Adsorption of heavy metal ions from aqueous solutions by activated carbon prepared from apricot stone

Apricot stones were carbonised and activated after treatment with sulphuric acid (1:1) at 200 degrees C for 24 h. The ability of the activated carbon to remove Ni(II), Co(II), Cd(II), Cu(II), Pb(II), Cr(III) and Cr(VI) ions from aqueous solutions by adsorption was investigated. Batch adsorption experiments were conducted to observe the effect of pH (1-6) on the activated carbon. The adsorptions of these metals were found to be dependent on solution pH. Highest adsorption occurred at 1-2 for Cr(VI) and 3-6 for the rest of the metal ions, respectively. Adsorption capacities for the metal ions were obtained in the descending order of Cr(VI) > Cd(II) > Co(II) > Cr(III) > Ni(II) > Cu(II) > Pb(II) for the activated carbon prepared from apricot stone (ASAC).     

Determination of the biosorption heats of heavy metal ions on Zoogloea ramigera and Rhizopus arrhizus

The biosorption of Fe(III), Cr(VI), Pb(II), Cu(II) and Ni(II) ions on Zoogloea ramigera (activated sludge bacterium) and Rhizopus arrhizus (filamentous fungus) has been studied as a function of initial metal ion concentration and temperature. The applicability of the Langmuir model for each metal-microorganism system has been tested at different temperatures. The enthalpy change for the biosorption process has been evaluated by using the Langmuir constant b, related to the energy of adsorption. Thermodynamic parameters indicate the exothermic nature of Cu(II) and Ni(II) biosorption on both microorganisms. Fe(III), Cr(VI) and Pb(II) biosorption is determined to be an endothermic process since increased binding occurs as the temperature is increased in the range 15-45 degrees C.     

Effects of Municipal Sewage Sludge Doses on the Chlorophyll Contents and Heavy Metal Concentration of Sugar Beet (Beta vulgaris var. saccharifera)

The present study was conducted to assess the suitability of sewage sludge amendment (SSA) in soil for Beta vulgaris var. saccharifera (sugar beet) by evaluating the heavy metal accumulation and physiological responses of plants grown at a 10%, 25%, and 50% sewage sludge amendment rate. The sewage sludge amendment was modified by the physicochemical properties of soil, thus increasing the availability of heavy metals in the soil and consequently increasing accumulation in plant parts. Cd, Pb, Ni, and Cu concentrations in roots were significantly higher in plants grown at 25% as compared to 50% SSA; however, Cr and Zn concentration was higher at 50% than 25% SSA. The concentrations of heavy metal showed a trend of Zn > Ni > Cu > Cr > Pb > Cd in roots and Zn > Cu > Ni > Cr > Pb > Cd in leaves. The only instance in which the chlorophyll content did not increase after the sewage sludge treatments was 50%. There were approximately 1.12-fold differences between the control and 50% sewage sludge application for chlorophyll content. The sewage sludge amendment led to a significant increase in Pb, Cr, Cd, Cu, Zn, and Ni concentrations of the soil. The heavy metal accumulation in the soil after the treatments did not exceed the limits for the land application of sewage sludge recommended by the US Environmental Protection Agency (US EPA). The increased concentration of heavy metals in the soil due to the sewage sludge amendment led to increases in heavy metal uptake and the leaf and root concentrations of Ni, Zn, Cd, Cu, Cr, Pb, and Zn in plants as compared to those grown on unamended soil. More accumulation occurred in roots and leaves than in shoots for most of the heavy metals. The concentrations of Cd, Cr, and Pb were more than the permissible limits of national standards in the edible portion of sugar beet grown on different sewage sludge amendment ratios. The study concludes that the sewage sludge amendment in the soil for growing sugar beet may not be a good option due to risk of contamination of Cr, Pb, and Cd.     

