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Biosorption of copper by Sphaerotilus natans in different conditions of ionic strength and pH was studied by performing sorption tests in batch and membrane reactors. Equilibrium batch tests evidenced the negative effect of ionic strength and the positive effect of pH on biosorption performances: the highest determined value for copper specific uptake, q, was about 60 mg/g at pH 6 and about 15 mg/g at pH 4. A competitive equilibrium model was successfully fitted to experimental data at different ionic strength levels to account for copper-sodium competition. In membrane reactor tests, experimental profiles of copper concentration in the permeate vs. time did not evidence a significant effect of ionic strength at low pH values (4 and 5). On the other hand a more remarkable effect of ionic strength on copper concentration in the permeate was observed at pH 6. Experimental profiles of continuous biosorption in the membrane reactors were successfully simulated by developing a dynamic model accounting for Cu-Na competition and for binding ability of cells fragments.

The capacity of Salvinia herzogii and Pistia stratiotes to remove Cr (III) from water and their behaviour at different Cr (III) concentrations were studied in outdoor experiments. Cr distribution in aerial parts and roots with time and the possible mechanisms of Cr uptake were analyzed. Both macrophytes efficiently removed Cr from water at concentrations of 1, 2, 4 and 6 mgCrL(-1). S. herzogii was the best adapted species. At a greater initial concentration, greater bioaccumulation rates were observed. Root Cr uptake was a rapid process that was completed within the first 24h. Cr uptake through direct contact between the leaves and the solution is the main cause of the increase of Cr in the aerial parts, Cr being poorly translocated from the roots to the aerial parts. Both mechanisms were fast processes. The Cr uptake mechanism involves two components: a fast component and a slow one. The former occurs mainly due to the roots and leaves adsorption and is similar for both species. The slow component is different for each species probably because in P. stratiotes a Cr precipitation occurs induced by the roots.

This paper reports a study into the deployment of a metal adsorbent in situ to estimate bioavailable Cd(II) in marine waters. Eight adsorbents were screened in the laboratory to test their ability to accumulate Cd(II) from deionised water and artificial seawater, and an oxidised activated carbon was selected for further investigation. The adsorption isotherm at Cd(II) concentrations 0.16-38 microgl(-1) and at salinity 15 followed the Freundlich equation. The adsorbent was contained in nylon bags (pore size 35 microm) and dialysis tubes (membrane pore size 2 nm) to produce deployable devices and to investigate the effect of housing material on Cd(II) accumulation. The devices were tested in the laboratory and deployed at four field sites for up to 3 weeks. The adsorbent in the nylon bags reached equilibrium towards the end of this period and the measured contents were in good agreement with expected contents predicted from known seawater Cd(II) concentrations and the adsorption isotherm. The dialysis tubes accumulated significantly lower amounts of Cd(II) than the nylon bags, probably due to an initial lag as Cd(II) diffused into the dialysis bag and due to biofouling which reduced diffusion. The relationship between concentrations of Cd(II) accumulated by the mussels (indicating the bioavailable Cd(II) fraction) and the devices at different field sites could be described by the Freundlich model. The goodness of fit of this relationship was better for the dialysis tubes than the nylon bags. The adsorbent in the nylon bags may have collected small particles from seawater which affected the Cd(II) analysis. Both devices demonstrate potential as indicators of the relative bioavailable fraction of Cd(II) to Mytilus edulis in marine waters.

The biosorption of cadmium(II) and zinc(II) ions onto dried Fontinalis antipyretica, a widely spread aquatic moss, was studied under different values of temperature, initial pH and water hardness. The equilibrium was well described by Langmuir adsorption isotherms. Maximum biosorption capacity of cadmium was independent on temperature and averaged 28.0 mg g(-1) moss, whereas for zinc, capacity increased with temperature, from 11.5 mg g(-1) moss at 5 degrees C to 14.7 mg g(-1) moss at 30 degrees C. Optimum adsorption pH value was determined as 5.0 for both metal ions. Cadmium uptake was unaffected by the presence of calcium ions, but zinc sorption was improved when water hardness increased from 101.1 to 116.3 mg CaCO(3)l(-1). Inversely, as hardness increases, the competition with calcium ions strongly reduces the affinity of the biosorbent for zinc.

