Sorption studies of Zn(II)- and Cd(II)ions from aqueous solution on treated sawdust of sissoo wood

Sawdust, an inexpensive material, has been utilized as an adsorbent for the removal of Zn(II)- and Cd(II)ions from aqueous solution. The effects of time of equilibrium, pH, temperatures and dosage of the adsorbent on the removal of Zn(II)- and Cd(II)ions have been studied. The equilibrium nature of Zn(II)- and Cd(II)ions adsorption at different temperatures (25–60 °C) has been studied. The percent adsorption of Zn(II)- and Cd(II)ions increased with an increase in pH, temperature and dosage of treated sawdust. The applicability of the Langmuir isotherm suggests the formation of monolayer coverage of Zn(II)- and Cd(II)ions at the surface of the adsorbent. The thermodynamic parameters like free energy, enthalpy and entropy changes for the adsorption of Zn(II)- and Cd(II)ions has also been computed and discussed. The heat of adsorption [ΔH=17.706 kJmole^-1 for Zn(II) and ΔH=16.949 kJmole^-1 for Cd(II)] implied that the adsorption was an endothermic adsorption. The sawdust was found to be a metal adsorbent as effective as activated carbon.     

Sorption of aromatic organic contaminants by biopolymers: effects of pH, copper (II) complexation, and cellulose coating

Sorption of hydrophobic organic compounds (HOCs) (i.e., pyrene, phenanthrene, naphthalene, and 1-naphthol) by original and coated biopolymers was examined. Lignin yielded nonlinear isotherms due to its glassy character. Except for pyrene, cellulose showed linear isotherms for other compounds, indicating a partitioning dominant mechanism. Sorption of 1-naphthol by lignin decreased with increasing pH, attributed to both the increased pi e theta-pi e theta repulsion and weakened hydrogen bonds, while the affinity reduction of cellulose for 1-naphthol with increasing pH resulted from only the decrease in H-bonding due to its absence of benzene ring. Complexation of lignin with Cu2+ increased the sorption affinity for phenanthrene (2.6 times) and slightly enhanced its isotherm nonlinearity. For 1-naphthol, lignin-Cu2+ complex had a much higher sorption capacity (7 times)than the original lignin, accompanied bythe increased isotherm nonlinearity. Cellulose-coated lignin showed increased sorption affinity and more pronounced nonlinearity for 1-naphthol than the lignin-Cu2+ complex. In comparison, cellulose coating exhibited little effect on sorption affinity for phenanthrene relative to the lignin-Cu2+ complex. Isotherm nonlinearity of coated lignins increased with increasing cellulose coating, indicating more condensed domains produced, supported by an increase (from 68.9 degrees C for the original lignin to 82.4 degrees C for the highest cellulose coating level) in glass transition temperature (Tg). Results of this study highlightthe importance of structure, polarity, surface O-containing functional groups, and surface charges of biopolymers in controlling HOC sorption.     

Removal of Cd(II) ions by oxidized coconut coir

Biosorption potential of oxidized coconut coir (OCC) for removal of Cd(II) from aqueous medium at batch and column level was studied. Lignin and cellulose groups of coir were modified to acidic groups. Optimum biosorption was observed at pH 6. Isotherm data revealed that Langmuir gives best fit for experimental results with maximum adsorption capacity of 12.35 mg/g compared to unmodified coconut coir (5.29 mg/g). The column experiments were conducted as a function of flow rate, bed height, and influent Cd(II) concentration. Biosorption has best performance at 10 mg/L inlet concentration, 5 ml/min flow rate and 7 cm bed height.     

Sequential fluorescent determination of copper (II) and cobalt (II) in food samples by flow injection analysis

Copper (II) can react with a new fluorescence reagent, 5-(4-chlorophenylazo)-8-aminoquinoline (APAQCL), forming a fluorescence product only in slightly acidic medium, while the fluorescence product of cobalt (II) with APAQCL forms only in basic medium and in the presence of H₂O₂. Based on the difference of the reaction between cobalt (II) and copper (II) with APAQCL, a new flow injection method for the sequential determination of cobalt and copper in binary mixtures by use of a fluorimetric detector and APAQCL as reagent was proposed. Linear calibration graphs were obtained over the concentration range 0.010–1.20 (μg/ml) of cobalt (II) and 0.050–5.00 (μg/ml) of copper (II) with the detection limit of 0.0030 (μg/ml) of cobalt (II) and 0.010 (μg/ml) of copper (II), respectively. The applicability of the method to the sequential determination of cobalt (II) and copper (II) in food samples was demonstrated by investigating the potential interference and by the analysis of synthetic mixtures of copper (II) and cobalt (II). The method was successfully applied to the determination of copper and cobalt in food samples.     

