Removal of cadmium(II), lead(II), and chromium(VI) ions from aqueous solution using clay

Removal of cadmium(II), lead(II), and chromium(VI) from aqueous solution using clay, a naturally occurring low-cost adsorbent, under various conditions, such as contact time, initial concentration, temperature, and pH has been investigated. The sorption of these metals follows both Langmuir and Freundlich adsorption isotherms. The magnitude of Langmuir and Freundlich constants at 30°C for cadmium, lead, and chromium indicate good adsorption capacity. The kinetic rate constants (K _ad) indicate that the adsorption follows first order. The thermodynamic parameters: free energy change (ΔG ^o), enthalpy change (ΔH ^o), and entropy change (ΔS ^o) show that adsorption is an endothermic process and that adsorption is favored at high temperature. The results reveal that clay is a good adsorbent for the removal of these metals from wastewater.     

Sorption of cadmium(II) and copper(II) by soil humic acids: temperature effects and sorption heterogeneity

Sorption by humic acids is known to modify the bioavailability and toxicity of metals in soils and aquatic systems. The sorption of cadmium(II) and copper(II) to two soil humic acids was measured at pH 6.0 using ion-selective electrode potentiometric titration at different temperatures. Sorption reactions were studied with all components in aqueous solution, or with the humates in suspension. Adsorption reactions were described using a multiple site-binding model, and a model assuming a continuous log-normal distribution of adsorption constants. Adsorption of Cu²⁺ was more favourable than adsorption of Cd²⁺. The log-normal distribution model provided the closest fit to observations and allowed parameterisation of adsorption data using a mean adsorption constant (log K _μ). Sorption of Cd²⁺ to dissolved humic acids increased slightly in extent and sorption affinity with increasing temperature, but the effect was small (log K _μ 2.96–3.15). A slightly greater temperature effect occurred for sorption of Cd²⁺ to solid-phase humic acids (log K _μ 1.30–2.08). Sorption of copper(II) to both aqueous- and colloidal-phase humates showed more pronounced temperature dependence, with extent of sorption, and sorption affinity, increasing with increasing temperature (log K _μ 3.4–4.9 in solution and 1.4–4.5 in suspension). The weaker adsorption of Cd²⁺ than Cu²⁺, and smaller temperature effects for dissolved humates than suspended humates, suggested that the observed temperature effects had a kinetic, rather than thermodynamic, origin. For any metal-to-ligand ratio, free metal ion concentration, and by inference metal bioavailability, decreased with increasing temperature. The consistency of the data with kinetic rather than thermodynamic control of metal bioavailability suggests that equilibrium modelling approaches to estimating bioavailability may be insufficient.     

Influence of complexation on lead(II) and cadmium(II) percolation through a clay liner

Wastes are usually stocked in waste disposals without any pre-treatment. Runoff waters lead to the formation of leachates containing mineral and organic pollutants. In order to prevent groundwater contamination, a double barrier is placed on the landfill bottom. The first one is an active barrier made up of a draining system and a geomembrane, and the second one, consisting of a clay liner allowing pollutant retention, is considered as a passive system. The aim of this work is to evaluate the complexation impact on the organic and inorganic retention. Percolations on columns filled with clay are performed, which allow a better knowledge of the transfer of metallic pollutants, complexed or not, through a model porous media, considering charge and conditional stability of complexes.     

Influence of complexation on lead(II) and cadmium(II) percolation through a clay liner

Wastes are usually stocked in waste disposals without any pre-treatment. Runoff waters lead to the formation of leachates containing mineral and organic pollutants. In order to prevent groundwater contamination, a double barrier is placed on the landfill bottom. The first one is an active barrier made up of a draining system and a geomembrane, and the second one, consisting of a clay liner allowing pollutant retention, is considered as a passive system. The aim of this work is to evaluate the complexation impact on the organic and inorganic retention. Percolations on columns filled with clay are performed, which allow a better knowledge of the transfer of metallic pollutants, complexed or not, through a model porous media, considering charge and conditional stability of complexes.     