Synthesis and characterisation of anthracene-based fluorophore and its interactions with selected metal ions

An anthracene-based novel ligand (L), 9,10-bis((4,6-dimethylpyrimidin-2-ylthio)methyl)anthracene, was synthesised and fully characterised. Interactions of the ligand with selected metal ions, Hg(II), Cu(II), Ag(I), Pb(II), Zn(II), Ni(II), Co(II), and Cr(III), were spectroscopically investigated. Of the examined metal ions, both Hg(II) and Cu(II) showed responses in both UV-Vis and fluorescent spectroscopy towards the ligand in acetonitrile solution. Spectroscopic titration indicated that the ligand forms complexes with the two metal ions in 1:1 and 1:2 ratios, respectively. DFT calculations revealed that Hg(II) binds possibly with two pairs of donor-set {SN} of the ligand to form a mononuclear complex in a distorted planar geometry whereas Cu(II) forms likely a binuclear complex in a tetrahedral geometry in which each Cu(II) is further coordinated with possibly two acetonitrile molecules.     

Use of silica-immobilized humin for heavy metal removal from aqueous solution under flow conditions

Humin extracted from Sphagnum peat moss was immobilized in a silica matrix and column experiments were performed in order to evaluate the removal and recovery of metal ions from aqueous solution under flow conditions. These experiments also allowed testing the recycling capacity of the column. Single-element solutions of Cu(II) and Pb(II), and a multi-metal solution containing Cd(II), Cu(II), Pb(II), Ni(II), and Cr(III) were passed through the columns at a flow rate of 2 ml/min. A 0.5 M sodium citrate solution was used as the stripping agent in the metal-ion recovery process. Humin immobilized in the silica matrix exhibited a similar, and in some cases, even a higher capacity than other biosorbents for the removal of metal ions from aqueous solutions under flow conditions. The sodium citrate was effective in removing Cu(II), Pb(II), Cd(II), and Ni(II) from the metal saturated column. The selectivity of the immobilized biomass was as follows: Cr(III)>Pb(II)>Cu(II)>Cd(II)>Ni(II). This investigation provides a new, environmentally friendly and cost-effective possibility to clean up heavy-metal contaminated wastewaters by using the new silica-immobilized humin material.     

Biosorption of Pb(II) and Cu(II) by activated sludge in batch and continuous-flow stirred reactors

Biosorption of Pb(II) and Cu(II) ions in single component and binary systems was studied using activated sludge in batch and continuous-flow stirred reactors. In biosorption experiments, the activated sludge in three different phases of the growth period was used: growing cells; resting cells; dead or dried cells. Because of the low adsorption capacity of the non-viable activated sludge especially in the case of Pb(II) ions, biosorption of the Cu(II) and Pb(II) ions from the binary mixtures was carried out by using the resting cells. The biosorption data fitted better with the Freundlich adsorption isotherm model. Using a mathematical model based on continuous system mass balance for the liquid phase and batch system mass balance for the solid phase, the forward rate constants for biosorption of Pb(II) and Cu(II) ions were 0.793 and 0.242 1 (mmolmin)(-1), respectively.     

重金属离子对黑斑蛙胚胎及蝌蚪的毒性影响

本文研究了5种重金属对黑斑蛙胚胎期及蝌蚪期的毒性作用,结果表明,各重金属离子对胚胎期中的孵化期和开口期毒性较大,其余各期毒性较小。各重金属离子对胚胎的毒性顺序为Hg     

Sorption of Cr(VI), Cu(II) and Pb(II) by growing and non-growing cells of a bacterial consortium

This paper reports the sorption of three metallic ions, namely Cr(VI), Cu(II) and Pb(II) in aqueous solution by a consortium culture (CC) comprising an acclimatised mixed bacterial culture collected from point and non-point sources. Metal sorption capability of growing and non-growing cells at initial pH of between 3 and 8 in the 1-100mg/L concentration range were studied based on Q(max) and K(f) values of the Langmuir and linearised Freundlich isotherm models, respectively. Maximal metal loading was generally observed to be dependent on the initial pH. Growing cells displayed significant maximal loading (Q(max)) for Pb(II) (238.09 mg/g) and Cu(II) (178.87 mg/g) at pH 6 and at pH 7 for Cr(VI) (90.91 mg/g) compared to non-growing cells (p < 0.05). At the pH range of 6-8, growing cells showed higher loading capacity compared to non-growing cells i.e. 38-52% for Cr, 17-28% for Cu and 3-17% for Pb. At lower metal concentrations and at more acidic pH (3-4) however, non-growing cells had higher metal loading capacity than growing cells. The metal sorption capacity for both populations were as follows: Pb(II) > Cu(II) > Cr(VI).     

