Microbial Sensing and Removal of Heavy Metals: Bioelectrochemical Detection and Removal of Chromium(VI) and Cadmium(II).

The presence of inorganic pollutants such as Cadmium(II) and Chromium(VI) could destroy our environment and ecosystem. To overcome this problem, much attention was directed to microbial technology, whereas some microorganisms could resist the toxic effects and decrease pollutants concentration while the microbial viability is sustained. Therefore, we built up a complementary strategy to study the biofilm formation of isolated strains under the stress of heavy metals. As target resistive organisms, Rhizobium-MAP7 and Rhodotorula ALT72 were identified. However, Pontoea agglumerans strains were exploited as the susceptible organism to the heavy metal exposure. Among the methods of sensing and analysis, bioelectrochemical measurements showed the most effective tools to study the susceptibility and resistivity to the heavy metals. The tested Rhizobium strain showed higher ability of removal of heavy metals and more resistive to metals ions since its cell viability was not strongly inhibited by the toxic metal ions over various concentrations. On the other hand, electrochemically active biofilm exhibited higher bioelectrochemical signals in presence of heavy metals ions. So by using the two strains, especially Rhizobium-MAP7, the detection and removal of heavy metals Cr(VI) and Cd(II) is highly supported and recommended.

Green and efficient removal of heavy metals from Porphyra haitanensis using natural deep eutectic solvents.

BACKGROUND: Porphyra haitanensis now faces serious heavy metal pollution problems. Natural deep eutectic solvents (NADESs) have been recognized as a novel class of sustainable solvents, which can be used for heavy metal removal. In this study, 28 kinds of NADESs were prepared and investigated as eluent in the removal of lead (Pb), cadmium (Cd), chromium (Cr), arsenic (As), and copper (Cu) from P. haitanensis for the first time, and the adsorption mechanism of NADESs was also studied. RESULTS: The removals were greatly improved by NADESs compared with control where the removal rates of Pb, Cd, Cr, As and Cu were 17.4-87.54%, 57.54-100%, 9.8-48.59%, 21.32-78.24% and 11.68-79.73%, respectively. The optimal condition was 10% water content and solid-liquid ratio of 1:20. Moreover, the addition of 20% natural surfactant arabic gum can further increase the heavy metals removal rates of NADESs. The adsorption mechanism experiments showed that the pseudo second-order model and the Freundlich adsorption model can better explain the adsorption mechanism of NADESs on heavy metals removal. CONCLUSION: Taken together, a green and efficient method for removing heavy metals from P. haitanensis was established. © 2020 Society of Chemical Industry.

Removal of Cd(II) using dithiocarboxyl cornstalk and the waste filtrate.

A novel adsorbent, called dithiocarboxyl cornstalk (DTCS), was developed, and the effects of various parameters on the adsorption performance for Cd(II) with DTCS were investigated in this work. The results suggested that DTCS presented the efficient removal capacity for Cd(II) when the pH values, adsorption temperature, and oscillation rate were 3.0 to 6.0, 313 K, and 150 rpm, respectively. The adsorption kinetic data were more agreed with pseudo-second-order kinetic model, and the isotherm data could be characterized by Freundlich model. The thermodynamic data indicated the adsorption process was endothermic and spontaneous. The FTIR and SEM confirmed the chemisorption between Cd(II) and DTCS. Furthermore, to eliminate the secondary pollution, the waste filtrate generated in the preparation of DTCS was employed to remove Cd(II) through flocculation experiments. The results showed that the waste filtrate is a potential flocculant for the treatment of wastewater containing Cd(II).

Preparation and characterization of PAN nanofibers containing boehmite nanoparticles for the removal of microbial contaminants and cadmium ions from water.

