Nitrate reduction by fluoride green rust modified with copper

Nitrate reduction by the fluoride form of green rust modified with copper (GR-F(Cu)) was investigated using a batch reactor system. The extent of nitrate reduction was measured by measuring the increase in concentration of ammonia, which is the final product of nitrate reduction by GR. This approach was required, because nitrate could be removed from solution by ion exchange without reduction. The rate of ammonium production was investigated over the range of pH 7.8-11. The fastest reaction was achieved at pH 9 when GR was present at a concentration of 0.083M as Fe(II) and 1mM of Cu(II) was added. The rate at pH 9 was enhanced by a factor of 2.5 compared to that at pH 7.8 by comparing the time elapsed to transform all nitrate to ammonium. Kinetics of nitrate reduction by GR-F at pH 7.8 were affected by the concentration of Cu(II) added. The rate constants for ammonium production increased from 0.012 to 1.52h(-1) as Cu(II) additions increased from 0 to 2.5mM, but the reaction rate at 5mM was slightly decreased to 1.25h(-1). The mechanism of enhanced rates of nitrate reduction by addition of Cu(II) could not be fully determined in this study. However, XRD results showed that magnetite was produced in the reaction of Cu(II) and GR-F and SEM shows the production of nano-size particles which were not fully identified in this study. In addition, the concentration of Fe(II) in GR was observed to linearly decrease with concentration of Cu(II) added.     

Copper binding by peat fulvic and humic acids extracted from two horizons of an ombrotrophic peat bog

We studied the binding of Cu(II) to humic acids and fulvic acids extracted from two horizons of an ombrotrophic peat bog by metal titration experiments at pH 4.5, 5.0, 5.5, and 6.0 and 0.1 M KNO3 ionic strength. Free metal ion concentrations in solution were measured using an ion selective electrode. The amounts of base required to maintain constant pH conditions were recorded and used to calculate H+/Cu2+ exchange ratios. The amount of Cu(II) bound to the humic fractions was greater than the amount bound to the fulvic fractions and only at the highest concentrations of metal ion the amount of Cu(II) sorbed by both fractions became equal. The proton to metal ion exchange ratios are similar for all humic substances, with values ranging from 1.0 to 2.0, and decreasing with increased pH. The amount of Cu(II) bound is practically independent of the horizon from which the sample was extracted. The results indicate that the humic substances show similar cation binding behaviour, despite the differences in chemical composition. The copper binding data are quantitatively described with the NICA-Donnan model, which allows to characterize only the carboxylic type binding sites. The values of the binding constants are higher for the humic acids than for the fulvic acids.     

Cadmium in soil solutions from a transect of soils away from a fertiliser bin

The effects of high inputs of phosphate fertiliser on Cd concentrations were studied in soil solutions extracted from topsoils. Soils were sampled along a transect at distances of 1-100 m away from a fertiliser bin. The transect was sampled four times during 1 year. Soil solutions were analysed for Cd, pH, major cations and anions, and other heavy metals (As, Cr, Cu, Pb). For one of the transect samplings, soil total Cd, Cr, Cu, Pb and P were also measured. Cd speciation in the soil solutions was calculated by the GEO-CHEM-PC computer program. Chemical composition varied substantially along the transect, and also between samplings, indicative of seasonal effects and the influence of a fresh application of superphosphate fertiliser during the year. Application of fertiliser decreased soil solution pH and increased the levels of heavy metals in soil solution. Generally, soil total Cd, Cr, Cu, Pb, and P decreased with increasing distance from the fertiliser bin. Correlations between P and the four heavy metals were: P and Cd (R2 = 0.978), P and Cr (R2 = 0.712), P and Pb (R2 = 0.538), P and Cu (R2 = 0.267). Less than 1% of the total Cd in the soil samples was found in the soil solution. The free metal ion Cd2+ accounted for 55-90% of solution Cd. Of the complexed species of Cd, the chloride and sulphate complexes were usually the most important, even when nitrate and phosphate concentrations were relatively high. The presence of As, Cr, Cu and Pb had no effect on Cd speciation.     