Impact of Pyrolysis Treatment on Heavy Metals in Sediment

This paper describes a laboratory study that examined the effect of pyrolysis treatment on the behavior of Hg, Cr, Zn, Pb, Cu and Cd in a stream sediment. The influences of pyrolysis on the evaporation, sequential extraction and leaching behavior of these metals were investigated. Cr, Zn, Pb and Cu were retained quantitively in the solid residue at temperatures up to 800°C while mercury and cadmium were completely or partially evaporated. The metal form distribution in the sludge samples was determined by the sequential extraction procedure. The procedure revealed that as a consequence of pyrolysis, the metals were more strongly fixed in the treated sediment, as could be seen by the decrease with temperature of the first two sequential-extracted fractions and increase of the residue fraction. The leaching results showed that the quantities of the studied metals leached in the two pyrolysis samples were lower than those in the untreated sediment. The amounts of metals leached from the pyrolysis residues correlated significantly with the first extracted fraction (exchangeable fraction).     

METAL‐INDUCED REACTIVE OXYGEN SPECIES PRODUCTION IN CHLAMYDOMONAS REINHARDTII (CHLOROPHYCEAE)1

Toxic effects of metals appear to be partly related to the production of reactive oxygen species (ROS), which can cause oxidative damage to cells. The ability of several redox active metals [Fe(III), Cu(II), Ag(I), Cr(III), Cr(VI)], nonredox active metals [Pb(II), Cd(II), Zn(II)], and the metalloid As(III) and As(V) to produce ROS at environmentally relevant metal concentrations was assessed. Cells of the freshwater alga Chlamydomonas reinhardtii P. A. Dang. were exposed to various metal concentrations for 2.5 h. Intracellular ROS accumulation was detected using an oxidation‐sensitive reporter dye, 5‐(and‐6)‐carboxy‐2′,7′‐dihydrodifluorofluorescein diacetate (H₂DFFDA), and changes in the fluorescence signal were quantified by flow cytometry (FCM). In almost all cases, low concentrations of both redox and nonredox active metals enhanced intracellular ROS levels. The hierarchy of maximal ROS induction indicated by the increased number of stained cells compared to the control sample was as follows: Pb(II) > Fe(III) > Cd(II) > Ag(I) > Cu(II) > As(V) > Cr(VI) > Zn(II). As(III) and Cr(III) had no detectable effect. The effective free metal ion concentrations ranged from 10^?6 to 10^?9 M, except in the case of Fe(III), which was effective at 10^?18 M. These metal concentrations did not affect algal photosynthesis. Therefore, a slightly enhanced ROS production is a general and early response to elevated, environmentally relevant metal concentrations.     

Phytoextraction capacity of the Chenopodium album L. grown on soil amended with tannery sludge

The metal accumulation potential of Chenopodium album L. grown on various amendments of tannery sludge (TS) was studied after 60 days of sapling planted. The analysis of the results showed that the levels of pH, cation exchange capacity, organic carbon, organic matter and DTPA extractable metals (except Mn) of amendments increased by the addition of tannery sludge ratio. Shoot length of the plant increased by the addition of sludge, whereas, no marked change was observed in root length, fresh and dry weight of the plant. Accumulation of the metals in the plants was found in the order; Fe > Mn > Zn > Cr > Cu > Pb > Ni > Cd. Translocation of toxic metals (Cr, Pb, Cd) in different parts of the tested plant was found in the order; leaves > stems > roots. An increase in the photosynthetic pigments, carotenoid and leaf protein contents of the plants were found to increase with increase in sludge amendments. Correlation analysis between metal accumulation in the plants with DTPA extractable metals emphasized that Mn, Ni, Cr, Pb and Cd showed positive correlation (p < 0.05), whereas, Fe, Zn and Cu showed negative correlation. Transfer factor analysis emphasized that 10% TS amendments were suitable for phytoextraction of Cr. Overall analysis of the data exhibited that the plants may be used for phytoextraction of Cr from tannery waste contaminated soil as most of the metal was accumulated in harvestable part which is a matter of serious concern, whenever used for edible purposes.     