Sorption versus biomineralization of Pb(II) within Burkholderia cepacia biofilms

X-ray spectroscopy measurements have been combined with macroscopic uptake data and transmission electron microscopy (TEM) results to show that Pb(II) uptake by Burkholderia cepacia is due to simultaneous sorption and biomineralization processes. X-ray microprobe mapping of B. cepacia biofilms formed on alpha-Al2O3 surfaces shows that Pb(II) is distributed heterogeneously throughout the biofilms because of the formation of Pb "hot spots". EXAFS data and TEM observations show that the enhanced Pb accumulation is due to the formation of nanoscale crystals of pyromorphite (Pb5(PO4)3(OH)) adjacent to the outer-membrane of a fraction of the total population of B. cepacia cells. In contrast, B. cepacia cell suspensions or biofilms that were heat-killed or pretreated with X-rays do not form pyromorphite, which suggests that metabolic activity is required. Precipitation of pyromorphite occurs over several orders of magnitude in [H-] and [Pb] and accounts for approximately 90% of the total Pb uptake below pH 4.5 but only 45-60% at near-neutral pH because of the formation of additional Pb(II) adsorption complexes. Structural fits of Pb L(III) EXAFS data collected for heat-treated cells at near-neutral pH suggest that Pb(II) forms inner-sphere adsorption complexes with carboxyl functional groups in the biofilms.     

Modification of sawdust from pine and beech wood with the succinic anhydride

The aim of this study was to compare the reactivity of the succinic anhydride with the comminuted softwood (Pinus sylvestris L.) and hardwood (Fagus sylvatica L.). By extending the time of reaction (from 4 to 8 hours), products with different degrees of modification were obtained. It was demonstrated that in comparison with beech wood, the wood of Scots pine enters the reaction with the succinic anhydride easier. The results of the thermogravimetric analysis showed that the esterification of softwood and hardwood reduced the initial temperature of their thermal degradation. Wood modified with the succinic anhydride is characterised by poorer thermostability in comparison with natural wood.     

Interaction between Cyanidin 3-glucoside and Cu(II) ions

The interaction between cyanidin 3-glucoside (Cy 3-glc) and Cu(II) in a binary solvent (methanol–water, 1:1, (v/v)) and in a phosphate buffer was studied. It is demonstrated that Cy 3-glc and Cu(II) ions form a complex that is manifested by appearance of a new absorption band. In the complex, the reduction of Cu(II)–Cu(I) and oxidation of Cy 3-glc takes place. The association constant of the complex formation was calculated using the Rose–Drago method. The complex stoichiometry in the binary solvent was 1:1, and the association constant was K = (28,600 ± 2600) M⁻¹. Interaction of Cy 3-glc and Cu(II) ions has two stages “fast” and “slow”. The kinetics of these processes has been investigated. Thermodynamic data for the “fast” process: enthalpy (ΔH^∗) and entropy (ΔE^∗) of activation, were calculated.     

Sorption of copper,zinc and cobalt by oat and oat products

We determined copper, zinc and cobalt sorption by oat and its products under variable pH conditions as well as the content of neutral dietary fiber (NDF) and its fractional composition. Adsorbents in a model sorption system were: oat, dehulled oat, oats bran and oats flakes. Three various buffers (pH 1.8, 6.6 and 8.7) were used as dispersing solutions. Results collected during this study indicate that copper, zinc and cobalt sorption is significantly affected by the type of cereal raw material. Zinc and copper ions are subjected to higher sorption than cobalt ions. Examined metal ions were subjected to high sorption under conditions corresponding to the duodenum environment (pH 8.7( regardless of the kind of adsorbent. A little lower sorption capacity is observed under conditions close to the neutral environment, while the lowest one is found in environment reflecting conditions of stomach juice (pH 1.8). Zinc ions are bound intensively by dehulled oat, while oats flakes bound mostly copper and cobalt, independently on environmental conditions. Contents of dietary fiber in oat, dehulled oat, oat bran and oat flakes were: 40.1, 19.3, 20.3 and 14.3%, respectively. The dominating fraction in all oat products was the fraction of hemicelluloses. The content of remaining fractions varies in dependence on the product.     