Cu(II) removal from aqueous solution using Dogantepe (Amasya) zeolites

This paper investigates the effects of zeolite particle size, zeolite/ solution ratio and stirring time on the performance of zeolites from Dogantepe in removing Cu(II) from aqueous solution to establish optimum operating conditions. The results indicated that the size of the zeolite samples, the concentration of Cu(II) and the zeolite/solution ratio affected the removal efficiencies, whilst the stirring time was found to have no significant effect on the removal efficiencies. The equivalent numbers of sodium, magnesium, calcium and potassium ions passed into the Cu(II) solution were found to be 1.196, 0.208, 0.117 and 0.009 meq/l, respectively, and the passing percentages of these ions were calculated to be 11.27, 2.45, 1.57 and 0.37%, respectively. The removal mechanism of Cu(II) with zeolite samples was mainly ion exchange with a fraction of approximately 65%. The maximum exchange capacities obtained by using Dogantepe zeolites, Yavu zeolites, and synthetic resin were found to be 9.2, 7.0 and 72.7 mg/g, respectively. However, in relatively low concentrations of Cu(II), the differences in the removal efficiencies or exchange capacities obtained for above different three materials were significantly decreased.     

Degradation of aqueous carbon tetrachloride by nanoscale zerovalent copper on a cation resin

Nanoscale zerovalent copper supported on a cation resin was successfully synthesized to enhance the removal of carbon tetrachloride (CCl(4)) from contaminated water. The use of the cation resin as a support prevents the reduction of surface area due to agglomeration of nanoscale zerovalent copper particles. Moreover, the cation resin recycles the copper ions resulting from the reaction between CCl(4) and Cu(0) by simultaneous ion exchange. The decline in the amount of CCl(4) in aqueous solution results from the combined effects of degradation by nanoscale zerovalent copper and sorption by the cation resin; thus the amount of CCl(4) both in aqueous solution and sorbed onto the resin were measured. The pseudo-first-order rate constant normalized by the surface-area and the mass concentration of nanoscale zerovalent copper (k(SA)) was 2.1+/-0.1 x 10(-2)lh(-1)m(-2), approximately twenty times that of commercial powdered zerovalent copper (0.04 mm). Due to the exchange between Cu(2+) and the strongly acidic ions (H(+) or Na(+)), the pH was between 3 and 4 in unbuffered solution and Cu(2+) at the concentration of less than 0.1 mg l(-1) was measured after the dechlorination reaction. In the above-ground application, resin as a support would facilitate the development of a process that could be designed for convenient emplacement and regeneration of porous reductive medium.     

Soil solution dynamics of Cu and Zn in a Cu- and Zn-polluted soil as influenced by gamma-irradiation and Cu-Zn interaction

A pot experiment was conducted to study soil solution dynamics of Cu and Zn in a Cu/Zn-polluted soil as influenced by gamma-irradiation and Cu-Zn interaction. A slightly acid sandy loam was amended with Cu and Zn (as nitrates) either singly or in combination (100 mg Cu and 150 mg Zn kg(-1) soil) and was then gamma-irradiated (10 kGy). Unamended and unirradiated controls were included, and spring barley (Hordeum vulgare L. cv. Forrester) was grown for 50 days. Soil solution samples obtained using soil moisture samplers immediately before transplantation and every ten days thereafter were used directly for determination of Cu, Zn, pH and absorbance at 360 nm (A360). Cu and Zn concentrations in the solution of metal-polluted soil changed with time and were affected by gamma-irradiation and metal interaction. gamma-Irradiation raised soil solution Cu substantially but generally decreased soil solution Zn. These trends were consistent with increased dissolved organic matter (A360) and solution pH after gamma-irradiation. Combined addition of Cu and Zn usually gave higher soil solution concentrations of Cu or Zn compared with single addition of Cu or Zn in gamma-irradiated and non-irradiated soils, indicating an interaction between Cu and Zn. Cu would have been organically complexed and consequently maintained a relatively high concentration in the soil solution under higher pH conditions. Zn tends to occur mainly as free ion forms in the soil solution and is therefore sensitive to changes in pH. The extent to which gamma-irradiation and metal interaction affected solubility and bioavailability of Cu and Zn was a function of time during plant growth. Studies on soil solution metal dynamics provide very useful information for understanding metal mobility and bioavailability.     

