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.     

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     

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.     

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.     

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.     

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.     

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     

Uptake,binding and clearance of divalent cadmium in Glycera dibranchiata (Annelida: Polychaeta)

The bloodworm Glycera dibranchiata Ehlers, 1968 accumulates cadmium through the general body surface and the intestine. Absorption through the gut accounts for cadmium which rapidly binds to coelomic proteins. Intracoelomic injection of ¹⁰⁹Cd demonstrates that cadmium binds readily to hemoglobin and other proteins. The degree of cadmium binding is pH-dependent. The apparent pK of binding sites in body wall and musculature homogenates is 5.39. Cadmium ions injected into the coelom at 7 g g^-1 tissue increase proline incorporation rates into the positively charged hemoglobin (cathode fraction) by 15-fold in 3 days. A 3-fold increase of proline incorporation was observed in the anode hemoglobin fraction over the same time period. Radioactivity in various protein fractions decreases at different rates after injection of ¹⁰⁹Cd. Comparisons between the function of mammalian metallothionein and the coelomic fluid proteins of G. dibranchiata as a detoxification mechanism are discussed.     

The boll weevil (Coleoptera: Curculionidae) feeding process: A simulation model

A model is presented for predicting boll weevil, Anthonomus grandis Boheman, feeding damage to cotton. The model uses appropriate probability theory based on behavioral components of male and nonreproducing female boll weevils and includes the effects of (1) differential feeding site preferences, (2) previous damage to the sites, and (3) individual insect behavior extended to feeding damage caused by a population of insects. The model is sensitive to both crop and insect parameters. An example of how this model can be used in an insect-crop ecosystem simulation is offered.     

The effects of feeding by the black bean aphidAphis fabae Scop. (Homoptera: Aphididae) on copper and cadmium accumulation in broad bean (Vicia faba L.)

Broad beans (Vicia faba L.), cultured hydroponically were supplied with 100 g mL^–1 copper or 50 g mL^–1 cadmium in nutrient solution. Samples of plant material from both nutrient regimes were analysed before and after infestation by the black bean aphid (Aphis fabae Scop.). Heavy aphid infestation resulted in a significant reduction in copper content of shoots in comparison with uninfested plants. A similar, but less well- defined, situation occurred in the case of cadmium.Further investigations examined the effects of different levels of aphid infestation on the above phenomena. In all cases the presence of feeding aphids reduced elemental accumulation in plant shoots. Long term infestation with population densities as low as three adult aphids showed a reduction in shoot copper and cadmium content.     

A role forAmanita muscaria L. in the circulation of cadmium and vanadium in a non-polluted woodland

The sporophore of the fungusAmanita muscaria L. contains greatiy elevated levels of cadmium (29.9 g g^–1 dwt) and vanadium (344.9 g g^–1 dwt) in comparison with the soil in a birch woodland (total (HNO₃-extractabie Cd 0.4 g g^–1 dwt, V 11.7 g g^–1 dwt). The significance of this remarkable concentration of normally rare and dispersed elements in terms of their circulation in the woodland has been investigated. Both elements are released from sporophore tissue in a form which can be taken up by a test plant (lettuce), cultivated in the woodland soil amended with different quantities of sporophore tissue, Cadmium levels in all plant tissues were elevated in comparison to the non-amended controls; only root vanadium levels responded to the amendment of the soil. The results are discussed in terms of their significance for the natural cycling of both elements. It is calculated that an abundant population of sporophores could circulate 1.4% of the total cadmium and 0.65% of the total vanadium pool found in the litter layer and 0–5 cm soil horizon in the sampled woodland over a period of 14 days (mean life span of a sporophore).     

The role of internal and external information in foraging decisions of Melipona workers (Hymenoptera: Meliponinae)

Social insect foragers have to make foraging decisions based on information that may come from two different sources: information learned and memorised through their own experience (“internal” information) and information communicated by nest mates or directly obtained from their environment (“external” information). The role of these sources of information in decision-making by foragers was studied observationally and experimentally in stingless bees of the genus Melipona. Once a Melipona forager had started its food-collecting career, its decisions to initiate, continue or stop its daily collecting activity were mainly based upon previous experience (activity on previous days, the time at which foraging was initiated the day(s) before, and, during the day, the success of the last foraging flights) and mediated through direct interaction with the food source (load size harvested and time to collect a load). External information provided by returning foragers advanced the start of foraging of experienced bees. Most inexperienced bees initiated their foraging day after successful foragers had returned to the hive. The start of foraging by other inexperienced bees was stimulated by high waste-removal activity of nest mates. By experimentally controlling the entries of foragers (hence external information input) it was shown that very low levels of external information input had large effect on the departure of experienced foragers. After the return of a single successful forager, or five foragers together, the rate of forager exits increased dramatically for 15 min. Only the first and second entry events had large effect; later entries influenced forager exit patterns only slightly. The results show that Melipona foragers make decisions based upon their own experience and that communication stimulates these foragers if it concerns the previously visited source. We discuss the organisation of individual foraging in Melipona and Apis mellifera and are led to the conclusion that these species behave very similarly and that an information-integration model (derived from Fig. 1) could be a starting point for future research on social insect foraging. Received: 16 April 1997 / Accepted after revision: 30 August 1997     

Direct, residual and direct + residual effects of sulphur in garlic (Allium sativum)-maize (Zea mays) cropping sequence

Significant positive effects of 30 kg/ha of sulphur as manifested on yield and yield parameters of garlic were further carried over to following maize crop. Garlic bulb and foliage yield (6.3 and 0.8 t/ha respectively) obtained at 30 kg/ha of sulphur dose was significantly higher over without sulphur (3.7 and 0.5 t/ha respectively) as revealed from two years' pooled data. Similarly number of leaves/plant, weight of cloves/5bulbs and weight/100 cloves at the said sulphur dose significantly increased over without sulphur from 10.5 to 11.9, 98.3 to 141.2 g and from 159 to 217 g in respective manner Increase in grain yield of maize (residual effect) and in the economic yield of the whole cropping sequence (Bulb yield of garlic and grain yield of maize) i.e. direct plus residual effect at 30 kg/ha of sulphur dose over without sulphur was from 28.3 to 47.2 and from 71 to 116 q/ha in respective manner i.e. with significant differences. Sulphur use efficiencies (kg yield/kg sulphur) of these crops at 15, 30 and 45 kg/ha over no sulphur were 57, 43 and 32; 53, 63 and 6 and 160, 150 and 67, all in respective order An optimum sulphur dose of 44.3 kg/ha produced increased bulb yield (over no S) worth Rs 34892 over fertilizer cost giving B:C ratio of 31.5:1. Utilization of sulphur added at 15, 30 and 45 kg/ha rates was 24.1, 19.3 and 15.7% by the garlic crop; and 29.6. 24.5 and 9.02% by the following maize crop, thus, adding up to 54.1, 43.8 and 24.9% by the cropping sequence, all in respective order.