Thermal stability of organosilica and their forms modified by ions of copper(II)

Thermal stability of two-component organosilica sorbents – silico-polymethylsiloxanes with the ratio of hydrophilic and hydrophobic components of 50:50 and 70:30 mass%, and their forms, modified by copper(II), was investigated using thermal analysis (DTG, DTA, TG). The influence of the composition of modified organosilica sorbents and copper(II) content on the endothermic (removal of adsorbed water) and exothermic (decomposition by oxidation of methyl groups, possible hydration of surface) peak temperatures and on mass loss is shown. It was found that thermal stability of organosilica modified by copper(II) was lower than that of initial sorbents and depends on the content of modifying component and ratio of silanol and methylsilil groups in organosilica composition.     

Determination of gold,palladium and copper by flame atomic absorption spectrometry after preconcentration on silica gel modified with 3-(2-aminoethylamino)propyl group

A preconcentration method of gold, palladium and copper based on the sorption of Au (III), Pd (II) and Cu (II) ions on a column packed with 3-(2-aminoethylamino)propyl bonded silica gel is described. The modified silica gel was synthesized and characterized by FT-IR and C, H, N elemental analysis. At column preconcentration, the effects of parameters such as pH, volume, flow rate, matrix constituents of solutions and type of eluent on preconcentration of gold, palladium and copper were studied. The recoveries of Au (III), Pd (II) and Cu (II) were 98.93±0.51, 98.81±0.36 and 99.21±0.42 % at 95 % confidence level, respectively. The detection limits (δ) of the elements were 0.032, 0.016 and 0.012 μg ml⁻¹, respectively. The preconcentration method was applied for determination of gold and palladium in certified reference material SARM 7B and copper in river and synthetic seawater by FAAS. Gold, palladium and copper were determined with relative error lower than 10 %.     

Synthesis and properties of new chelating resin with a spacer containing alpha-nitroso-beta-naphthol as the functional group

A new chelating ion-exchange resin with a spacer CH₂-NH-C₆H₄- based on a microreticular chloromethylated styrene-divinylbenzene copolymer containing α-nitroso-β-naphthol as a functional group has been synthesized. The sorption characteristics for manganese(II), iron(III), cobalt(II), nickel(II), copper(II), and zinc(II) have been investigated over the pH range 1.0–7.0. The resin is highly stable in acidic and alkaline medium. Iron(III) and cobalt(II); copper(II) and iron(III) are separated very effectively in a column operation by stepwise elution.     

Nanoporous Lanthanum Tungstate: A Viable Adsorbent for Heavy Metals and Organic Pollutants

Removal of heavy metal cations from synthetic and industrial electroplating effluents by means of mesoporous lanthanum tungstate sorbents was thoroughly investigated. Three types of such sorbents, namely I‐LT, II‐LT and III‐LT, uncalcined and calcined, were produced and characterized by means of X‐ray diffraction, nitrogen sorption isotherms and thermogravimetry analysis (TGA). Results of the experiments for chromium, copper, mercury, iron and lead removal from both synthetic and real industrial wastewater solutions, using these novel sorbents, exhibit promising. Details of this new approach towards wastewater treatment have been discussed and the potentials of technological advancement using mesoporous lanthanum tungstate for environmental purposes addressed. Comparison with the literature shows superiority of the produced adsorbents over reported products.     

