Heavy metal pollution, such as lead, can cause contamination of water resources and harm human life. Many techniques have been explored and utilized to overcome this problem, with adsorption technology being the most common strategies for water treatment. In this study, carbon nanofibers, polyacrylonitrile (PAN)/sago lignin (SL) carbon nanofibers (PAN/SL CNF) and PAN/SL activated carbon nanofibers (PAN/SL ACNF), with a diameter approximately 300 nm, were produced by electrospinning blends of polyacrylonitrile and sago lignin followed by thermal and acid treatments and used as adsorbents for the removal of Pb(II) ions from aqueous solutions. The incorporation of biodegradable and renewable SL in PAN/SL blends fibers produces the CNF with a smaller diameter than PAN only but preserves the structure of CNF. The adsorption of Pb(II) ions on PAN/SL ACNF was three times higher than that of PAN/SL CNF. The enhanced removal was due to the nitric acid treatment that resulted in the formation of surface oxygenated functional groups that promoted the Pb(II) ions adsorption. The best-suited adsorption conditions that gave the highest percentage removal of 67%, with an adsorption capacity of 524 mg/g, were 40 mg of adsorbent dosage, 125 ppm of Pb(II) solution, pH 5, and a contact time of 240 min. The adsorption data fitted the Langmuir isotherm and the pseudo-second-order kinetic models, indicating that the adsorption is a monolayer, and is governed by the availability of the adsorption sites. With the adsorption capacity of 588 mg/g, determined via the Langmuir isotherm model, the study demonstrated the potential of PAN/SL ACNFs as the adsorbent for the removal of Pb(II) ions from aqueous solution.
A novel synthesis and characterization of cellulose, hydroxyapatite and chemically-modified carbon electrode (Cellulose-HAp-CME) composite was reported for the analysis of trace Pb(II) ions detection and its validation in blood serum. The Field Emission Scanning Electron Microscopy (FESEM) analyses showed that the composite retained the orderly porous structure but with scattered particle size agglomeration. The Fourier Transform Infrared Spectroscopy (FTIR) spectra suggested the presence of functional groups associated with the bending and stretching of carbon bonds and intermolecular H-bonding. X-ray Diffraction (XRD) analyses further elucidated that the crystallite size could have influenced the properties of the electrode. Based on Thermo-gravimetric Analysis (TGA/DTG), the composites showed thermal stability with more than 60% residual content at 700°C. The sensor was successfully developed for trace Pb(II) ions detection in complex medium such as blood serum, in the physiologically relevant range of 10-60ppb, with resulting Limit of Detection (LOD) of 0.11±0.36ppb and Limit of Quantification (LOQ) of 0.36±0.36ppb. The newly fabricated electrode could be advantageous as a sensing platform with favourable electrochemical characteristics for robust, in situ and rapid environmental and clinical analyses of heavy metal ions.
We report a green synthesis of oatmeal ZnO/silver composites in the presence of L-glutamine as an electrochemical sensor for Pb2+ detection. The synthesis was performed via the direct reduction of Ag+ in the presence of L-glutamine in NaOH. X-ray diffraction indicated that the Ag+ was completely reduced to metallic Ag. The field emission scanning electron microscopy (FESEM) and energy dispersive X-ray results confirmed an oatmeal-like morphology of the ZnO with the presence of Ag. The FESEM images showed the effect of L-glutamine on the ZnO morphology. The EIS results confirmed a significant decrease in the charge transfer resistance of the modified glassy carbon electrode due to the presence of Ag. From the differential pulse voltammetry results, a linear working range for the concentration of Pb2+ between 5 and 6 nM with LOD of 0.078 nM (S/N = 3) was obtained. The sensitivity of the linear segment is 1.42 μA nM-1 cm-2. The presence of L-glutamine as the capping agent and stabilizer decreases the size of Ag nanoparticles and prevents the agglomeration of ZnO, respectively. Graphical abstract ᅟ.
This paper presents the results of research on heavy metals removal from water by filtration using low cost coarse media which could be used as an alternative approach to remove heavy metals from water or selected wastewater. A series of batch studies were conducted using different particle media (particle size 2.36-4.75 mm) shaken with different heavy metal solutions at various pH values to see the removal behaviour for each metal. Each solution of cadmium (Cd), lead (Pb), zinc (Zn), nickel (Ni), copper (Cu) and chromium (Cr(III)) with a concentration of 2 mg/L was shaken with the media. At a final pH of 8.5, limestone has significantly removed more than 90% of most metals followed by 80% and 65% removals using crushed bricks and gravel, respectively. The removal by aeration and settlement methods without solid media was less than 30%. Results indicated that the removal of heavy metals was influenced by the media and not directly by the pH. Investigations on the removal behaviour of these metals indicated that rough solid media with the presence of carbonate were beneficial for the removal process. Adsorption and precipitation as metals oxide and probably as metals carbonate were among the two mechanisms that contributed to the removal of metals from solution.