Sorption of copper,zinc and cobalt by oat and oat products

We determined copper, zinc and cobalt sorption by oat and its products under variable pH conditions as well as the content of neutral dietary fiber (NDF) and its fractional composition. Adsorbents in a model sorption system were: oat, dehulled oat, oats bran and oats flakes. Three various buffers (pH 1.8, 6.6 and 8.7) were used as dispersing solutions. Results collected during this study indicate that copper, zinc and cobalt sorption is significantly affected by the type of cereal raw material. Zinc and copper ions are subjected to higher sorption than cobalt ions. Examined metal ions were subjected to high sorption under conditions corresponding to the duodenum environment (pH 8.7), regardless of the kind of adsorbent. A little lower sorption capacity is observed under conditions close to the neutral environment, while the lowest one is found in environment reflecting conditions of stomach juice (pH 1.8). Zinc ions are bound intensively by dehulled oat, while oats flakes bound mostly copper and cobalt, independently on environmental conditions. Contents of dietary fiber in oat, dehulled oat, oat bran and oat flakes were: 40.1, 19.3, 20.3 and 14.3%, respectively. The dominating fraction in all oat products was the fraction of hemicelluloses. The content of remaining fractions varies in dependence on the product.     

Sorption of mercuric ion by synthetic nanocrystalline mackinawite (FeS)

Iron sulfides are known to be efficient scavengers of heavy metals. In this study, Hg(II) sorption was investigated using synthetic nanocrystalline mackinawite (a disordered phase) as a function of initial Hg(II) concentration [Hg(II)]0, initial FeS concentration [FeS]0, total chloride concentration CIT, and pH. Hg(II) sorption mechanisms are dependent on relative concentrations of [Hg(II)]0 and [FeS]0 (the molar ratio of [Hg(II)0/[FeS]0). When the molar ratio of [Hg(II)]0/[FeS]o is as low as 0.05, adsorption is mainly responsible for Hg(II) removal, with its contribution to the overall sorption increasing at lower Cl(T). As the molar ratio increases, the adsorption capacity becomes saturated, resulting in precipitation of a sparingly soluble HgS(s). XRD analysis indicates formation of metacinnabar (beta-HgS). Concurrently with HgS(s) precipitation, the released Fe(II) from FeS(s) is resorbed by adsorption at acidic pH and either adsorption or precipitation as Fe (hydr)-oxides at neutral to basic pH. Subsequently, the Fe precipitate formed at neutral to basic pH serves as an adsorbent for Hg(II). Under the conditions where either adsorption or HgS(s) precipitation is dominant, more than 99% of [Hg(II)]0 is immobilized. When the molar ratio of [Hg(II)]0/[FeS]0 exceeds 1, the sulfide concentration is no longer sufficient for HgS(s) precipitation, and formation of chloride salts (Hg2Cl2 at acidic pH and HgCl2 x 3HgO at basic pH) occurs.     

Simple and efficient elimination of copper(II) in sugar-cane spirits

Cachaça is a distilled alcoholic beverage, produced in large quantities in Brazil, from fermentation of sugar cane juice. It is normally distillated in copper stills, which can sometimes cause contamination with this element, at toxic levels. An efficient method to remove copper ions to lower than 5 ppm in such alcoholic distillates, without perceptible changes in organoleptical properties, was herein developed. This method is based on a treatment with either CaCO₃ or MgCO₃, which behave as cationic exchangers.     

Simultaneous separation and preconcentration of Ni(II) and Cu(II) ions by coprecipitation without any carrier element in some food and water samples

A simple and highly sensitive separation and preconcentration procedure, which has minimal impact on the environment, has been developed. The procedure is based on the carrier element‐free coprecipitation of Ni(II) and Cu(II) ions by using 2‐{4‐[2‐(1H‐Indol‐3‐yl)ethyl]‐3‐(4‐chlorobenzyl)‐5‐oxo‐4,5‐dihydro‐1H‐1,2,4‐triazol‐1‐yl}‐N′‐(pyrrol‐2‐ylmethyliden)acetohydrazide (ICOTPA), as an organic coprecipitant. The levels of analyte ions were determined by flame atomic absorption spectrometry. The detection limits for Ni(II) and Cu(II) ions were found to be 0.27 and 0.58 μg L^?1, respectively, and the relative standard deviations for the analyte ions were lower than 4.0%. Spike tests and certified reference material analyses were performed to validate the method. The method was successfully applied for the determination of Ni(II) and Cu(II) ions levels in sea and stream water as liquid samples and red lentil and rice as solid samples.     