Nanofibers of polyacrylonitrile (PAN)/boehmite were prepared by electrospinning a homogeneous solution of PAN/DMF (dimethyl formamide). Enhancing the amount of boehmite nanoparticles (NPs) led to increase in the nanofibers' diameter. Samples had high pure water flux, which did not change significantly with boehmite concentration, but decreased with increasing electrospinning duration. Escherichia coli bacteria removal was remarkably more efficient, as it was enhanced from 72.33% to 97.37% with increase in the boehmite NPs' concentration from 0 to 10% wt. High bacterial removal efficiency could be attained by the large surface area of NPs, as well as the electrostatic force of attraction between NPs and microorganisms. The increase in boehmite concentration from 10 to 30 and 50% did not noticeably affect bacterial removal. Prolonging electrospinning time significantly enhanced bacteria removal. Hence, it was shown that 6-hour electrospinning of PAN/boehmite nanofiber layers composed of 50% boehmite led to 99.7%, 99.39%, 99.8%, and 74% E. coli, Staphylococcus aureus bacteria removal, particles' separation efficiency of 2 µm and cadmium adsorptivity, respectively, which were better than those obtained by using pure PAN nanofibers. E. coli bacterial removal efficiency of the sample was increased to 99.99% by repeating filtering four times. Considering the results, this PAN/boehmite nanofibers' membrane has potential application to purification of drinking water.

Efficiency and mechanisms of cadmium removal via core-shell zeolite/Zn-layer double hydroxides.

To investigate the removal mechanisms of cadmium (Cd) by Zn-layer double hydroxides-modified zeolites substrates in constructed rapid infiltration systems (CRIS), the ZnAl-LDHs and ZnFe-LDHs were synthesized and in-situ coated on the original zeolites through co-precipitation method. The prepared Zn-LDHs-modified and original zeolites were characterized by scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS) methods, whose results provided the evidences that the Zn-LDHs were successfully coated on the original zeolites. From the results of purification experiments, the average Cd removal rates of ZnAl-LDHs-modified, ZnFe-LDHs-modified and original zeolites were 88.40, 86.00 and 32.52%, respectively; demonstrating that the removal rates of zeolites could significantly improve. Additionally, the modification of Zn-LDHS could enhance the theoretical adsorption ability. According to the results of isothermal adsorption and desorption tests, the desorption rates of Zn-LDHs-modified zeolites were higher than that of original zeolites. Cd adsorption capacity of ZnFe-LDHs-modified zeolites was 1428.57 mg kg-1 and original zeolites was 434.783 mg kg-1. In the adsorption kinetic studies, the pseudo-second-order models were used to well describe the experimental results of Zn-LDHs-modified zeolites, indicating that their adsorption types were attributed to be more stable chemisorption. Besides, the relevant microbial tests also confirmed that microbial enzymatic activity and extracellular polymeric substances (EPS) were significantly promoted on surface of Zn-LDHs-modified zeolites. The contents of EPS on the surface of zeolites were as following: ZnAl-LDHs-modified zeolites (78.58128 µg/g) > ZnFe-LDHs-modified zeolites (71.85445 µg/g) > original zeolites (68.69904 µg/g). Meanwhile, the results of high-throughput sequencing showed that modification by Zn-LDHs improved microbial diversity and relative abundance. The Proteobacteria was the dominant phylum and the Acidobacteria was conducive to Cd removal. Overall, it could be concluded that ZnAl-LDHs-modified zeolites might be applied as an efficient substrate for Cd removal in CRIS.

Optimization for Liquid-Liquid Extraction of Cd(II) over Cu(II) Ions from Aqueous Solutions Using Ionic Liquid Aliquat 336 with Tributyl Phosphate.