Dead calcareous skeletons (CSs) as low-cost adsorbents were studied to remove lead ions (Pb (II)) in an aqueous solution. Factors influencing the efficiency of CSs were evaluated by adsorbent size, contact time, initial concentration, dosage concentration and pH. The optimum CS size for removal of Pb (II) was 710 μm at an equilibrium time of 720 min. The best dosage of CS was 10 g/L for a 99% removal efficiency without pH adjustment. Pb (II) ions were effectively removed in the initial pH of the metal solution. CS was able to remove a high concentration (100 mg/L) of Pb (II) at a removal efficiency of 99.92% and at an adsorption capacity of 13.06 mg/g. Our results demonstrated the potential of CS as a metal adsorbent in the aqueous phase with a high-removal efficiency and distinct physical characteristics.
This paper proposes a new technique for real-time single cell stiffness measurement using lead zirconate titanate (PZT)-integrated buckling nanoneedles. The PZT and the buckling part of the nanoneedle have been modelled and validated using the ABAQUS software. The two parts are integrated together to function as a single unit. After calibration, the stiffness, Young's modulus, Poisson's ratio and sensitivity of the PZT-integrated buckling nanoneedle have been determined to be 0.7100 N·m-1, 123.4700 GPa, 0.3000 and 0.0693 V·m·N-1, respectively. Three Saccharomyces cerevisiae cells have been modelled and validated based on compression tests. The average global stiffness and Young's modulus of the cells are determined to be 10.8867 ± 0.0094 N·m-1 and 110.7033 ± 0.0081 MPa, respectively. The nanoneedle and the cell have been assembled to measure the local stiffness of the single Saccharomyces cerevisiae cells The local stiffness, Young's modulus and PZT output voltage of the three different size Saccharomyces cerevisiae have been determined at different environmental conditions. We investigated that, at low temperature the stiffness value is low to adapt to the change in the environmental condition. As a result, Saccharomyces cerevisiae becomes vulnerable to viral and bacterial attacks. Therefore, the proposed technique will serve as a quick and accurate process to diagnose diseases at early stage in a cell for effective treatment.
The ability of Pycnoporus sanguineus to adsorb heavy metals from aqueous solution was investigated in fixed-bed column studies. The experiments were conducted to study the effect of important design parameters such as column bed height, flow rate and initial concentration of solution. The breakthrough profiles were obtained in these studies. A mathematical model based on external mass transfer and pore diffusion was used for the prediction of mass transfer coefficient and effective diffusivity of metals in macro-fungi bed. Experimental breakthrough profiles were compared with the simulated breakthrough profiles obtained from the mathematical model. Bed Depth Service Time (BDST) model was used to analyse the experimental data and evaluated the performance of biosorption column. The BDST model parameters needed for the design of biosorption columns were evaluated for lead, copper and cadmium removal in the column. The columns were regenerated by eluting the metal ions using 0.1 M hydrochloric acid solution after the adsorption studies. The columns were subjected to repeated cycles of adsorption of same metal ions and desorption to evaluate the removal efficiency after adsorption-desorption.
The main challenge in the lead removal simulation is the behaviour of non-linearity relationships between the process parameters. The conventional modelling technique usually deals with this problem by a linear method. The substitute modelling technique is an artificial neural network (ANN) system, and it is selected to reflect the non-linearity in the interaction among the variables in the function. Herein, synthesized deep eutectic solvents were used as a functionalized agent with carbon nanotubes as adsorbents of Pb2+. Different parameters were used in the adsorption study including pH (2.7 to 7), adsorbent dosage (5 to 20 mg), contact time (3 to 900 min) and Pb2+ initial concentration (3 to 60 mg/l). The number of experimental trials to feed and train the system was 158 runs conveyed in laboratory scale. Two ANN types were designed in this work, the feed-forward back-propagation and layer recurrent; both methods are compared based on their predictive proficiency in terms of the mean square error (MSE), root mean square error, relative root mean square error, mean absolute percentage error and determination coefficient (R2) based on the testing dataset. The ANN model of lead removal was subjected to accuracy determination and the results showed R2 of 0.9956 with MSE of 1.66 × 10-4. The maximum relative error is 14.93% for the feed-forward back-propagation neural network model.