Comparative adsorption of Pb(II) and Cd(II) ions on chestnut shell in aqueous system

In this study, high capacity Chestnut shell, a waste product from the chestnut sugar production industry, was successfully applied to remove Pb (II) and Cd (II) ions from aqueous solutions. Maximum adsorption capacities were found as 541.25?mg/g and 75.86?mg/g for Pb(II), and Cd(II) respectively. Several important parameters influencing the adsorption of Pb(II) and Cd(II) ions such as contact time, pH, temperature and effect of metal concentration were investigated systematically by batch experiments. Langmuir and Freundlich adsorption models were used to describe adsorption isotherms and constants. The thermodynamic parameters, such as standard free energy (ΔG°), standard enthalpy (ΔH°), and standard entropy (ΔS°), of the adsorption process were calculated. The adsorbents were characterised by scanning electron microscopy. It has been observed from the experimental results that in case of both Cd (II) and Pb (II), pseudo 2nd order kinetic model. From the results, Chestnut Shell are considered as an effective, low cost and environmental friendly adsorbent for the removal of Pb (II) and Cd (II) from wastewater.     

Lead(II) and cadmium(II) removal from aqueous solution using processed walnut shell: kinetic and equilibrium study

The biosorption potential of processed walnut shell for Pb(II) and Cd(II) ions from aqueous solutions was explored. The effects of pH, contact time, initial ion concentration, and amount of dried adsorbent were studied in batch experiments. The maximum adsorption was achieved within the pH range 4.0–6.0. The equilibrium data were well fitted by the Langmuir isotherm model. The maximum monolayer adsorption capacities were found to be 32?g?kg^?1 and 11.6?g?kg^?1 for Pb(II) and Cd(II) ions, respectively. Kinetic data were best described by the pseudo-second-order model. The structural features of the adsorbent were characterized by Fourier transform infrared spectroscopy, which confirmed the involvement of hydroxyl (–OH), carboxyl (–COO^–), and carbonyl (C=O) groups in metal sorption. This readily available adsorbent is efficient in the uptake of Pb(II) and Cd(II) ions from an aqueous solution and could be used for the treatment of wastewater streams bearing these metal ions.     

Biosorption of chromium(VI), nickel(II) and copper(II) ions from aqueous solutions using Pithophora algae

The biosorption of heavy metals is considered to be one of the best alternatives for the treatment of wastewater. The metal binding capacity of algae and acid-treated algae is investigated to find out the removal characteristics of Cr(VI), Ni(II) and Cu(II) ions from single metal solutions. Batch experiments are conducted and the study is extended to investigate the effect of pH, amount of adsorbent and adsorbate concentration on the extent of biosorption. The results indicate that the adsorption capacity of algae depends strongly on pH. The maximum adsorption of Cr(VI), Ni(II) and Cu(II) occurs at pH values of 2, 7 and 4.3, respectively. The adsorption process follows first-order kinetic equation. The data obtained are correlated with Freundlich and Langmuir adsorption isotherms.     

Trace-metal detoxification in the ventral caeca of Orchestia gammarellus (Crustacea: Amphipoda)

The talitrid amphipod crustacean Orchestia gammarellus (Pallas) was collected from metal-contaminated (Dulas Bay, Gironde) and control (Millport) sites in the UK and France. Irrespective of site of origin, the amphipods showed the same physiological mechanism of trace-metal detoxification, involving the ventral caeca. Copper was always present in lysosomal residual bodies in the ventral caeca. Following laboratory exposure to zinc and cadmium, the lysosomes usually contained both copper and zinc but cadmium was not detectable. The lysosomal copper concentration is positively correlated to that of sulphur, while the concentration of lysosomal zinc is related to that of phosphorus. Results are interpreted in terms of the differential rates of turnover of metallothioneins chelating copper, zinc or cadmium. Received: 9 February 1999 / Accepted: 2 December 1999     

Suitability of various chemically prepared activated carbons for the removal of copper(II) ions