Sorption of Cobalt on Modified Silica Gel Materials

Various silica gel materials were chemically modified with imidazole, diaza-18-crown-6 (DA18C6) and dibenzod-18-crown-6 (DB18C6). The degree of functionalization of the covalently attached molecule was calculated from C, H, N analysis and ranged between 0.270 and 0.552 mmol/g (for sorbents with imidazole) and between 0.043 and 0.062 mmol/g (for sorbents with DA18C6 and DB18C6). The degree of functionalization depends on the reflux time and silica gel matrix used. Experimental sorption capacity ranged between 0.038 and 0.228 mmol/g (for sorbents with imidazole) and between 0.019 and 0.050 mmol/g (for sorbents with DA18C6 and DB18C6). Synthesized hexagonal mesoporous silica matrix MCM-41 with uniform pore diameter <40 Å was used too. Change of pore diameters of silica gel support to larger pores should have a positive influence on access of cobalt ion to sorption centers to increase of sorption capacity of sorbents. The sorption kinetics of cobalt and the influence of cobalt concentration, pH of various kinds of silica gel matrix with immobilized imidazole group in static conditions on sorption were measured. The sorption of cobalt in various conditions (pH, contact time of phases) with constant liquid-solid ratio (V/m = 50 ml/g) was studied. The distribution coefficients ranged between 200 and 50 000 ml/g (for imidazole), 85 and 120 ml/g (for DB18C6) and between 230 and 500 ml/g (for DA18C6) according to silica gel matrix used and according to the method of sorbent preparation. pH plays important role in the sorption of cobalt on prepared sorbents with immobilized crown ethers due to protonization of crown ethers. Protons significantly competes to sorption of cobalt in acidic solutions. The influence of presence of other heavy or toxic metals (Hg(II), Cd(II), Mn(II), Zn(II), Cu(II), Fe(III), Cr(III), Al(III) and the influence of sodium and potassium on sorption Co(II) from aqueous solutions was investigated. Sorption of cobalt decreases in order Hg > Cu > Cd > Zn, Fe > Mn > Al, Cr. The presence of sodium and potassium ions at concentration 0.05 mol/l significantly influences on the sorption of cobalt with sorbent with immobilized DB18C6 functional group.     

汞离子天然吸附剂

汞离子是现代工业中剧毒的污染物之一,研究者致力于汞离子高效吸附剂的研制已有多年.本文基于国内外最新研究文献,系统论述了汞离子天然吸附剂如壳聚糖、矿物、微生物及其改性材料等的吸附性能,并详细比较了各种吸附剂的优缺点,指出天然吸附剂来源广泛、价格便宜,尤其是修饰后的壳聚糖吸附性能甚至可以和一些合成吸附剂相媲美.在所报道的天然吸附剂中,引入巯基后的戊二醛交联壳聚糖,对初始浓度为500 mg/L的汞离子的吸附容量可达1 604.7mg/g,属已知的汞离子天然吸附剂中之最.天然汞离子吸附剂在工业废水处理中显示出了广阔的应用前景.     

Synthesis and physicochemical properties of chelating sorbents containing functional groups of N-aryl-3-aminopropionic acids

Two types of chelating sorbents with different types of addition of iminodipropionate groups to a polymeric matrix were synthesized: carboxyethylated aminopolystyrene (sorbent 1) based on linear polystyrene and carboxyethylaminomethylpolystyrene (sorbent 2) based on the copolymer of styrene and divinylbenzene. The ionization constants and concentrations of functional groups of the sorbents (exchange capacity for hydrogen ions) were determined. The sorbents exhibit high selectivity for copper(II) ions with the maximum of sorption from ammonia—acetate buffer solutions lying in a range of pH 5.0–7.5. The time needed for a solution of copper(II)—sorbent system with continuous stirring to reach exchange equilibrium is 3.5 and 2 h for sorbents 1 and 2, respectively. The exchange capacity for copper(II) ions is 2.54 and 0.10 mmol g⁻¹, respectively. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 800–806, May, 2006.     

Synthesis,spectral characterization,redox and antimicrobial activity of Schiff base transition metal(II) complexes derived from 4-aminoantipyrine and 3-salicylideneacetylacetone