The purpose of this work is to remove Pb(II) from the aqueous solution using a type of hydrogel composite. A hydrogel composite consisting of waste linear low density polyethylene, acrylic acid, starch, and organo-montmorillonite was prepared through emulsion polymerization method. Fourier transform infrared spectroscopy (FTIR), Solid carbon nuclear magnetic resonance spectroscopy (CNMR)), silicon(-29) nuclear magnetic resonance spectroscopy (Si NMR)), and X-ray diffraction spectroscope ((XRD) were applied to characterize the hydrogel composite. The hydrogel composite was then employed as an adsorbent for the removal of Pb(II) from the aqueous solution. The Pb(II)-loaded hydrogel composite was characterized using Fourier transform infrared spectroscopy (FTIR)), scanning electron microscopy (SEM)), and X-ray photoelectron spectroscopy ((XPS)). From XPS results, it was found that the carboxyl and hydroxyl groups of the hydrogel composite participated in the removal of Pb(II). Kinetic studies indicated that the adsorption of Pb(II) followed the pseudo-second-order equation. It was also found that the Langmuir model described the adsorption isotherm better than the Freundlich isotherm. The maximum removal capacity of the hydrogel composite for Pb(II) ions was 430mg/g. Thus, the waste linear low-density polyethylene-g-poly (acrylic acid)-co-starch/organo-montmorillonite hydrogel composite could be a promising Pb(II) adsorbent.
The study examined the adsorption of Pb(II) ions from aqueous solution onto chitosan, chitosan-GLA and chitosan-alginate beads. Several important parameters influencing the adsorption of Pb(II) ions such as initial pH, adsorbent dosage and different initial concentration of Pb(II) ions were evaluated. The mechanism involved during the adsorption process was explored based on ion exchange study and using spectroscopic techniques. The adsorption capacities obtained based on non-linear Langmuir isotherm for chitosan, chitosan-GLA and chitosan-alginate beads in single metal system were 34.98, 14.24 and 60.27 mg/g, respectively. However, the adsorption capacity of Pb(II) ions were reduced in the binary metal system due to the competitive adsorption between Pb(II) and Cu(II) ions. Based on the ion exchange study, the release of Ca2+, Mg2+, K+ and Na+ ions played an important role in the adsorption of Pb(II) ions by all three adsorbents but only at lower concentrations of Pb(II) ions. Infrared spectra showed that the binding between Pb(II) ions and the adsorbents involved mostly the nitrogen and oxygen atoms. All three adsorbents showed satisfactory adsorption capacities and can be considered as an efficient adsorbent for the removal of Pb(II) ions from aqueous solutions.
Chitosan-tripolyphosphate (CTPP) beads were synthesized, characterized and were used for the adsorption of Pb(II) and Cu(II) ions from aqueous solution. The effects of initial pH, agitation period, adsorbent dosage, different initial concentrations of heavy metal ions and temperature were studied. The experimental data were correlated with the Langmuir, Freundlich and Dubinin-Radushkevich isotherm models. The maximum adsorption capacities of Pb(II) and Cu(II) ions in a single metal system based on the Langmuir isotherm model were 57.33 and 26.06 mg/g, respectively. However, the beads showed higher selectivity towards Cu(II) over Pb(II) ions in the binary metal system. Various thermodynamic parameters such as enthalpy (DeltaH degrees), Gibbs free energy (DeltaG degrees) and entropy (DeltaS degrees) changes were computed and the results showed that the adsorption of both heavy metal ions onto CTPP beads was spontaneous and endothermic in nature. The kinetic data were evaluated based on the pseudo-first and -second order kinetic and intraparticle diffusion models. Infrared spectra were used to elucidate the mechanism of Pb(II) and Cu(II) ions adsorption onto CTPP beads.
Heavy metal oxide glasses, containing bismuth and/or lead in their glass structure are new alternatives for rare eart (RE) doped hosts. Hence, the study of the structure of these vitreous systems is of great interest for science and technology. In this research work, GeO(2)-PbO-Bi(2)O(3) glass host doped with Er(3+)/Yb(3+) ions was synthesized by a conventional melt quenching method. The Fourier transform infrared (FTIR) results showed that PbO and Bi(2)O(3) participate with PbO(4) tetragonal pyramids and strongly distort BiO(6) octahedral units in the glass network, which subsequently act as modifiers in glass structure. These results also confirmed the existence of both four and six coordination of germanium oxide in glass matrix.
