types (CM1, CM2 and CM3) depending on different intercalation processes. X-ray diffraction spectra, the Fourier transform infrared (FTIR) spectra were used to analyze the structure of the raw and modified montmorillonites. X-ray photoelectron spectra of the simples have been studied to determine spectral characteristics to allow the identification of Fe(III) hydroxide. The specific surface area of the host montmorillonite (M0) is 73.2 m²/g, while for the modified montmorillonites it is 114.0 m²/g, 117.2 m²/g, and 115.8 m²/g, respectively. The mesopore volumes of the montmorillonites decrease after modification. Ions of copper and cobalt were selected as adsorbates to evaluate the adsorption performance of each montmorillonite. The adsorption data was analyzed by both Freundlich and Langmuir isotherm models and the data was well fit by the Langmuir isotherm model. The adsorption was efficient and significantly influenced by metal speciation, metal concentration, contact time, and pH. Higher adsorption capacity of the modified montmorillonites were obtained at pH 5–6. The results of desorption indicated that the metal ions were covalently bound to the modified montmorillonites.     

Blending effect of sucrose and surfactant templating agents on silica mesostructure

We report the blending effect of surfactant and sucrose as a nonsurfactant templating agent on the silica mesostructure. The CTAB/sucrose-templated mesoporous silica (SCS) was compared with CTAB-templated MCM-41. The MCM-41 showed spherical morphology with a particle diameter of 1.1–1.5 μm, and gave a bimodal size distribution, centered at 2.1 nm and 8.9 nm, which is assigned to hexagonally-arrayed cylindrical pores and interparticle-pores between small MCM-41 clusters, respectively. SCS gave unique and extraordinary morphology in which two different mesostructures have grown with both of them facing each other. The ordered MCM-41 pore structure clung to silica nanosphere-framed wormlike mesostructure, resulting in a bimodal pore size distribution centered at 2.1 nm and 7.0 nm. It was revealed that both of CTAB and sucrose act independently as a surfactant and a nonsurfactant template.     

Selective adsorption and release of cationic organic dye molecules on mesoporous borosilicates

Mesoporous materials can play a pivotal role as a host material for delivery application to a specific part of a system. In this work we explore the selective adsorption and release of cationic organic dye molecules such as safranine T (ST) and malachite green (MG) on mesoporous borosilicate materials. The mesoporous silica SBA-15 and borosilicate materials (MBS) were prepared using non-ionic surfactant Pluronic P123 as template via evaporation induced self-assembly (EISA) method. After template removal the materials show high surface areas and in some cases ordered mesopores of dimensions ca. 6–7 nm. High surface area, mesoporosity and the presence of heteroatom (boron) help this mesoporous borosilicate material to adsorb high amount of cationic dye molecules at its surface from the respective aqueous solutions. Furthermore, the mesoporous borosilicate samples containing higher percentage adsorbed dyes show excellent release of ST or MG dye in simulated body fluid (SBF) solution at physiological pH = 7.4 and temperature 310 K. The adsorption and release efficiency of mesoporous borosilicate samples are compared with reference boron-free mesoporous pure silica material to understand the nature of adsorbate–adsorbent interaction at the surfaces.