阳离子交换膜对Cu~（2＋）离子交换的动力学及热力学研究

对阳离子交换膜离子交换Cu2＋的动力学及热力学现象进行了研究,结果表明：温度25℃,溶液pH=6时,干膜对Cu2＋饱和交换容量为0.506 mmol/g;随Cu2＋初始浓度的升高,离子交换速率常数随之增加;随温度升高,离子交换速率常数随之增加;随转速升高,离子交换速率常数随之增加;离子交换过程与一级反应速率方程拟合结果良好;△G0〈0,表明离子交换反应能自发进行;△H0m〉0,表明的交换反应为吸热反应;△S0〉0,表明交换反应是熵变增加的反应。     

阳离子交换膜对Cu2+离子交换的动力学及热力学研究

对阳离子交换膜离子交换Cu2+的动力学及热力学现象进行了研究,结果表明:温度25℃,溶液pH=6时,干膜对Cu2+饱和交换容量为0.506 mmol/g;随Cu2+初始浓度的升高,离子交换速率常数随之增加;随温度升高,离子交换速率常数随之增加;随转速升高,离子交换速率常数随之增加;离子交换过程与一级反应速率方程拟合结果良好;△G0<0,表明离子交换反应能自发进行;△H0m>0,表明的交换反应为吸热反应;△S0>0,表明交换反应是熵变增加的反应。     

Electrokinetic remediation of a Cu contaminated red soil by conditioning catholyte pH with different enhancing chemical reagents

The effect of enhancement reagents on the efficiency of electrokinetic remediation of Cu contaminated red soil is evaluated. The enhancement agents were a mix of organic acids, including lactic acid+NaOH, HAc-NaAc and HAc-NaAc+EDTA. The soil was prepared to an initial Cu concentration of 438 mgkg(-1) by incubating the soil with CuSO4 solution in a flooded condition for 1 month. Sequential extraction showed that Cu was partitioned in the soil as follows: 195 mgkg(-1) as water soluble and exchangeable, 71 mgkg(-1) as carbonate bound and 105 mgkg(-1) as Fe and Mn oxides. The results indicate that neutralizing the catholyte pH maintains a lower soil pH compared to that without electrokinetic treatment. The electric currents varied depending upon the conditioning solutions and increased with an increasing applied voltage potential. The electroosmotic flow rate changed significantly when different conditioning enhancing reagents were used. It was observed that lactic acid+NaOH treatments resulted in higher soil electric conductivities than HAc-NaAc and HAc-NaAc+EDTA treatments. Ultimately, enhancement by lactic acid+NaOH resulted in highest removal efficiency (81% Cu removal) from the red soil. The presence of EDTA did not enhance Cu removal efficiencies from the red soil, because EDTA complexed with Cu to form negatively charge complexes, which slowly migrated toward the anode chamber retarding Cu2+ transport towards the cathode.     

Soil pH and anion abundance affects on copper adsorption

Copper (Cu) input to agricultural soils results from Cu containing pesticides and or that in soil amendments, such as manure or sewage sludge. Soil and soil solution properties influence the adsorption and desorption of Cu by the soil, which in turn determines its plant availability and/or phytotoxicities. Effects of different anion enrichment in the equilibrium solution on Cu adsorption by different soils (pH range of 6.2-9.9) were investigated in this study over a range of Cu concentrations. With Cu concentrations in the range of 0-100 mg L(-1) in the equilibration solution, 95-99% of applied Cu was adsorbed by all three soils. The adsorption of Cu was similar regardless of using either 0.01 M CaCl2 or Ca(NO3)2 as the equilibration solution. When the Cu concentration in the equilibration solution was further increased in the range of 500-2000 mg L(-1), the adsorption of Cu decreased from 60 to 24% of applied Cu in two soils with pH 6.2-7.9. In a high pH soil (pH=9.9), the Cu adsorption decreased from 77 to 34%. Addition of incinerated sewage sludge (ISS) to a Palouse silt loam soil (pH = 6.2) increased the Cu adsorption as compared to that by unamended soil. This was, in part, due to an increase in the soil suspension pH with ISS amendment.     