A study on the modification of rice husk by various carboxylic acids showed that tartaric acid modified rice husk (TARH) had the highest binding capacities for Cu and Pb. The carboxyl groups on the surface of the modified rice husk were primarily responsible for the sorption of metal ions. A series of batch experiments using TARH as the sorbent for the removal of Cu and Pb showed that the sorption process was pH dependent, rapid and exothermic. The sorption process conformed to the Langmuir isotherm with maximum sorption capacities of 29 and 108 mg/g at 27 +/- 2 degrees C for Cu and Pb, respectively. The uptake increased with agitation rate. Decrease in sorbent particle size led to an increase in the sorption of metal ions and this could be explained by an increase in surface area and hence binding sites. Metal uptake was reduced in the presence of competitive cations and chelators. The affinity of TARH for Pb is greater than Cu.
Electrokinetic process has emerged as an important tool for remediating heavy metal-contaminated soil. The process can concentrate heavy metals into smaller soil volume even in the absence of hydraulic flow. This makes it an attractive soil pre-treatment method before other remediation techniques are applied such that the chemical consumption in the latter stage can be reduced. The present study evaluates the feasibility of electrokinetic process in concentrating lead (Pb) and chromium (Cr) in a co-contaminated soil using different types of wetting agents, namely 0.01 M NaNO3, 0.1 M citric acid and 0.1 M EDTA. The data obtained showed that NaNO3 and citric acid resulted in poor Pb electromigration in this study. As for Cr migration, these agents were also found to give lower electromigration rate especially at low pH region as a result of Cr(VI) adsorption and possible reduction into Cr(III). In contrast, EDTA emerged as the best wetting agent in this study as it formed water-soluble anionic complexes with both Pb and Cr. This provided effective one-way electromigration towards the anode for both ions, and they were accumulated into smaller soil volume with an enrichment ratio of 1.55-1.82. A further study on the application of approaching cathode in EDTA test showed that soil alkalisation was achieved, but this did not provide significant enhancement on electromigration for Pb and Cr. Nevertheless, the power consumption for electrokinetic process was decreased by 22.5%.
Multiwall carbon nanotubes (MWCNTs) were synthesized using a tubular microwave chemical vapor deposition technique, using acetylene and hydrogen as the precursor gases and ferrocene as catalyst. The novel MWCNT samples were tested for their performance in terms of Pb(II) binding. The synthesized MWCNT samples were characterized using Fourier Transform Infrared (FT-IR), Brunauer, Emmett and Teller (BET), Field Emission Scanning Electron Microscopy (FESEM) analysis, and the adsorption of Pb(II) was studied as a function of pH, initial Pb(II) concentration, MWCNT dosage, agitation speed, and adsorption time, and process parameters were optimized. The adsorption data followed both Freundlich and Langmuir isotherms. On the basis of the Langmuir model, Qmax was calculated to be 104.2mg/g for the microwave-synthesized MWCNTs. In order to investigate the dynamic behavior of MWCNTs as an adsorbent, the kinetic data were modeled using pseudo first-order and pseudo second-order equations. Different thermodynamic parameters, viz., ∆H(0), ∆S(0) and ∆G(0) were evaluated and it was found that the adsorption was feasible, spontaneous and endothermic in nature. The statistical analysis revealed that the optimum conditions for the highest removal (99.9%) of Pb(II) are at pH5, MWCNT dosage 0.1g, agitation speed 160r/min and time of 22.5min with the initial concentration of 10mg/L. Our results proved that microwave-synthesized MWCNTs can be used as an effective Pb(II) adsorbent due to their high adsorption capacity as well as the short adsorption time needed to achieve equilibrium.
Rice straw/magnetic nanocomposites (RS/Fe3O4-NCs) were prepared via co-precipitation method for removal of Pb(II) and Cu(II) from aqueous solutions. Response surface methodology (RSM) was utilized to find the optimum conditions for removal of ions. The effects of three independent variables including initial ion concentration, removal time, and adsorbent dosage were investigated on the maximum adsorption of Pb (II) and Cu (II). The optimum conditions for the adsorption of Pb(II) and Cu(II) were obtained (100 and 60 mg/L) of initial ion concentration, (41.96 and 59.35 s) of removal time and 0.13 g of adsorbent for both ions, respectively. The maximum removal efficiencies of Pb(II) and Cu(II) were obtained 96.25% and 75.54%, respectively. In the equilibrium isotherm study, the adsorption data fitted well with the Langmuir isotherm model. The adsorption kinetics was best depicted by the pseudo-second order model. Desorption experiments showed adsorbent can be reused successfully for three adsorption-desorption cycles.