Role of the Ca-pectates on the accumulation of heavy metals in the root apoplasm

In order to better understand the processes that regulate the accumulation in the apoplasm of heavy metals and their mobilization by the plant metabolites it is essential to study the mechanisms that regulate the interactions between metal ions and pectins. In such a context, the sorption of Cd(II), Zn(II), Cu(II) and Pb(II) from single and multi-metal solutions, by a Ca-polygalacturonate gel with a degree of esterification of 18.0 (PGAM₁) and 65.5% (PGAM₂) was studied in the 3.0–6.0 pH range in the presence of CaCl₂ 2.5 mM. The sorption of Cr(III) from single metal solution was also considered. The results show that the amount of each metal ion sorbed increases with increasing the initial metal ion concentration and pH. The data from the single metal solution tests show that at pH 6.0 the affinity of the metal ions towards the PGAM₁ matrix follows the order: Cr(III) > Cu(II) ? Pb(II) ? Zn(II) ? Cd(II). The simultaneous sorption of the bivalent metal ions by the PGAM₁ gels indicates that Pb(II) is selectively sorbed. The FT-IR spectra show that the carboxylate groups are mainly responsible for the metal ion coordination. The ability of PGAM₂ to accumulate Cr(III), Cu(II), and Pb(II) was lower than that found in the PGAM₁ systems whereas the sorption of Zn(II) and Cd(II) was negligible.     

Application of Freundlich and Langmuir models to multistage purification process to remove heavy metal ions by using Schizomeris leibleinii

The adsorption of iron(III), lead(II) and cadmium(II) ions onto Schizomeris leibleinii, a green alga, was studied with respect to initial pH, temperature, initial metal ion and biomass concentration to determine the optimum adsorption conditions. Optimum initial pH for iron(III), lead(II) and cadmium(II) ions were 2.5, 4.5 and 5.0 at optimum temperature 30°C, respectively. The initial adsorption rates increased with increasing initial iron(III), lead(II) and cadmium(II) ion concentrations up to 100, 100 and 150 mg l⁻¹, respectively. The Freundlich and Langmuir adsorption isotherms were developed at various initial pH and temperature values. The adsorption of these metal ions to S. leibleinii was investigated in a two-stage mixed batch reactor. The residual metal ion concentrations (C_eq) at equilibrium at each stage for a given ‘quantity of dried algae (X₀)/volume of solution containing heavy metal ion (V₀)’ ratio were calculated using Freundlich and Langmuir isotherm constants. The experimental biosorption equilibrium data for iron(III), lead(II) and cadmium(II) ions were in good agreement with those calculated by both Freundlich and Langmuir models. The adsorbed iron(III), lead(II) and cadmium(II) ion concentrations increased with increasing X₀/V₀ ratios while the adsorbed metal quantities per unit mass of dried algae decreased.     

Potential utilisation of sewage sludge and paper mill waste for biosorption of metals from polluted waterways

The adsorption of cadmium, copper(II), lead and zinc ions from aqueous solution by sewage sludge, paper mill waste (PMW) and composted PMW was investigated along with the influence of pre-treatment on composted PMW. Langmuir adsorption isotherms were fitted where appropriate. Sewage sludge was the most effective biosorbent of the waste products for all metal ions examined, adsorbing, for example, up to 39.3 mg/g of Pb at an initial concentration of 77.8 mg/l. PMW was a less effective biosorbent than sewage sludge. However, it was found that composting the PMW resulted in an increase in metal uptake capacity and both sewage sludge and composted PMW have potential for low-cost remediation of high leachate wastewaters. The desorption of metal ions from PMW compost was most effective using 0.1 N H2SO4 and 1 mM nitrilotriacetic acid (NTA).     