A novel tetradentate N₂O₂ type Schiff base, synthesized from 1-phenyl-2,3-dimethyl-4-aminopyrazol-5-one(4-aminoantipyrine) and 3-salicylidene-acetylacetone, forms stable complexes with transition metal ions such as Cu ^II , Ni ^II , Co ^II and Zn ^II in ethanol. Microanalytical data, magnetic susceptibility, IR, UV-Vis.,¹H-NMR, ESR and Mass spectral techniques were used to confirm the structures. Electronic absorption spectra of the complexes suggest a square-planar geometry around the central metal ion. These complexes show higher conductance values, supporting their electrolytic nature. The monomeric nature of the complexes was confirmed from their magnetic susceptibility values. Cyclic voltammogram of the copper(II) and nickel(II) complexes in DMSO solution at 300 K were recorded and the results are discussed. The X-band ESR spectra of the copper complex were recorded and the molecular orbital coefficient values were calculated from the spectra. The in vitro antimicrobial activities of the investigated compounds were tested against bacteria such as Klebsiella pneumoniae, Staphylococcus aureus, Bacillus subtilis and Escherichia coli and fungi like Aspergillus niger and Rhizoctonia bataicola. Most of the metal chelates show higher antimicrobial activity for the above microorganisms than that of the free ligand.     

Equilibrium,kinetics and thermodynamics studies of Cd sorption onto a dithizone-impregnated Amberchrom CG-300m polymer resin

Amberchrom CG-300m, a styrene acrylic ester polymer resin, was studied for the first time as sorbent for metal ion sorption in a solid-phase extraction system. The polymer sorbent was modified via impregnation with dithizone to improve its efficiency. Efficiency of the modified sorbent improved by more than 47%. The loading capacity of the resin is 3.2 mg dithizone per gram of sorbent. The mechanisms of Cd(II) sorption from aqueous solutions are presented. Capacity of the modified resin for Cd(II) was investigated in batch experiments as a function of pH, initial metal ion concentration, temperature and time. Maximum capacity of 0.551 mg Cd(II) per gram of sorbent was achieved. The dimensionless separation factor, 0 < R_L < 1, associated with the Langmuir isotherm (at T = 294 K) signifies sorption of Cd(II) was favorable, as do negative values of free energy of sorption (ΔG) at temperatures exceeding 293 K. Sorption was endothermic (ΔH > 0) while ΔS > 0 reflects the affinity of the sorbent towards Cd(II). The pseudo-second order model proved to be the best fit model for Cd(II) sorption kinetics data. Particle-diffusion models suggest sorption follows film as well as pore diffusion mechanisms.     

Preparation of Sorbents Containing Straetlingite Phase from Zeolitic By-Product and Their Performance for Ammonium Ion Removal

In this study, straetlingite-based sorbents were used for NH₄⁺ ion removal from a synthetic aqueous solution and from the wastewater of an open recirculation African catfish farming system. This study was performed using column experiments with four different filtration rates (2, 5, 10, and 15 mL/min). It was determined that breakthrough points and sorption capacity could be affected by several parameters such as flow rate and mineral composition of sorption materials. In the synthetic aqueous solution, NH₄⁺ removal reached the highest sorption capacity, i.e., 0.341 mg/g with the S30 sorbent at a filtration rate of 10 mL/min and an initial concentration of 10 mg/L of NH₄⁺ ions. It is important to emphasize that, in this case, the Ce/C0 ratio of 0.9 was not reached after 420 min of sorption. It was also determined that the NH₄⁺ sorption capacity was influenced by phosphorus. In the wastewater, the NH₄⁺ sorption capacity was almost seven times lower than that in the synthetic aqueous solution. However, it should be highlighted that the P sorption capacity reached 0.512 mg/g. According to these results, it can be concluded that straetlingite-based sorbents can be used for NH₄⁺ ion removal from a synthetic aqueous solution, as well as for both NH₄⁺ and P removal from industrial wastewater. In the wastewater, a significantly higher sorption capacity of the investigated sorbents was detected for P than for NH₄⁺.     