This study investigates the separation of two heavy metals, Cd(II) and Cu(II), from the mixed synthetic feed using a liquid-liquid extraction. The current study uses tri-octyl methylammonium chloride (Aliquat 336) as the extractant (with tributyl phosphate (TBP) as a phase modifier), diluted in toluene, in order to investigate the selective extraction of Cd(II) over Cu(II) ions. We investigate the use of ethylenediaminetetraacetic acid (EDTA) as a masking agent for Cu(II), when added in aqueous feed, for the selective extraction of Cd(II). Five factors that influence the selective extraction of Cd(II) over Cu(II) (the equilibrium pH (pHeq), Aliquat 336 concentration (Aliquat 336), TBP concentration (TBP), EDTA concentration (EDTA), and organic to aqueous ratio (O:A)) were analyzed. Results from a 25-1 fractional factorial design show that Aliquat 336 significantly influenced Cd(II) extraction, whereas EDTA was statistically significant for the antagonistic effect on the E% of Cu(II) in the same system. Moreover, results from optimization experiment showed that the optimum conditions are Aliquat 336 concentration of 99.64 mM and EDTA concentration of 48.86 mM-where 95.89% of Cd(II) was extracted with the least extracted Cu(II) of 0.59%. A second-order model was fitted for optimization of Cd(II) extraction with a R2 value of 0.998, and ANOVA results revealed that the model adequately fitted the data at a 5% significance level. Interaction between Aliquat 336 and Cd(II) has been proven via FTIR qualitative analysis, whereas the addition of TBP does not affect the extraction mechanism.

Sustainable Development of Enhanced Luminescence Polymer-Carbon Dots Composite Film for Rapid Cd2+ Removal from Wastewater.

As a remedy for environmental pollution, a versatile synthetic approach has been developed to prepare polyvinyl alcohol (PVA)/nitrogen-doped carbon dots (CDs) composite film (PVA-CDs) for removal of toxic cadmium ions. The CDs were first synthesized using carboxymethylcellulose (CMC) of oil palms empty fruit bunch wastes with the addition of polyethyleneimine (PEI) and then the CDs were embedded with PVA. The PVA-CDs film possess synergistic functionalities through increasing the content of hydrogen bonds for chemisorption compared to the pure CDs. Optical analysis of PVA-CDs film was performed by ultraviolet-visible and fluorescence spectroscopy. Compared to the pure CDs, the solid-state PVA-CDs displayed a bright blue color with a quantum yield (QY) of 47%; they possess excitation-independent emission and a higher Cd2+ removal efficiency of 91.1%. The equilibrium state was achieved within 10 min. It was found that adsorption data fit well with the pseudo-second-order kinetic and Langmuir isotherm models. The maximum adsorption uptake was 113.6 mg g-1 at an optimal pH of 7. Desorption experiments showhe that adsorbent can be reused fruitfully for five adsorption-desorption cycles using 0.1 HCl elution. The film was successfully applied to real water samples with a removal efficiency of 95.34% and 90.9% for tap and drinking water, respectively. The fabricated membrane is biodegradable and its preparation follows an ecofriendly green route.

Low-cost field production of biochars and their properties.

Biochar has been intensively investigated for carbon sequestration, soil fertility enhancement, and immobilization of heavy metals and organic pollutants. Large-scale use of biochar in agricultural production and environmental remediation, however, has been constrained by its high cost. Here, we demonstrated the production of low-cost biochar ($20/ton) in the field from Robinia pseudoacacia biowaste via a combined aerobic and oxygen-limited carbonization process and a fire-water-coupled method. It involved aerobic combustion at the outer side of biomass, oxygen-limited pyrolysis in the inner core of biomass, and the termination of the carbonization by water spray. The properties of biochar thus produced were greatly affected by exposure time (the gap between a burning char fell to the ground and being extinguished by water spray). Biochar formed by zero exposure time showed a larger specific surface area (155.77 m2/g), a higher carbon content (67.45%), a lower ash content (15.38%), and a higher content of carboxyl and phenolic-hydroxyl groups (1.74 and 0.86 mol/kg, respectively) than biochars formed with longer exposure times (5-30 min). Fourier-transform infrared spectroscopic (FTIR) spectra indicated that oxygen-containing functional groups of biochar played a role in Cd and oxytetracycline sorption though a quantitative relationship could not be established as the relative contribution of carbon and ash moieties of biochar to the sorption was unknown. Outcomes from this research provide an option for inexpensive production of biochar to support its use as a soil amendment in developing countries.

Fabrication of biobeads expressing heavy metal-binding protein for removal of heavy metal from wastewater.