The pollution of aquatic ecosystem by heavy metals has assumed serious proportions due to their toxicity and accumulative behavior. The toxicity and fate of the water borne metal is dependent on its chemical form and therefore quantification of the different forms of metal is more meaningful than the estimation of its total metal concentrations. In this study fractionation of metal ions on bed sediments of River Yamuna has been studied to determine the eco-toxic potential of metal ions. The investigations suggest that copper have a tendency to remain associated with residual, reducible and carbonate fractions. The Risk Assessment Code reveal that about 30-50% of lead at most of the sites exist in exchangeable fraction while 30-50% of cadmium at almost all the sites is either exchangeable or carbonate bound and therefore comes under the high risk category and can easily enter the food chain. Most of the copper is in immobile fraction at Delhi while at other sites, a sizable portion (10-30%) is found in carbonate fraction thus posing medium risk for the aquatic environment. Fractionation pattern of zinc shows low to medium risk to aquatic environment.

Biosorption of lead, cadmium, nickel and zinc by live and dead Mucor rouxii biomass treated with NaOH was studied over a range of pH. In the case of dead biomass, low pH resulted in a decrease in the biosorption capacity. At pH 3.0 or less, the inhibition of biosorption of metal ions took place. At pH 4.0 or higher, the biosorption of metal ions increased sharply. Ho's pseudo-second-order model described the biosorption kinetics better than the Lagergren model. Live biomass had high biosorption capacity, i.e. 35.69, 11.09, 8.46 and 7.75 mg/g at pH 5.0 for Pb(2+), Ni(2+), Cd(2+) and Zn(2+), respectively. The dead biomass adsorbed metal ions in the order of Pb(2+), Zn(2+), Cd(2+) and Ni(2+), with the biosorption capability of 25.22, 16.62, 8.36 and 6.34 mg/g at pH 5.0, respectively. At pH 6.0, the capacity of the dead biomass increased to 53.75, 53.85, 20.31 and 20.49 mg/g, respectively. For bi- or multi-metal ion adsorption, biosorption capacity of individual metal ion was reduced in the presence of other metal ions, but the total biosorption capacity increased, indicating the capability of M. rouxii biomass in adsorbing multi-metal ions. In addition, M. rouxii biomasses cultured with different media exhibited the same level of capacity to bind metal ions. Metal ions adsorbed by the biomass could be eluted effectively with HNO(3), while distilled water demonstrated negligible metal elution capability. Regeneration of the biomass with NaOH regained or enhanced the biosorption capacity even after five cycles of adsorption-elution-regeneration.

The passive removal of toxic heavy metals such as Cd(2+), Cu(2+), Zn(2+), Pb(2+), Cr(3+), and Hg(2+) by inexpensive biomaterials, termed biosorption, requires that the substrate displays high metal uptake and selectivity, as well as suitable mechanical properties for applied remediation scenarios. In recent years, many low-cost sorbents have been investigated, but the brown algae have since proven to be the most effective and promising substrates. It is their basic biochemical constitution that is responsible for this enhanced performance among biomaterials. More specifically, it is the properties of cell wall constituents, such as alginate and fucoidan, which are chiefly responsible for heavy metal chelation. In this comprehensive review, the emphasis is on outlining the biochemical properties of the brown algae that set them apart from other algal biosorbents. A detailed description of the macromolecular conformation of the alginate biopolymer is offered in order to explain the heavy metal selectivity displayed by the brown algae. The role of cellular structure, storage polysaccharides, cell wall and extracellular polysaccharides is evaluated in terms of their potential for metal sequestration. Binding mechanisms are discussed, including the key functional groups involved and the ion-exchange process. Quantification of metal-biomass interactions is fundamental to the evaluation of potential implementation strategies, hence sorption isotherms, ion-exchange constants, as well as models used to characterize algal biosorption are reviewed. The sorption behavior (i.e., capacity, affinity) of brown algae with various heavy metals is summarized and their relative performance is evaluated.

Biosorption has been demonstrated to be a useful alternative to conventional treatment systems for the removal of toxic metals from dilute aqueous solution. The objective of this paper was to examine the main aspects of a possible strategy for the removal of arsenates, employing P. chrysogenum biomass. The pretreatment of biomass with common surfactants (as hexadecyl-trimethylammonium bromide and dodecylamine) and a cationic polyelectrolyte was found to improve the biosorption efficiency. The initial biomass showed a relative low affinity for metallic anions, whereas with the application of modified samples a significant uptake of arsenic was observed. Sorption data were well described by typical Langmuir and Freundlich adsorption isotherms. Promising results were obtained in laboratory experiments and effective As(V) removals were observed.