Removal of mercury(II) from aqueous solutions using the leaves of the Rambai tree (Baccaurea motleyana)

This study was undertaken to evaluate the biosorption potential of a natural, low-cost biosorbent, Rambai leaves (Baccaurea motleyana), to remove trace amounts of Hg(II) from aqueous solutions. It was found that the amount of Hg(II) biosorption by Rambai leaves increased with initial metal ion concentration, contact time, and solution pH but decreased as the amount of biosorbent increased. The maximum biosorption capacity was 121.95 mg/g for an initial concentration range of 5 to 120 ppb. Overall, kinetic studies showed that the Hg(II) biosorption process followed pseudo-second-order kinetics based on pseudo-first-order and intraparticle diffusion models. Isotherm data revealed that the biosorption process followed both Freundlich and Langmuir isotherms. The value of separation factor, R(L), from the Langmuir equation and rate of biosorption, n, from the Freundlich model also indicated favorable adsorption.     

Sequential removal of heavy metals ions and organic pollutants using an algal-bacterial consortium

The residual algal-bacterial biomass from photosynthetically supported, organic pollutant biodegradation processes, in enclosed photobioreactors, was tested for its ability to accumulate Cu(II), Ni(II), Cd(II), and Zn(II). Salicylate was chosen as a model contaminant. The algal-bacterial biomass combined the high adsorption capacity of microalgae with the low cost of the residual biomass, which makes it an attractive biosorbent for environmental applications. Cu(II) was preferentially taken-up from the medium when the metals were present both separately and in combination. There was no observed competition for adsorption sites, which suggested that Cu(II), Ni(II), Cd(II), and Zn(II) bind to different sites and that active Ni(II), Cd(II) and Zn(II) binding groups were present at very low concentrations. Therefore, special focus was given to Cu(II) biosorption. Cu(II) biosorption by the algal-bacterial biomass was characterized by an initial fast cell surface adsorption followed by a slower metabolically driven uptake. pH, Cu(II), and algal-bacterial concentration significantly affected the biosorption capacity for Cu(II). Maximum Cu(II) adsorption capacities of 8.5+/-0.4 mg g-1 were achieved at an initial Cu(II) concentration of 20 mg l-1 and at pH 5 for the tested algal-bacterial biomass. These are consistent with values reported for other microbial sorbents under similar conditions. The desorption of Cu(II) from saturated biomass was feasible by elution with a 0.0125 M HCl solution. Simultaneous Cu(II) and salicylate removal in a continuous stirred tank photobioreactor was not feasible due to the high toxicity of Cu(II) towards the microbial culture. The introduction of an adsorption column, packed with the algal-bacterial biomass, prior to the photobioreactor reduced Cu(II) concentration, thereby allowing the subsequent salicylate biodegradation in the photobioreactor.     

Removal of bisphenol A and some heavy metal ions by polydivinylbenzene magnetic latex particles

In this study, magnetic polydivinylbenzene latex particles MP_DVB with a core-shell structure were tested for the removal of bisphenol A (BPA), copper Cu(II), lead Pb(II), and zinc Zn(II) from aqueous solutions by a batch-adsorption technique. The effect of different parameters, such as initial concentration of pollutant, contact time, adsorbent dose, and initial pH solution on the adsorption of the different adsorbates considered was investigated. The adsorption of BPA, Cu(II), Pb(II), and Zn(II) was found to be fast, and the equilibrium was achieved within 30 min. The pH 5–5.5 was found to be the most suitable pH for metal removal. The presence of electrolytes and their increasing concentration reduced the metal adsorption capacity of the adsorbent. Whereas, the optimal pH for BPA adsorption was found 7, both hydrogen bonds and π–π interaction were thought responsible for the adsorption of BPA on MP_DVB. The adsorption kinetics of BPA, Cu(II), Pb(II), and Zn(II) were found to follow a pseudo-second-order kinetic model. Equilibrium data for BPA, Cu(II), Pb(II), and Zn(II) adsorption were fitted well by the Langmuir isotherm model. Furthermore, the desorption and regeneration studies have proven that MP_DVB can be employed repeatedly without impacting its adsorption capacity.     