Heavy metals, being toxic in nature, are one of the most persistent problems in wastewater. Unabated discharge of large amount of heavy metals into water bodies are known to cause several environmental and health impacts. Biological remediation processes like microbial remediation and phytoremediation are proved to be very effective in the reduction of heavy metal pollutants in wastewater. To circumvent the issues involved several peptides and proteins are being explored. Metal-binding capacity, accumulation, and tolerance of heavy metals in bacteria can be upsurge by overexpressing the genes which code for metal-binding proteins. In the present study, an attempt has been made to bioremediate heavy metal toxicity by overexpressing metal-binding proteins. Two expression cassettes harboring top4 metal-binding protein (T4MBP) and human metallothionein 3 (HMP3) were designed under the control of constitutive CaMV 35S promoter and transformed into E.coli TBI cells. E.coli over expressing HMP3 and T4MBP were immobilized in biobeads which were explored for the detoxification of water contaminated with copper and cadmium. Effects on the concentration of heavy metal before and after treatment with beads were estimated with the help of ICP-OES. Noteworthy results were obtained in the case of copper with 87.2% decrease in its concentration after treatment with biobeads. Significant decrement of 32.8% and 27.3% was found in case of zinc and cadmium, respectively. Mechanisms of binding of proteins with heavy metals were further validated by molecular modeling and metal-binding analysis. HMP3 protein was found to be more efficient in metal accumulation as compared with T4MBP. The fabricated biobeads in this study definitely offer an easy and user-handy approach towards the treatment of toxic wastewater.

Distribution and chemical forms of cadmium in Coptis chinensis Franch. determined by laser ablation ICP-MS, cell fractionation, and sequential extraction.

Coptis chinensis Franch., is a widely used medicinal plant in China. This plant is often contaminated by cadmium (Cd) and render health risk to human consumers. Understanding distribution of Cd and its chemical forms is important to evaluate accumulation of the metal and its detoxification mechanisms in this plant. Since few studies have focused on this aspect, we used laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) to spatially locate Cd in rhizome cross-sections, and ICP-MS to analyze the Cd subcellular distribution and the chemical forms of Cd in different tissues. Rhizome bioimaging results showed that Cd was distributed predominantly within the periderm, cortex, pith, and root trace vascular bundle. The LA-ICP-MS results suggested that Ca2+ channels might be a pathway for Cd entry into the plant. Subcellular distribution data indicated that most of Cd was associated with the cell wall (41.8-77.1%) and the soluble fraction (14.4-52.7%) in all tissues. Analysis of chemical forms revealed that majority Cd existed in less mobile and less toxic forms in all tissues, and P could convert to insoluble phosphate with Cd to moderate Cd toxicity. The new understanding of Cd accumulation and detoxification might provide novel strategies for reducing the levels of Cd in C. chinensis Franch., thereby mitigating its potential transfer to humans and providing a theoretical basis for evaluating the Cd status in other medicinal plants. Further, our findings might provide a basis for establishing a reasonable Cd limit level of traditional Chinese medicinal materials.

Combined nitrogen fertilizer and wheat straw increases the cadmium phytoextraction efficiency of Tagetes patula.

The soil cadmium (Cd) availability and uptake by Tagetes patula grown in two soil types contaminated with Cd and amended with N fertilizer and wheat straw were studied in a pot-culture experiment. The results indicated that N fertilizer treatment (N) and N fertilizer plus straw treatment (NS) promoted T. patula growth, while straw treatment (S) decreased T. patula biomass relative to the control. NS and S treatments increased Cd mobility in the soil and facilitated its uptake by T. patula in Acidic Ferralsols (AF) and Calcaric Cambisols (CC), but the promotion effect was much greater in CC than in AF. The Cd concentrations in the Tagetes shoots in the S and NS treatments were 40% and 27% greater, respectively, than those in the control treatment for AF, and 111% and 80% greater, respectively, for CC. Decreases in soil pH and increases in dissoluble organic carbon concentration after adding N fertilizer and straw were associated with an increase in soil Cd availability and in Cd uptake by T. patula. The results indicate that the NS treatment can alter the soil microenvironment, increasing Cd bioavailability and thus facilitating Cd uptake by T. patula. This work highlights that the combined application of N fertilizer with straw may be a useful way to increase the phytoextraction efficiency of Cd-contaminated soil by the Cd-hyperaccumulator T. patula.