Pesticide uptake by seeds depends on the properties of the chemical, such as structure, stability, log k(ow) and diffusion rate, type of water, pH, temperature, content of organic matter and composition, and on seed characteristics such as permeability of the seed coat. The efficiency with which Lupinus angustifolius seeds retain different herbicides (simazine, atrazine, isoproturon, linuron,) and insecticides (carbaryl, fenamiphos, permethrin) was evaluated using both a batch and a continuous system. Factors which affect pesticide uptake by seeds, such as flow rate, seed biomass, pesticide concentration, contact time, pH, seed saturation and also the speed of the retention process for 17 days, were tested. L. angustifolius showed a high retention capacity for the above mentioned pesticides. The extraction of pesticides from seeds using different organic solvents, such as methanol, acetonitrile, ethyl acetate and n-hexane was evaluated and no pesticide residues were detected in any of the solvents tested. This could be attributed to the capacity of the seed to degrade the pesticides. From the results obtained, L. angustifolius seems to be a promising seed to be applied for phytoremediation of industrial effluents or contaminated water.

Copper, zinc, cadmium and selenium were measured in the gastropod mollusc Bembicium nanum at two uncontaminated locations, Jervis Bay and Rosedale, NSW, to determine natural variability of metals associated with gender, mass, shore position and temporal variability. Trace metals were also measured in B. nanum at three industrialised locations to determine the accumulation of trace metals in contaminated environments.Copper, zinc, cadmium and selenium concentrations were not significantly different between male and female B. nanum. No significant relationships were found between zinc, cadmium and selenium concentrations and mass. There was a significant relationship between copper concentration and mass but only 19% of the variation was explained by mass. Generally inherent variability within samples had a greater influence than gender or variations in mass on trace metal concentrations. No trend was found in cadmium and selenium concentrations with variation in shoreline position. Copper and zinc concentrations increased further away from the low tide mark, with a decrease in metal concentrations at the furthest site from the water. Variability in metal concentrations is attributable to variations in food source, food availability and different immersion times.Copper, zinc, cadmium and selenium concentrations varied over a 12-month period. Copper, cadmium and selenium were taken up and lost over time, as metal body burden followed the same trend as metal concentrations. Zinc concentrations were influenced by mass. Copper and cadmium concentrations fluctuated throughout the 12-month period but with no clear seasonal trends. Selenium concentrations peaked in spring (October), with concentrations remaining uniform over the other months. These differences in mean concentrations between months were most likely due to inherent trace metal variability associated with differences in food availability and changes in metabolic rates associated with changes in temperature during the study period. Measurement of trace metals in B. nanum at contaminated sites showed that B. nanum accumulates metals in response to contamination.B. nanum meets most of the requirements to be a biomonitor of trace metal contamination as they are abundant, sedentary, easy to identify, provide sufficient tissue for analysis, tolerate high concentrations of pollutants and they accumulate trace metals in response to contamination. However, as trace metal concentration can vary with mass, shoreline position and temporally, care must be taken to collect individual organisms with similar mass from similar shoreline positions and times.

The estrogen receptor (ER) binding affinities of 25 compounds including 15 industrial phenolic chemicals, two phytoestrogens, three natural steroids and one man-made steroid were detected by a binding competition assay. The 17 industrial phenolic chemicals were selected as objective compounds because they are possibly released from epoxy and polyester-styrene resins used in lacquer coatings of concrete tank and lining of steel pipe in water supply system. A quantitative structure-activity relationship (QSAR) for structurally diverse phenols, nine alkylphenols with only one alkyl group, four hydroxyl biphenyls, bisphenol A and four natural and man-made estrogens was established by applying a quantum chemical modeling method. Logarithm of octanol-water coefficient (logPow), molecular volume (V(m)), and energies of the highest occupied molecular orbital ( epsilon (HOMO)) and lowest unoccupied molecular orbital ( epsilon (LUMO)) were selected as hydrophobic, steric (V(m)), and electronic chemical descriptors, respectively. Chemicals capable of ER binding had large V(m) and high epsilon (HOMO), while the effects of logPow and epsilon (LUMO) on the binding affinity could not be identified. The QSAR made successful predictions for the three phytoestrogens. Also, the successful prediction of ER-binding affinity for biochanin A, another phytoestrogen, two indicators of pH (phenolphthalin and phenolphthalein) and one alkylphenolic chemical with three alkyl groups (4-methyl-2,6-di-butyl-phenol), by amending the V(m) in the above-mentioned QSAR according to the electron-density distribution (or HOMO density) is an additional step in the elucidation of chemical steric and electronic parameters for predicting the binding affinities of phenolic compounds.