Studies on the suitability of various chemically prepared activated carbons (CPACs) like straw carbon (SC), sawdust carbon (SDC), dates nut carbon (DNC) and commercial activated carbon (CAC) for the removal of copper(II) ions by adsorption from simulated wastewater have been carried out under batch mode at 30?±?1°C and the results are compared. The percentage removal of Cu(II) ions increased with a decrease in initial concentration, particle size and added electrolytes (ionic strength) and increased with an increase in contact time, dose of adsorbent and initial pH of the solution. The adsorption data were fitted with the Langmuir isotherm. The applicability of the first order kinetic equation viz. Lagergren equation was tested by correlation analysis. The adsorption process is concluded to be a spontaneous, first order reaction, occurring with increased randomness at the solid–liquid interface. Studies on the desorption of Cu²⁺-loaded activated carbons (ACs) were carried out with nitric acid (0.2–1?N). The possibility of reuse of the regenerated ACs in cycle (in cue-one after another) was tested. SC was found to be a suitable adsorbent alternative to CAC among CPACs for the removal of metal ions, in general, and Cu²⁺ ions, in particular.     

The chelation of metal ions by the acylpolyamine toxins from the web-spider Nephilengys cruentata: effects in the intoxication/detoxification of preys

Summary. Orb-web-spiders present a series of different strategies for prey capture, involving the use of different types of silk for web building, the use of adhesive traps in the webs, the secretion of toxic compounds to the spider’s preys in the adhesive coating of the capture web and the biosynthesis of a wide range of structurally related acylpolyamine toxins in their venoms. The polyamine toxins usually block neuromuscular junctions and/or the central nervous system (CNS) of Arthropods, targeting specially the ionotropic glutamate receptors; this way these toxins are used are as chemical weapons to kill / paralyze the spider’s prey. Polyamine toxins contain many azamethylene groups involved with the chelation of metal ions, which in turn can interact with the glutamate receptors, affecting the toxicity of these toxins. It was demonstrated that the chelation of Ni⁺², Fe⁺², Pb⁺², Ca⁺² and Mg⁺² ions by the desalted crude venom of Nephilengys cruentata and by the synthetic toxin JSTX-3, did not cause any significant change in the toxicity of the acylpolyamine toxins to the model-prey insect (honeybees). However, it was also reported that the chelation of Zn⁺² ions by the acylpolyamines potentiated the lethal / paralytic action of these toxins to the honeybees, while the chelation of Cu⁺² ions caused the inverse effect. Atomic absorption spectrometry and Plasma-ICP analysis both of N. cruentata venom and honeybee’s hemolymph revealed that the spider’s venom concentrates Zn⁺² ions, while the honeybee’s hemolymph concentrates Cu⁺² ions. These results are suggesting that the natural accumulation of Zn⁺² ions in N. cruentata venom favors the prey catching and/or its maintenance in the web, while the natural accumulation of Cu⁺² ions in prey’s hemolymph minimizes the efficiency of the acylpolyamine toxins as killing/paralyzing tool.     

Biosorption of Cu (II) ions by indigenous copper-resistant bacteria isolated from polluted coastal environment

The concentrations of copper in water and sediment samples of Cuddalore coastal area, Tamil Nadu, India were examined. The isolation, characterization, screening, and metal sorption capabilities of copper-resistant bacteria (CURB) also were investigated. Biosorption capabilities and growth time varied among the resistant isolates. All isolates reduced more than 80% of copper from copper-treated broth. However, Bacillus cereus CURB-4 strain absorbed more copper ions (99.9%) than other resistant isolates. Changes in structural group position and synthesis of extracellular polysaccharides (EPS) of CURB-4 strain under copper stress and controlled conditions also were examined. Under copper stress condition, CURB-4 produced more EPS (71 ± 0.6%) compared to control conditions (66 ± 0.4%). Fourier transform infrared spectroscopy revealed that the changes in functional group position of EPS were observed in stressed condition. Overall, synthesis of EPS in bacteria is a protective barrier against environmental stress.     