Selective adsorption of apoferritin on immobilized Fe(III): demonstration of Fe(III) binding sites

Immobilized metal ion affinity chromatography has been used to demonstrate and partially characterize Fe(III) binding sites on apoferritin. Binding of Fe(III) to these sites is influenced by pH, but not affected by high ionic strength. These results suggest that both ionic and coordinate covalent interactions are important in the formation of the Fe(III): apoferritin complex. This is, to our knowledge, the first demonstration of direct Fe(III) binding to apoferritin. Other immobilized metal ions, including Zn(II), Ni(II), Cu(II), Cr(III), Co(II), and Tb(III), displayed little or no adsorption of apoferritin. The analytical technique of immobilized metal ion affinity chromatography also shows great promise in the purification of apoferritin, ferritin, and other iron-binding proteins.     

Heavy metal content of sediments in the Calcasieu River/Lake Complex,Louisiana

The heavy metals Cd, Cr, Cu, Pb, Hg, Ag, and Zn, and the metalloid As were measured in surface sediments at permanent stations located in the Calcasieu River/Lake Complex. The relationships among metal concentrations in different areas of the system were investigated to determine sources, source strength, and transport. The point-source inputs of heavy metals were assumed to be industrial outfalls (Bayou d'Inde) and sewage outfalls (Bayou d'Inde and Contraband Bayou). Although these inputs have not seriously affected the entire river/lake system, stressed regions exist within each bayou.The background levels of arsenic and heavy metals were: 0.60 (As), 0.3 to 1.4 (Cd), 25 (Cr), 10 (Cu), 15 (Pb), < 0.05 (Hg), 0.07 (Ag), and 40 mg kg^–1 (Zn). Stations near sewage outfalls and industrial outfalls had increased metal concentrations above these background levels, but the increases were restricted to the regions near the outfalls. The metals discharged into the bayous were not being transported to the remainder of the river/lake complex.     

Movement of water and heavy metals (Zn, Cu, Pb and Ni) through sand and sandy loam amended with biosolids under steady-state hydrological conditions

New guidelines for using biosolids in UK agriculture favour the use of enhanced treated biosolids, such as dried and composted cakes, due to concerns about the potential for transfer of pathogens into the food chain. However, there is a need to ensure that their use is environmentally acceptable and does not increase the risk to potable water supplies or the food chain from other contaminants such as heavy metals and xenobiotic organic chemicals. The objective of this study was to determine whether the use of composted and dried mesophilic anaerobically digested dewatered (MADD) biosolids would increase the risk of heavy metal leaching from cultivated horizons when compared to more conventionally used MADD cake. Three biosolids (MADD sewage sludge cake - fresh, dried and composted) were mixed with a sand (typic quartzipsamments, %OM = 3.0, pH = 6.5) or a sandy loam (typic hapludalf, %OM = 4.8, pH = 7.6) at an application rate equivalent to 250 kg N/ha/y resulting in loadings of approximately Zn: 6 microg, Cu: 2 microg, Pb: 5 microg and Ni: 0.2 microg/g of soil dry weight basis. These amended soils were repacked into columns (0.4 m by 0.1 m internal diameter) and leaching of Zn, Cu, Pb and Ni was investigated following application of two 24 h simulated rainfall events of 4.5 mm/h. Water balance data and the use of conservative tracers (Cl- and Br ) showed that the hydrological regimes of each core were comparable and, thus, unlikely to account for differences in metal leaching observed. Although no significant difference (P = 0.05) was observed between biosolid amended and control soils, those amended with composted sludge consistently gave higher loss of all metals than did the control soils. Total losses of metals from compost amended soil over the two rainfall events were in the ranges, Zn:20.5-58.2, Cu:9.0-30.5, Pb:24.2-51.2 and Ni:16.0-39.8 microg metal/kg amended soil, compared with Zn:16.4-41.1, Cu:6.2-25.3, Pb:16.9-41.7, and Ni:3.7-25.4 microg metal/kg soil from the control soils. Losses of Zn, Cu, Pb and Ni from fresh MADD cake amended soils (19.8-41.3, 3.2-25.8, 21.6-51.6 and 7.6-36.5 microg metal/kg amended soil, respectively) and from dry MADD cake amended soils (10.7-36.7, 1.8-23.8, 21.2-51.2 and 6.8-39.2 microg metal/kg amended soil, respectively) were similar to the controls. Generally, quantities of metals leached followed the order Zn = Pb > Cu > Ni, which was consistent with the levels of metals in the original sludge/soil mixtures. These results suggest that composting or drying MADD biosolids is unlikely to increase the risk of groundwater contamination when compared to the use of MADD cake; therefore, the changes in UK sludge use in agriculture guidelines are satisfactory in this respect.     