Decolorization of kraft bleaching effluent by advanced oxidation processes using copper (II) as electron acceptor

Two advanced oxidation processes (AOPs), TiO2/UV/O2 and TiO2/UV/Cu (II), were used to remove color from a Kraft bleaching effluent. The optimal decoloration rate was determined by multivariate analysis, obtaining a mathematical model to evaluate the effect among variables. TiO2 and Cu (II) concentrations and the reaction times were optimized. The experimental design resulted in a quadratic matrix of 30 experiments. Additionally, the pH influence on the color removal was determined by multivariate analysis. Results indicate that color removal was 94% at acidic pH (3.0) in the presence of Cu (11) as an electron acceptor. Under this condition, the biodegradation of the effluent increased from 0.3 to 0.6. Moreover, 70% of COD (chemical oxygen demand) was removed, and the ecotoxicity, measured by Daphnia magna, was reduced. Photocatalytic oxidation to remove the color contained in the Kraft mill bleaching effluent was effective under the following conditions: short reaction time, acidic pH values, and without the addition of oxygen due to the presence of Cu (II) in the effluent. Moreover, residual Cu (II) was a minimum (0.05.mg L(-1)) and was not toxic to the next biological stage. The experimental design methodology indicated that a quadratic polynomial model may be used to representthe efficiencyfor degradation of the Kraft bleach pulp effluent by a photocatalytic process.     

Adsorption and cosorption of tetracycline and copper(II) on montmorillonite as affected by solution pH

Land application of wastes generated from concentrated animal feeding operations may result in accumulation of tetracyclines (TCs) and metals in agricultural soils. Adsorption of TCs and metals on soil minerals strongly affects their mobility. This study was conducted to evaluate the interaction between tetracycline (TC) and Cu(ll) with regard to their adsorption and cosorption on montmorillonite as affected by solution pH. When solution pH was below 6.5, the presence of TC increased Cu(ll) adsorption on montmorillonite, which could be due to increasing Cu(II) adsorption via the TC bridge, or due to the stronger affinity of TC-Cu(II) complex to the mineral than Cu2+ ion itself. Zeta potential of the montmorillonite significantly decreased after the adsorption of TC, suggesting a strong interaction between TC and montmorillonite. Addition of Cu(ll) ions increased TC adsorption on the mineral in a wide range of pH. The experimental data were well fit with the weighted sum model. The complexes of TC and Cu(II) (CuH2L(2+), CuHL+, and CuL) had higher sorption coefficients (K(d)) than that of the corresponding TC species (H3L+, H2L, and HL-). Increasing adsorption of TC and Cu(II) on montmorillonite as they coexist in the normal pH environment may thus reduce their mobility.     

The influence of Cu(II) ions on physicochemical properties of potato starch oxidised by hydrogen peroxide

The study investigates the influence of Cu(II) ions used as a catalyst on the effectiveness of potato starch oxidation by hydrogen peroxide, and compares the physicochemical properties of the modified starches. The starch was oxidised by H₂O₂ alone and with the addition of Cu(II) ions at three concentrations: 0.1, 0.2 or 0.3 g per 100 g d.m. of starch. The oxidised starches were examined for the content of carboxyl groups, carbonyl groups, amylose and copper, and for water‐binding capacity and water solubility at temperatures of 60 and 80°C. Colour parameters (L*a*b*), susceptibility to retrogradation, thermodynamic characteristics of pasting, intrinsic viscosity and pasting characteristic by RVA were also determined. The results indicate that the concentration of Cu(II) ions added as a catalyst has an effect on both the effectiveness of the oxidation process and the physicochemical properties of starch.     

多肽荧光探针HWEHH对水中铜离子的高通量检测

目的:开发组氨酸—色氨酸—谷氨酸—组氨酸—组氨酸(HWEHH)水溶性荧光探针结合酶标仪实现水中Cu²⁺的高通量检测。方法:通过选择性试验研究荧光探针结合Cu²⁺的特异性;滴定试验确定探针检测Cu²⁺的线性范围以及检测限,样品加标回收探究探针检测水中Cu²⁺的准确度。结果:多肽探针溶液浓度为2μmol/L时,其检测Cu²⁺的线性范围为0～1.5μmol/L,线性方程Y=-1 135.085 7X+2 048.187 6,络合常数为1.3×10⁶ mol/L,检测限为0.036μmol/L,高通量检测的线性范围为0～1.5μmol/L,加标回收率为93.6%～101.9%。结论:HWEHH多肽荧光探针可以实现水溶液中Cu²⁺的高通量检测。