Removal of Cu（ll） ions from aqueous solution by activated carbon impregnated with humic acid

Humic acid （HA） was impregnated onto powdered activated carbon to improve its Cu（II） adsorption capability. The optimum pH value for Cu（II） removal was 6. The maximum adsorption capacity of HAimpregnated activated carbon was up to 5.98mg.g-1, which is five times the capacity of virgin activated carbon. The adsorption processes were rapid and accompanied by changes in pH. In using a linear method, it was determined that the equilibrium experimental data were better represented by the Langmuir isotherm than by the Freundlich isotherm. Surface charges and surface functional groups were studied through zeta potential and FTIR measurements to explain the mechanism behind the humicacid modification that enhanced the Cu（II） adsorption capacity of activated carbon.     

Determination of Au(III) and Pd(II) ions by flame atomic absorption spectrometry in some environmental samples after solid phase extraction

A simple and sensitive solid phase extraction method was developed for simultaneous separation and preconcentration of gold and palladium ions with N-(4-methylphenyl)-2-{[(4-phenyl-5-pyridine-4-yl-4H-1,2,4-triazol-3-yl)thio]acetyl}hydrazine carbo thioamide complex on Amberlite XAD-1180 resin before their determination by flame atomic absorption spectrometry. Some analytical parameters such as HNO₃ concentration of the sample solution, amount of complexing agent, sample volume, eluent type and volume, effects of foreign ions and adsorption capacity of the resin were investigated for quantitative recovery of gold and palladium ions. The effects of some anions and cations were also examined. Under optimum conditions, the detection limits for gold and palladium ions were found to be 0.29 and 0.19 μg L^?1, respectively. The preconcentration factor for gold and palladium was 250. After being validated by standard addition and analysis of standard reference material, the procedure was successfully applied to the analysis of sea and stream water, anodic slime, gold ore, soil and electronic waste.     

Manganese in natural waters II. Evidence for microbiological oxidation of Mn (II)

The oxidation of Mn(II) to Mn(IV) in natural waters has been investigated. Various hypotheses have been put forward for the mechanism of oxidation of Mn(II) of which only biological oxidation was found to occur in the aquatic system studied. The effect of adsorption, usually associated with the oxidation of Mn(II) was not observed in our study. The oxidation kinetics can be divided into three periods. The first period is the induction time corresponding to the growth of microorganisms that act as oxidising agents for Mn² _aq ⁺. During this stage Mn² _aq ⁺ remains constant. This period is followed by a decrease in Mn² _aq ⁺ concentration following zero order rate law. Finally in the third period the decrease in Mn² _aq ⁺ follows a first order rate law. The microorganisms acting as oxidising agents for Mn(II) have been identified to be filamentous Gallionella type bacteria and Leptothrix discophora.     

The biology of colonial hydroids. II. The morphology and ultrastructure of the medusa of Eirene viridula (Thecata-Leptomedusa: Campanulinidae)

The free-swimming medusae of Eirene viridula are typical marine hydroids, with distinct subdivisions into body regions, which were studied by comparison of light and electron microscopy. Particular attention is given to the epithelio-muscular and digestive muscle cells. The epidermis — apart from a few nerve cells and cnidocytes-consists of epitheliomuscular cells. At their bases these cells form a musculature and at the apex many secretory vesicles. In the velum, large expansions of the intercellular space are found. The gastrodermis — apart from the mucous and zymogen cells in the manubrium — consists of digestive muscle cells, the structure of which corresponds in principle to that of the epitheliomuscular cells. In its apex, this type of cells contains both normal coated vesicles and discoidal coated vesicles. In the solid tentacles, the digestive muscle cells form a turgescent vesicular tissue. The central nervous system consists of the exumbrellar, subumbrellar, and gastrodermal nerve rings. They are composed of ganglion cells, their processes, and intraepithelial flagella. The static organs are purely ectodermal statocysts which have only one lithocyte and only one sensory cell.     