Sorption of tylosin on clay minerals

The equilibrium sorption of tylosin (TYL) on kaolinite and montmorillonite was measured at different solution pH using batch reactor systems. The results showed that all the sorption isotherms were nonlinear and that the nonlinearity decreased as the solution pH increased for a given clay. At a specific aqueous concentration, the single-point sorption distribution coefficient (K_D) of TYL decreased rapidly as the solution pH increased. A speciation-dependent sorption model that accounted for the contributions of the cationic and neutral forms of TYL fit the data well, suggesting that the sorption may be dominated by both ion exchange and hydrophobic interactions. The isotherm data also fit well to a dual mode model that quantifies the contributions of a site-limiting Langmuir component (ion exchange) and a non-specific linear partitioning component (hydrophobic interactions). X-ray diffraction analyses revealed that the interlayers of montmorillonite were expanded due to the uptake of TYL. TYL molecules likely form a monolayer surface coverage.     

Kinetics and mechanism of color removal of methylene blue with hydrogen peroxide catalyzed by some supported alumina surfaces

The catalyzed kinetics of the oxidative mineralization of the cationic dye methylene blue, phenothiazonium, 3,7-bis(dimethylamino)-chloride, with hydrogen peroxide were studied both in buffered and unbuffered solutions. The supported alumina catalysts used were in the form of copper(II), cobalt(II), manganese(II), and nickel(II)-ions. Also, some copper(II)-complexes were used, e.g. copper(II)-ammine ([Cu(amm)4]2+), copper(II)-ethylenediamine ([Cu(en)2]2+) and copper(II)-monoethanolamine ([Cu(mea)2]2+). The reaction is first order with respect to methylene blue. On the other hand, the order with respect to hydrogen peroxide is concentration range dependent. This range depends strongly on the catalyst used. At lower [H2O2], the order was 1 which then decreases with increasing [H2O2] passing through 0 at the maximum rate and finally becomes negative. This phenomenon is parallel to the formation of a colored intermediate on the surface of the catalyst. This suggests that the intermediate has an inhibiting effect on the rate of color removal. Moreover, the rate of the reaction was found to be strongly dependent on the pH of the solution and its ionic strength. It increases with increasing both pH and the concentration of added potassium chloride. Also, the rate of reaction is inhibited in presence of sodium dodecylsulfate anionic surfactant. The repeated use of the different catalysts showed that their catalytic activities are almost unaffected. A reaction mechanism was proposed with the formation of free radicals as reactive intermediates.     

Impacts of pH and ammonia on the leaching of Cu(II) and Cd(II) from coal fly ash

Many coal-fired power plants are implementing ammonia-based technologies to reduce NO(x) emissions. Excess ammonia in the flue gas often deposits on the coal fly ash. Ammonia can form complexes with many heavy metals and change the leaching characteristics of these metals. This research tends to develop a fundamental understanding of the ammonia impact on the leaching of some heavy metals, exemplified by Cu(II) and Cd(II), under different pH conditions. Batch results indicated that the adsorption is the main mechanism controlling Cu(II) and Cd(II) leaching, and high concentrations of ammonia (>5,000 mg/l) can increase the release of Cu(II) and Cd(II) in the alkaline pH range. Based on the chemical reactions among fly ash, ammonia, and heavy metal ion, a mathematical model was developed to quantify effects of pH and ammonia on metal adsorption. The adsorption constants (logK) of Cu(2+), Cu(OH)(+), Cu(OH)(2), and Cu(NH(3))(m)(2+) for the fly ash under investigation were respectively 6.0, 7.7, 9.6, and 2.9. For Cd(II), these constants were respectively 4.3, 6.9, 8.8, and 2.6. Metal speciation calculations indicated that the formation of less adsorbable metal-ammonia complexes decreased metal adsorption, therefore enhanced metal leaching.     