A facile electrochemical sandwich immunosensor for the detection of a breast cancer biomarker, the human epidermal growth factor receptor 2 (HER2), was designed, using lead sulfide quantum dots-conjugated secondary HER2 antibody (Ab2-PbS QDs) as a label. Using Ab2-PbS QDs in the development of electrochemical immunoassays leads to many advantages such as straightforward synthesis and well-defined stripping signal of Pb(II) through acid dissolution, which in turn yields better sensing performance for the sandwiched immunosensor. In the bioconjugation of PbS QDs, the available amine and hydroxyl groups from secondary anti-HER2 and capped PbS QDs were bound covalently together via carbonyldiimidazole (CDI) acting as a linker. In order to quantify the biomarker, SWV signal was obtained, where the Pb2+ ions after acid dissolution in HCl was detected. The plated mercury film SPCE was also detected in situ. Under optimal conditions, HER2 was detected in a linear range from 1-100 ng/mL with a limit of detection of 0.28 ng/mL. The measures of satisfactory recoveries were 91.3% to 104.3% for the spiked samples, displaying high selectivity. Therefore, this method can be applied to determine HER2 in human serum.
The lead (Pb2+) bioaccumulation capacities and mechanisms of three different physiological structures (vegetative cells, decay cells and spores) of B. coagulans R11 isolated from a lead mine were examined in this study. The results showed that the total Pb2+ removal capacity of vegetative cells (17.53 mg/g) was at its optimal and higher than those of the spores and decay cells at the initial lead concentration of 50 mg/L. However, when the initial lead concentration surpassed 50 mg/L, Pb2+ removal capacity of decay cells was more efficient. Zeta potential, Fourier transform infrared (FTIR) and functional group modification analyses demonstrated that the electrostatic attraction and chelating activity of the functional groups were the primary pathways involved in the extracellular accumulation of Pb2+ by the vegetative cells and spores. However, the primary Pb2+ binding pathway in the decay cells was hypothesized to be due to physical adsorption, which easily led to Pb2+ desorption. Based on these results, we conclude that the vegetative cell is the ideal lead sorbent. Therefore, it is important to inhibit the transformation of the vegetative cells into decay cells and spores, which can be achieved by culturing the bacteria under anaerobic conditions to prevent spore formation. Heat stimulation can effectively enhance spore germination to generate vegetative cells.
A study was carried out to investigate the fractionation of Cd, Cr, Cu, Fe, Mn, Pb, and Zn in shrimp aquaculture sludge from Selangor, Malaysia, using original (unmodified) and modified four-steps BCR (European Community Bureau of Reference, now known as the Standards Measurements and Testing Program) sequential extraction scheme. Step 2 of the unmodified BCR procedure (subsequently called Method A) involves treatment with 0.1 M hydroxylammonium chloride at pH 2, whereas 0.5 M hydroxylammonium chloride at pH 1.5 was used in the modified BCR procedure (subsequently called Method B). Metal analyses were carried out by flame atomic absorption spectrometry. A pseudo-total aqua-regia digest of BCR CRM 701 has also been undertaken for quality assurance purposes. The recovery of Method A for all metals studied ranges from 96.14% to 105.26%, while the recovery for Method B ranges from 95.94% to 122.40%. Our results reveal that Method A underestimated the proportion of metals bound to the easily reducible fraction except for copper. Therefore, the potential mobility of these elements is higher than others. Thus, to use this sludge as a fertilizer we have to first find a remediation for reduction of heavy metal contamination.
In the present study, ZnO nanoparticles (NPs) were synthesized in zerumbone solution by a green approach and appraised for their ability to absorb Pb(II) ions from aqueous solution. The formation of as-synthesized NPs was established by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), and UV-visible studies. The XRD and TEM analyses revealed high purity and wurtzite hexagonal structure of ZnO NPs with a mean size of 10.01 ± 2.6 nm. Batch experiments were performed to investigate the impact of process parameters viz. Pb(II) concentration, pH of solution, adsorbent mass, solution temperature, and contact time variations on the removal efficiency of Pb(II). The adsorption isotherm data provided that the adsorption process was mainly monolayer on ZnO NPs. The adsorption process follows pseudo-second-order reaction kinetic. The maximum removal efficiencies were 93% at pH 5. Thermodynamic parameters such as enthalpy change (ΔH⁰), free energy change (ΔG⁰), and entropy change (ΔS⁰) were calculated; the adsorption process was spontaneous and endothermic. The good efficiency of the as-synthesized NPs makes them attractive for applications in water treatment, for removal of heavy metals from aqueous system.