Adsorption of volatile hydrocarbons on natural zeolite-clay material

This study investigated the vapor-phase sorption of hydrocarbons (HC) of various chemical nature (n-hexane, iso-octane, benzene, toluene and p-xylene) on zeolite-clay material (ZCM) of Tatarsky-Shatrashansky deposit (Tatarstan, Russia). For comparison, we also studied HC sorption on natural high-grade zeolite (Z) of St. Cloud Mine (New Mexico, USA), two local bentonite clays and synthetic zeolite-molecular sieve Ms5A. As a result, sorption capacity of ZCM towards aliphatic and aromatic HC was significantly higher than the sorption capacity of Z but lower than that of clays. In addition, the data showed that HC sorption on ZCM occurs as surface adsorption. The comparison with Ms5A and erionite ZAPS, a natural Mexican zeolite, revealed that both ZCM and Z do not interact as microporous selective sorbents with linear alkanes. The main differences in HC sorption on ZCM and Z were ZCM higher sorption capacity towards both aliphatic and aromatic HC, as well as its lower sorption sensitivity to the type of HC. We found that the reason for these differences is the presence of large amount of clay minerals in ZCM. To summarize, ZCM can be considered as a suitable adsorbent for protection and remediation of HC-contaminated soils.     

Accumulation of cadmium,lead, and nickel by fungal and wood biosorbents

Native fungal biomass of fungiAbsidia orchidis, Penicillium chrysogenum, Rhizopus arrhizus, Rhizopus nigricans, and modified spruce sawdust (Picea engelmanii) sequestered metals in the following decreasing preference pb>Cd>Ni. The highest metal uptake was q_max = 351 mg Pb/gA. orchidis biomass. P.chrysogenum biomass could accumulate cadmium best at 56 mg Cd/g. The sorption of nickel was the weakest always at < 5 mg Ni/g. The spruce sawdust was modified by crosslinking, oxidation to acidic oxoforms, and by substitution. The highest metal uptake was observed in phosphorylated sawdust reaching q_max = 224 mg Pb/g, 56 mg Cd/g, and 26 mg Ni/g. The latter value is comparable to the value of nickel sorption by wet commercial resin Duolite GT-73. Some improvement in metal uptake was also observed after reinforcement of fungal biomass.     

Features of transition metal complexation with hydrogels

The sorption of cobalt(II), copper(II), nickel(II), iron(III), chromium(VI), and manganese(II) by polymeric strongly swelled hydrogels separately and in combination was studied by ESR and inductively coupled plasma atomic emission spectrometry (ICP-AES). The use of such hydrogels as sorbents is the novel area of their application. The features of metal ion complexation and preconcentration depending on sorption conditions are noted.     

Biosorption of Copper and Cadmium in Packed Bed Columns with Live Immobilized Fungal Biomass of <Emphasis Type="Italic">Phanerochaete chrysosporium</Emphasis>

Biosorption of copper (II) and cadmium (II) by live Phanerochaete chrysosporium immobilized by growing onto polyurethane foam material in individual packed bed columns over two successive cycles of sorption–desorption were investigated in this study. Initial pH and concentrations of the metals in their respective solutions were set optimum to each of those: 4.6 and 35 mg·l⁻¹ in case of copper and 5.3 and 11 mg·l⁻¹ for cadmium. The breakthrough curves obtained for the two metals during sorption in both the cycles exhibited a constant pattern at various bed depths in the columns. The maximum yield of the columns in removing these metals were found to be, respectively, 57% and 43% for copper and cadmium indicating that copper biosorption by the immobilized fungus in its column was better than for cadmium. Recovery values of the sorbed copper and cadmium metals from the respective loaded columns by using 0.1 N HCl as eluant was observed to be quite high at more than 65% and 75%, respectively, at the end of desorption in both the cycles. Breakthrough models of bed-depth service time, Adams–Bohart, Wolborska, and Clark were fitted to the experimental data on sorption of copper and cadmium in the columns, and only the Clark model could fit the sorption performance of the columns well over the entire range of ratios of concentrations of effluent to influent, i.e., C/C ₀ for both copper and cadmium biosorption. The kinetic coefficients of mass transfer and other suitable parameters in the system were determined by applying the experimental data at C/C ₀ ratios lower than 0.5 to the other three models.     