Flux of radioactive cadmium through the sea-skater Halobates (Heteroptera: Gerridae)

Uptake of ¹⁰⁹Cd in freshly caught sea-skaters Halobates nereis and H. flaviventris was measured under the influence of abiotic parameters as salinity and stable Cd concentration. After 6 d of accumulation a concentration factor of 8 over the seawater level was reached with no indication for an equilibration. The calculated biological half-life of ¹⁰⁹Cd amounted to 9.3 d. Cadmium uptake from food (wingless Drosophila sp. flies reared on cadmium enriched agar) can be considerable. A large pond-skater Limnogonus fossarum, measured for comparative purposes, accumulated cadmium, but at a much lower rate. The results are discussed with respect to observed natural cadmium concentrations in open ocean sea-skater populations.     

Effects of cadmium on Pontoporeia affinis (Crustacea: Amphipoda) in laboratory soft-bottom microcosms

Laboratory soft bottom microcosms, containing sediment with natural populations of meio-and microfauna and the amphipod Pontoporeia affinis Lindström, were used to investigate chronic effects of cadmium on a typical Baltic Sea benthic community. Temperature, salinity, organic content of the sediment and the life cycles of the amphipods in laboratory control microcosms were in good agreement with conditions in the Baltic Sea. In Experiment 1, P. affinis was exposed to four assayed cadmium concentrations, 0 (control), 6.3, 41 and 127 g Cd·1^-1, for 265 d. At the lowest cadmium concentration (6.3 g Cd·1^-1), the sediment contained about 700 times, and P. affinis about 1 700 times, the water concentration at the end of the experiments. In microcosms without P. affinis, the sediments accumulated less cadmium. Effects on P. affinis embryogenesis were detected after 105 d of exposure in all tested cadmium concentrations. Mortality of juveniles was significantly increased after 265 d of exposure in mean assayed concentrations of 41 and 127 g Cd·1^-1. In Experiment 2, P. affinis was exposed to cadmium in assayed concentrations, 0, 6.5 and 46 g Cd·1^-1 for 460 d. At the lowest water concentration (6.5 g Cd·1^-1), the prolonged exposure did not increase the sediment concentration, which indicates a steady state, while concentrations in P. affinis reached about 3 500 times the lowest water concentration after 460 d. Juvenile P. affinis matured sexually and reproduced normally in all microcosms, but their offspring died in all microcosms with added Cd. This occurred at water concentrations not uncommon in polluted marine areas. The effects are serious in comparison to those found in conventional short-term laboratory experiments with the same concentrations and demonstrate the importance of long-term experiments in ecotoxicology.     

The aggregation pheromone ofIps duplicatus and its role in competitive interactions withI. typographus (Coleoptera: Scolytidae)

Summary Ips duplicatus withI. typographus co-inhabiting Norway spruce (Picea abies (L.) Karst.) would benefit from a pheromone blend distinct from that of the larger competitorI. typographus. GC-MS analysis showed thatI. duplicatus males feeding in the host produced ipsdienol (Id),cis-verbenol (cV),trans-verbenol (tV), myrtenol (Mt), andE-myrcenol (EM) and traces of 2-methyl-3-buten-2-ol (MB).I. duplicatus produced Id in approximately racemic form (48.9-54.5% (+)-(S)-isomer). The amounts of Id and EM released over a 9 day period had a maximum of 250 and 5 ng/h/male, respectively, on day 2. Exposure ofI. duplicatus males to myrcene and -pinene resulted in the production of small amounts of Id, cV, tV, Mt, andtrans-pinocarveol, but not of EM. In laboratory bioassays with walking beetles, the pheromone component Id alone was weakly attractive while EM was inactive, but in binary combination with Id strongly synergized attraction. A combination of EM and Id at a release rate equivalent to 100–200 males was more attractive in the field than 70 unmated males in a spruce log. The addition of myrcene ( a suggested pheromone precursor of Id) to Id did not enhance trap caches, while addition of EM increased catches > 10-fold. Subtracting EM from a blend of Id, EM, cV and MB drastically reduced trap catches while subtraction of cV or MB or both had no significant effect. Addition of EM over a wide concentration range to the synthetic pheromone ofI. typographus did not reduce the attraction of females of this species in the laboratory. A two-species pheromone interaction field test releasingI. typographus pheromone components (MB + cV) at 10–1000 male equivalents (ME) andI. duplicatus pheromone (Id + EM) at 0, 10–1000 ME in all possible combinations showed both positive intraspecific dose-response effects and an interspecific inhibition. Higher release rates of EM appeared to inhibitI. typographus, especially males. In a tree colonization model, the response of the two competing species to their respective pheromones show a good separation during the mass-attack with a small initial cross-attraction. It remains to be shown whether either of the two pheromone systems have in fact evolved in the present sympatry, or if they are an incidental effect of ancestry of these phylogenetically distantIps.     