Copper flotation waste from KGHM as potential sorbent for heavy metal removal from aqueous solutions

Sorption affinity of copper flotation waste from KGHM toward Cd(II), Cr(III), Cu(II), and Pb(II) ions was investigated in this work. Batch sorption studies, using single-element synthetic aqueous solutions at various pH (2–12), contact time (10–300 min), initial concentration (100–5000 mg dm^?3; 1–100 mg dm^?3 for Cd(II)) and adsorbent dose (25–200 g dm^?3), were performed. Bonding strength of adsorbed metals was tested from the degree of desorption. The maximum metal removal was observed at pH 5–8, ≥120 min reaction time, and 25 g dm^?3 adsorbent dose. Maximum sorption capacities of studied material were 41.6, 58.8, and 83.8 mg g^?1 for Cr(III), Cu(II), and Pb(II), respectively, for 5000 mg dm^?3 initial concentration, and 0.86 mg g^?1 for Cd(II) for initial concentration of 50 mg dm^?3. Sorption isotherms were very well fitted to Langmuir (Cd, Cr, Pb) and Freundlich (Cu) models. Sorption kinetics was nearly ideally fitted to pseudo-second-order kinetic model. Desorption studies showed that most of Cr(III) (98.5%) and Pb(II) (67.3%) ions remained bound to the surface, indicating that the chemisorption dominated as a controlling process. On the other hand, mostly desorbed were Cd(II) (98.5%) and Cu(II) (90.3%) ions, which indicated that processes like physisorption or precipitation were prevailing.     

Study of the mutagenicity of metal derivatives with Salmonella typhimurium TA102

The mutagenic potential of 16 metal derivatives was studied with a new mutant of Salmonella typhimurium, the strain TA102 (Levin et al., 1983). Some of these compounds are known as carcinogens (As, Cr VI, Cd, Ni) or suspected carcinogens in man (Pb, Hg), others are known as non-carcinogens (Cr III, Al, Cu, Mn, Fe). Among these 16 derivatives, only the two Cr(VI) compounds are strong mutagens (K2Cr2O7 or K2CrO4).     

Heavy metal contamination in water,soil, and milk of the industrial area adjacent to Swan River,Islamabad, Pakistan

Trace heavy metals such as Cr(III), Ni(II), Cd(II), Zn(II), Pb(II), and Cu(II) are hazardous pollutants and are rich in areas with high anthropogenic activities. Their concentrations were analyzed using atomic absorption spectroscopy, and it was found that their concentrations were several fold higher in downstream Swan River water samples of the Kahuta Industrial Triangle as compared to upstream. Heavy metal soil concentrations taken from the downstream site were 149% for Cr, 131% for Ni, 176% for Cd, 139% for Zn, 224% for Pb, and 182% for Cu when compared to samples from the upstream site. Quantitative analysis concluded that these metals were higher in milk samples collected from downstream as compared to the samples from upstream water-irrigated sites. The order of metal in milk was as Zn > Cr > Cu > Cd > Pb = Ni. Heavy metal contaminations may affect the drinking water quality, food chain, and ecological environment. It was also suggested that the toxicity due to such polluted water, soil, and milk are seriously dangerous to human health in future.