Heavy metals removal from wastewaters using organic solid waste—rice husk

In this study, the removal of Cr(III) and Cu(II) from contaminated wastewaters by rice husk, as an organic solid waste, was investigated. Experiments were performed to investigate the influence of wastewater initial concentration, pH of solution, and contact time on the efficiency of Cr(III) and Cu(II) removal. The results indicated that the maximum removal of Cr(III) and Cu(II) occurred at pH 5–6 by rice husk and removal rate increased by increased pH from 1 to 6. It could be concluded that the removal efficiency was enhanced by increasing wastewater initial concentration in the first percentage of adsorption and then decreased due to saturation of rice husk particles. Also according to achieved results, calculated saturation capacity in per gram rice husk for Cr(III) and Cu(II) were 30 and 22.5 mg?g^?1, respectively. The amounts of Cr(III) and Cu(II) adsorbed increased with increase in their contact time. The rate of reaction was fast. So that 15–20 min after the start of the reaction, between 50 and 60 % of metal ions were removed. Finally, contact time of 60 min as the optimum contact time was proposed.     

Electrochemical monitoring of methylparathion degradation in an acid aqueous medium in presence of Cu(II)

A study was undertaken to determine the effect of Cu(II) in degradation of methylparathion (o,o-dimethyl o,4-nitrophenyl phosphoriotioate) in acid medium. Initial electrochemical characterization of Cu(II) and methylparathion was done in an aqueous medium at a pH range of 2-7. Cu(II) was studied in the presence of different anions and it was observed that its electroactivity depends on pH and is independent of the anion used. Methylparathion had two reduction signals at pH < or = 6 and only one at pH > 6. The pesticide's transformation kinetic was then studied in the presence of Cu(II) in acid buffered aqueous medium at pH values of 2, 4, and 7. Paranitrophenol appeared as the only electroactive product at all three pH values. The reaction was first order and had k values of 5.2 x 10(-3) s(-1) at pH 2, 5.5 x 10(-3) s(-1) at pH 4 and 9.0 x 10(-3) s(-1) at pH 7. It is concluded that the principal degradation pathway of methylparathion in acid medium is a Cu(II) catalyzed hydrolysis reaction.     

Use of natural clinoptilolite to improve water quality: sorption and selectivity studies of lead(II), copper(II), zinc(II), and nickel(II).

Natural clinoptilolite can be used as an ion exchanger for removal of heavy metals and treatment of environmental pollution because of its desirable characteristics of high ion exchange selectivity and resistance to different media. In this work, the potential of natural clinoptilolite from G?rdes mines (West Anatolia, Turkey) for the uptake of lead(II), nickel(II), copper(II), and zinc(II), from their single and mixed ion solutions, was evaluated using the batch method. The mineralogical and chemical properties of the sorption material were carried out by X-ray diffraction, X-ray fluoremetry, scanning electron microscopy, and wet analysis. Contact time, initial solution pH, solid-to-liquid ratio, and initial metal cation concentration were determined as single ion sorption parameters. The silicon/aluminum ratio and the theoretical and equivalent exchange capacities, both in single and mixed solutions, were established. Corresponding adsorption constants and distribution coefficients have been found.     

Detection of copper(II) and zinc(II) binding to humic acids from pig slurry and amended soils by fluorescence spectroscopy

The effect of the consecutive annual additions of pig slurry at rates of 0 (control), 90 and 150 m3 ha(-1) yr(-1) after a 7-year period on the Cu(II) and Zn(II) binding behavior of soil HAs was investigated in a field experiment. A fluorescence titration method and a single site model were used for determining metal ion complexing capacities and stability constants of metal ion complexes of HAs isolated from pig slurry and unamended and amended soils. With respect to control soil HA, pig-slurry HA featured much smaller Cu(II) and Zn(II) binding capacities and stability constants. Pig-slurry application to soil decreased Cu(II) and Zn(II) complexing capacities and binding affinities of soil HA. These effects increased with increasing the rate per year of PS application to soil, and are expected to have a large impact on bioavailability, mobilization, and transport of Cu(II) and Zn(II) ions in pig slurry-amended soils.