Selection of the Optimal Spectral Resolution for the Cadmium-Lead Cross Contamination Diagnosing Based on the Hyperspectral Reflectance of Rice Canopy.

This paper proposed an optimal spectral resolution for diagnosing cadmium-lead (Cd-Pb) cross contamination with different pollution levels based on the hyperspectral reflectance of rice canopy. Feature bands were sequentially selected by two-way analysis of variance (ANOVA2) and random forests from the high-dimensional hyperspectral data after preprocessing. Then Support Vector Machine (SVM) was applied to diagnose the pollution levels using different feature bands combination with different spectral resolutions and cross validation was conducted to evaluate the distinguishing accuracies. Finally, the optimal spectral resolution could be determined by comparing the diagnosing accuracies of the optimal feature bands combination in each spectral resolution. In the experiments, the hyperspectral reflectance data of rice canopy with ten different spectral resolutions was captured, covering 16 pretreatments of Cd and Pb pollution. The experimental results showed the optimal spectral resolution was 9 nm with the highest average accuracy of 0.71 and relatively standard deviation of 0.07 for diagnosing the categories and levels of Cd-Pb cross contamination. The useful exploration provided an evidence for optimal spectral resolution selection to reduce the cost of heavy metal pollution diagnose.

A Biosensor Platform for Metal Detection Based on Enhanced Green Fluorescent Protein.

Microbial cell-based biosensors, which mostly rely on stress-responsive operons, have been widely developed to monitor environmental pollutants. Biosensors are usually more convenient and inexpensive than traditional instrumental analyses of environmental pollutants. However, the targets of biosensors are restricted by the limited number of genetic operon systems available. In this study, we demonstrated a novel strategy to overcome this limitation by engineering an enhanced green fluorescent protein (eGFP). It has been reported that combining two fragments of split-eGFP can form a native structure. Thus, we engineered new biosensors by inserting metal-binding loops (MBLs) between ß-strands 9 and 10 of the eGFP, which then undergoes conformational changes upon interaction between the MBLs and targets, thereby emitting fluorescence. The two designed MLBs based on our previous study were employed as linkers between two fragments of eGFP. As a result, an Escherichia coli biosensor exhibited a fluorescent signal only when interacting with cadmium ions, revealing the prospect of a new biosensor for cadmium detection. Although this study is a starting stage for further developing biosensors, we believe that the proposed strategy can serve as basis to develop new biosensors to target various environmental pollutants.

Modified Rice Straw Enhanced Cadmium (II) Immobilization in Soil and Promoted the Degradation of Phenanthrene in Co-Contaminated Soil.

Very limited information is available about heavy metal-polycyclic aromatic hydrocarbons (PAHs) depollution involving the modified natural material in soil. Using phenanthrene and cadmium (Cd) as model, this study investigated the effect(s) of modified rice straw by a NaOH solution and on PAHs, heavy metal availability, and their interactions. Treatment included chemical contaminant with/without modified/unmodified rice straw. Fourier Transform Infrared (FTIR) analysis revealed that certain functional groups including anionic matters groups, which can a complex with Cd2+, were exposed on the modified rice straw surfaces. Therefore, Cd concentration was significantly reduced by about 60%, 57%, 62.5 %, and, 64% in the root, shoot, CaCl2, diethylenetriaminepentaacetic acid (DTPA), and extractable Cd, respectively. Subsequently, the prediction of the functional profile of the soil metagenome using Clusters Orthologous Groups (COGs) and the Kyoto Encyclopedia of Genes and Genomes (KEGG) database revealed that the significantly changed individual COGs belonged to the carbohydrate metabolism, ion transports, and signaling (including cytochrome P450s) categories. This indicated that ion transports might be involved in Cd management, while carbohydrate metabolism, including bisphenol, benzoate, ethylbenzene degradation, and cytochrome P450s, were rather involved in phenanthrene metabolism. The exposed functional group might serve as an external substrate, and P450s might serve as a catalyst to activate and initiate phenanthrene metabolism process. These finding offer confirmation that modified straw could promote the reduction of heavy metal and the degradation of PAHs in soil.