Beryllium(II) sorption from aqueous solutions by polystyrene-based chelating polymer sorbents

Optimal parameters of beryllium(II) sorption from aqueous solutions by polystyrene-based sorbents have been studied, namely: optimal sorption acidity (pH_opt), pH providing 50% sorption (pH₅₀), optimal time (τ, min) and temperature of quantitative sorption. The sorption capacities of the sorbents under study (SCSs) for beryllium(II) have also been determined; sorption isotherms have been constructed. The parameters determined for beryllium(II) sorption by chelating polymer sorbents (CPSs) make it possible to select the most efficient sorbent for practical use.     

Strontium(II) sorption by complexing o-hydroxy-azo-o’-hydroxy functionalized polystyrene polymer sorbents

Optimal parameters for strontium(II) complexing and sorption from aqueous solutions by sorbents based on styrene/divinylbenzene copolymers functionalized with a complexing o-hydroxy-azo-o-hydroxy functionality have been studied, namely, pH_opt, 50% sorption pH (pH₅₀), and the time and temperature of quantitative strontium(II) sorption. Strontium(II) sorption capacities have been determined for the sorbents under study; sorption isotherms have been constructed. For a complex formed with polystyrene-o-hydroxy-azo-o’-hydroxy-sulfobenzene, which is an efficient sorbent, the structure has been determined.     

Selective determination of estrogenic compounds in water by microextraction by packed sorbents and a molecularly imprinted polymer coupled with large volume injection-in-port-derivatization gas chromatography-mass spectrometry

A fully automated protocol consisting of microextraction by packed sorbents (MEPS) coupled with large volume injection-in-port-derivatization-gas chromatography–mass spectrometry (LVI-derivatization-GC–MS) was developed to determine endocrine disrupting compounds (EDCs) such as alkylphenols, bisphenol A, and natural and synthetic hormons in river and waste water samples. During method optimization, the extraction parameters as ion strength of the water sample, the MEPS extraction regime, the volume of organic solvent used for the elution/injection step, the type of elution solvents and the selectivity of the sorbents were studied. For optimum in-port-derivatization, 10 μL of the derivatization reagent N,O-bis(trimethylsilyl)triufloroacetamide with 1% of trimethylchlorosilane (BSTFA + 1% TMCS) was used. 17β-Estradiol-molecularly imprinted polymer (MIP) and silica gel (modified with C-18) sorbents were examined for the enrichment of the target analytes from water samples and the obtained results revealed the high selectivity of the MIP material for extraction of substances with estrogen-like structures. Recovery values for most of the analytes ranged from 75 to 109% for the C18 sorbent and from 81 to 103% for the MIP material except for equilin (on C18 with only 57–66% recovery). Precision (n = 4) of the entire analysis protocol ranged between 4% and 22% with both sorbents. Limits of detection (LODs) were at the low ng L⁻¹ level (0.02–87, C18 and 1.3–22, MIP) for the target analytes.     

Strontium(II) sorption by complexing polymeric sorbents with various structures

Optimal conditions for strontium(II) sorption by new complexing polymeric sorbents (CPSs) from aqueous solutions were studied, namely, optimal solution acidity (pH_opt), pH of 50% sorption (pH₅₀), and optimal time and temperature of quantitative sorption. The strontium(II) sorption capacities of the test sorbents (SCSs) were determined, and sorption isotherms were plotted. The strontium(II) sorption parameters determined were used to recognize the most efficient CPSs.     

Synthesis and magneto-structural correlation of a new maleato bridged copper(II) coordination polymer

A one-dimensional (1-D) copper(II) coordination polymer [Cu(maleate)(2,2′-bipyridyl)] _n ·2H₂O has been synthesised. Single crystal X-ray diffraction study reveals that maleate ion bridges two adjacent copper(II) centres along the chain in a syn–anti fashion. A complete cryomagnetic investigation of the title complex correlates well with the distorted square pyramidal geometry of the central copper(II) ion and bridging nature of the maleate. A τ value of 0.26 indicates the distortion towards tbp coordination allowing the magnetic orbital to acquire some character leading to a weak antiferromagnetic interaction having J = −0.26 cm⁻¹. The complex has also been firmly established from several other instrumental techniques like Fourier transform infrared (FT-IR) and EPR spectroscopies.