The role of colonization in determining spatial patterns of Proscoloplos bondi sp. nov. (Orbiniidae: Annelida) in coralline algal turf

We describe Proscoloplos bondi sp. nov., a new species of orbinid polychaete found in coralline algal turf on rocky intertidal shores near Sydney, Australia. We used field sampling to describe P. bondi's patterns of spatial and temporal variation on a number of shores. P. bondi was significantly more abundant in low- than in mid-shore areas (ANOVA, P<0.05), but local populations were extremely variable in space and time. Despite extensive sampling, we did not find evidence of sexual reproduction in P. bondi, but commonly observed worms with regenerating heads and tails, which indicated the importance of asexual reproduction. We, therefore, tested the hypothesis that adult colonization contributes to its patterns of abundance. First, patches of artificial turf were placed near to and away from natural coralline turf and sampled after 2, 4 and 12 months. Generally, populations established themselves more quickly in patches of new habitat directly adjacent to coralline turf than in patches that were isolated. Second, patches of turf were deployed for 2-week periods in low- and mid-shore areas (repeated four times). Proscoloplos bondi were found significantly more often in patches in low-shore areas than in mid-shore areas and at some sites more than others (ANOVA, P<0.05), demonstrating the importance of adult colonization in determining patterns of abundance. Overall, the limited dispersal from spatially and temporally ephemeral populations of P. bondi combined with the patchiness of coralline turfs suggest that metapopulation dynamics may be important in the persistence of P. bondi on rocky shores.Communicated by G.F. Humphrey, Sydney     

Apoptosis in marine sponges: a biomarker for environmental stress (cadmium and bacteria)

The marine demosponge Suberites domuncula is abundantly present on muddy sand bottoms, both in the open sea and in harbors. In the present study it is shown that exposure of S. domuncula to cadmium (CdCl₂) in concentrations ranging from 0.01 to 5.0 g ml⁻¹ for up to 5 d results in apoptotic fragmentation of DNA. Kinetics experiments revealed that after 24 h a significant increase of DNA fragmentation already occurred. Besides cadmium a second stimulus was identified to also cause apoptosis in this species, namely exposure to heat-treated Escherichia coli. In order to support the finding that both cadmium and E. coli induce apoptosis in the sponge, expression of the apoptotic gene MA-3 was studied. The cDNA, SDMA3, was isolated and found to be 2247 nucleotides long. The deduced amino acid sequence (M_r 50 765) shares high similarity with the corresponding mouse molecule. Like the mouse gene, the sponge MA-3 gene undergoes increased expression in response to apoptotic stimuli. While the specimens remained alive after treatment with cadmium, the sponges treated with E. coli died after approximately 12 d. The E. coli-treated animals started to form gemmules 10 to 12 d after addition of the bacteria. Hence, the process of apoptosis in sponges is triggered by two different pathways, one which is initiated by exogenous factors, e.g. heavy metals, and a second one, caused by endogenous factors, which leads to gemmule formation and a shift of the presumably immortal cells to mortal cells. The latter assumption is supported by the finding that during the process of bacteria-induced apoptosis, which results in the death of the specimens, the activity of the telomerase drops. It is concluded that the cells which appear to be immortal and telomerase-positive undergo apoptosis during the process of gemmule formation. In consequence cells not involved in the production of gemmules become mortal. Based on these data, it is proposed that apoptosis is a suitable biomarker in the bioindicator organism S. domuncula to monitor unfavorable environmental conditions, at least in this animal phylum. Received: 10 November 1997 / Accepted: 6 March 1998