Supramolecular Hybrid Material Based on Engineering Porphyrin Hosts for an Efficient Elimination of Lead(II) from Aquatic Medium.

Porphyrins show great promise for future purification demands. This is largely due to their unique features as host binding molecules that can be modified at the synthetic level, and largely improved by their incorporation into inorganic based materials. In this study, we assessed the efficacy of a hybrid material obtained from the immobilization of 5,10,15,20-tetrakis(pentafluorophenyl)-porphyrin on silica surface to remove Pb(II), Cu(II), Cd(II), and Zn(II) ions from water. The new organic-inorganic hybrid adsorbent was fully characterized by adequate techniques and the results show that the hybrid exhibits good chemical and thermal stability. From batch assays, it was evaluated how the efficacy of the hybrid was affected by the pH, contact time, initial metal concentration, and temperature. The adsorption kinetic and isotherms showed to fit the recent developed fractal-like pseudo-second-order model and Langmuir⁻Freundlich model respectively. The highest adsorption capacities for Pb(II), Cu(II), Cd(II), and Zn(II) ions were 187.36, 125.17, 82.45, and 56.23 mg g-1, respectively, at pH 6.0 and 25 °C. This study also shows that metal cations from real river water samples can be efficient removed in the presence of the new adsorbent material.

Determination of cadmium in bread and biscuit samples using ultrasound-assisted temperature-controlled ionic liquid microextraction.

BACKGROUND: In the present work, a simple and rapid method was proposed for the preconcentration of cadmium using ultrasound-assisted temperature-controlled ionic liquid microextraction (TC-IL-LPME). The dispersion of the ionic liquid (1-Hmim[PF6 ]) in the aqueous phase was performed by heating it in an ultrasonic bath, followed by cooling in an ice bath. After centrifugation, the enriched phase was dissolved in 45% (w/w) nitric acid solution to reduce viscosity, and the cadmium content was measured employing electrothermal atomic absorption spectrometry (ET-AAS). The 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol reagent (Br-PADAP) was used as a complexing agent. RESULTS: Under optimized conditions, the method had a detection limit of 2.0 ng L-1 and an enrichment factor of 24. The accuracy of the method was evaluated through the analysis of the certified reference material of brown bread (BCR-191). The method was applied to the determination of cadmium in samples of bread and biscuit. The limit of detection of the solid samples was 0.10 µg kg-1 . The recovery of cadmium in the samples varied between 93% and 107%. CONCLUSION: The proposed method is presented as a simple, cheap, ecological and a sensitive alternative for the determination of cadmium in bread and biscuit samples. © 2019 Society of Chemical Industry.

Combining potassium chloride leaching with vertical electrokinetics to remediate cadmium-contaminated soils.

This study evaluated the feasibility of combining potassium chloride (KCl) leaching and electrokinetic (EK) treatment for the remediation of cadmium (Cd) and other metals from contaminated soils. KCl leaching was compared at three concentrations (0.2%, 0.5%, and 1% KCl). EK treatment was conducted separately to migrate the metals in the topsoil to the subsoil. The combined approach using KCl leaching before or after EK treatment was compared. For the single vertical EK treatment, the removal of Cd, lead (Pb), copper (Cu) and zinc (Zn) from the topsoil (0-20 cm) was 9.38%, 4.80%, 0.95%, and 10.81%, respectively. KCl leaching at 1% KCl removed 84.06% Cd, 9.95% Pb, 4.34% Cu, and 19.93% Zn from the topsoil, with higher removal efficiency than that of the 0.2% and 0.5% KCl leaching treatments. By combining the KCl leaching and EK treatment, the removal efficiency of heavy metals improved, in particular for the 1% KCl + EK treatment, where the removal rate of Cd, Pb, Cu, and Zn from the upper surface soil reached 97.79%, 17.69%, 14.37%, and 41.96%, respectively. Correspondingly, the soil Cd content decreased from 4 to 0.21 mg/kg, and was below the Chinese standard limit of 0.3 mg/kg soil. These results indicate that 1% KCl + EK treatment is a good combination technique to mitigate Cd pollution from contaminated soils used for growing rice and leafy vegetables.

A fully bio-sourced adsorbent of heavy metals in water fabricated by immobilization of quinine on cellulose paper.

The fabrication of a fully bio-sourced adsorbent of Cd(II) by covalent immobilization of quinine on cellulose paper is described. The double bond of commercially available quinine was converted to a terminal alkyne function which was reacted with cellulose paper, chemically modified with azide functions, through a 1,3-dipolar cycloaddition, leading to Cell-Quin. The adsorption efficiency of Cell-Quin was investigated to determine the optimal pH, contact time and dose of adsorbent, ultimately leading to high levels of removal. The mechanism of adsorption of Cell-Quin was deeply rationalized through kinetic experiments and isotherm modeling. We also showed that Cell-Quin could adsorb other heavy metals such as Cu(II), Pb(II), Ni(II) and Zn (II).

Ion cum molecularly dual imprinted polymer for simultaneous removal of cadmium and salicylic acid.

Ion cum molecularly dual imprinted polymer (DMIP) was synthesized for the simultaneous removal of salicylic acid (SA) and cadmium (Cd) by suspension polymerization method using chitosan (CTS) as functional polymer, epichlorohydrin as cross-linker, and 4-hydroxy benzoic acid (4HBA) as well as Cd as organic and inorganic templates, respectively. Use of the dummy template 4HBA during the synthesis of DMIP had the advantage of creating imprinted cavities in DMIP, which depicted good uptake for SA. Scanning electron microscopy and Fourier transform infrared spectroscopy indicated successful preparation of DMIP. Particle size analysis confirmed polydispersity, and thermal and swelling studies indicated the mechanical stability in DMIP. The rebinding capacities of the DMIP for Cd and SA were found to be 38.46 and 23.81 mgg-1 , respectively, under the optimize condition of the time, dose, and concentration. Adsorption isotherm results fitted into Langmuir adsorption isotherm model with the R2 values of 0.994 and 0.995 for Cd and SA, respectively. The presence of intramolecular hydrogen bonding in SA, stability of the template-monomer complexes (CTS-SA and CTS-4HBA), and the involvement of the hydroxyl groups on DMIP for the uptake of SA has been supported by molecular modeling studies using Gaussian 03 software. The electron doublet of the amino groups of DMIP was involved for the uptake of Cd. Lower binding efficiency of DMIP for SA as compared to Cd may be due to the partial participation of hydroxyl group in cross-linking with epichlorohydrin during the synthesis of DMIP.

Magnetic ionic liquid-based dispersive liquid-liquid microextraction technique for preconcentration and ultra-trace determination of Cd in honey.

A simple, highly efficient, batch, and centrifuge-less dispersive liquid-liquid microextraction method based on a magnetic ionic liquid (MIL-DLLME) and electrothermal atomic absorption spectrometry (ETAAS) detection was developed for ultra-trace Cd determination in honey. Initially, Cd(II) was chelated with ammonium diethyldithiophosphate (DDTP) at pH 0.5 followed by its extraction with the MIL trihexyl(tetradecyl)phosphonium tetrachloroferrate(III) ([P6,6,6,14]FeCl4) and acetonitrile as dispersant. The MIL phase containing the analyte was separated from the aqueous phase using only a magnet. A back-extraction procedure was applied to recover Cd from the MIL phase using diluted HNO3 and this solution was directly injected into the graphite furnace of ETAAS instrument. An extraction efficiency of 93% and a sensitivity enhancement factor of 112 were obtained under optimal experimental conditions. The detection limit (LOD) was 0.4 ng L-1 Cd, while the relative standard deviation (RSD) was 3.8% (at 2 µg L-1 Cd and n = 10), calculated from the peak height of absorbance signals. This work reports the first application of the MIL [P6,6,6,14]FeCl4 along with the DLLME technique for the successful determination of Cd at trace levels in different honey samples. Graphical abstract Preconcentration of ultratraces of Cd in honey using a magnetic ionic liquid and dispersive liquid-liquid microextraction technique.