Concentrations of cadmium, copper, mercury, lead and zinc were determined by atomic absorption spectrophotometry in the muscle, gill and liver of bream Abramis brama L. to study the relationship between the heavy metal load of fish and their age and size, and the seasonal variation of pollutant loads. Fish were collected from the Western basin of Lake Balaton (Hungary) in October 1999 and May 2000. The average metal concentrations of different organs varied in the following ranges: Cd 0.42-2.10; Cu 1.77-56.2; Hg 0.01-0.19; Pb 0.44-3.24; Zn 10.9-82.5 microg g(-1) dry weight. The highest Cd, Cu, Pb and Zn concentrations were detected in the gill or liver of fish, whereas the highest Hg concentrations were measured in the muscle. In the liver of bream for cadmium, copper and mercury the Pearson correlation analysis revealed positive associations related to age and size (length, net weight), as well as for the mercury load of all three investigated organs. In the muscle and gill the copper, lead and zinc concentrations, similarly to the lead and zinc concentrations of the liver, the associations related to age and size were negative. The correlations between the heavy metal concentrations of organs and the individual condition factors of fish samples proved to have opposite trends compared to those related to the age and size of fish. The seasonal variations in the heavy metal load of bream could be attributed rather to the seasonal change in the condition factor of fish than to variations in the pollutant load of the site.

A gram-negative bacterium Pseudomonas putida 5-x with high Cu2+ accumulating capability was isolated from electroplating effluent in Kwun Tong, Hong Kong. The pretreated cells without superficial layer-capsule, isolated cell envelopes and the separated peptidoglycan layer materials were obtained from fresh P. putida 5-x cells, their Cu2+ adsorption capacities and properties were compared with that of the fresh cells. Pretreatment by 0.1 mol L(-1) HCl enhanced Cu2+ adsorption capacity due to the degradation of cell superficial layer-capsule of P. putida 5-x cells. Isolated cell envelopes possessed five times more Cu2+ adsorption capacity than that of fresh intact cell. The Cu2+ adsorption of separated peptidoglycan layer materials indicated that the peptidoglycan layer only played 10-15% part of the Cu2+ adsorption capacity, and implied other cell surface components such as outer membrane or inner membrane might play an important role in such high Cu2+ binding of the cell envelopes. The adsorption process of fresh cells, pretreated cells and cell envelopes of P. putida 5-x could be described with Freundlich isotherm, while the adsorption of Cu2+ by separated peptidoglycan layer materials was better described with Langmuir isotherm.

A dynamic model that links biokinetics and consumer-resource dynamics for describing zinc (Zn) accumulation in abalone Haliotis diversicolor supertexta has been developed and then applied to Zn data from real abalone farms. The biokinetic parameters used in this study, uptake and depuration rate constants of abalone and their food source, red alga Gracilaria tenuistipitata var. liui, were obtained from a laboratory 14-d exposure experiment. We carried out a sensitivity analysis of the model by using the fractional factorial design technique, taking into account the influence of consumer-resource-related parameters such as growth and death rates and biomass and biokinetic parameters characterized by bioconcentration factor. Results indicate that the response time of biomagnification dynamics of Zn accumulation in abalone was influenced mainly by the growth rate of algae and biomass and the death rate of abalone and by interactions algae biomass and abalone death rate and abalone and algae biomass. New algae production results in substantially higher values of biomagnification factor. The linked model was then applied to field observations from a real-life situation of variable Zn concentrations occurring in abalone farms. Simulation results show that the predicted values are within a factor of 2 of the measured values (% errors range from 5.3 +/- 4% to 44.1+/- 8%). Both model analysis and model application to the abalone farms suggest that the linking influences between biokinetics and consumer-resource dynamics support Zn accumulation in H. diversicolor supertexta and in G. tenuistipitata var. liui as functions of Zn concentration in water and abundance of food occurring in abalone farms.

The zinc uptake and posterior release by an aquatic bryophyte-Fontinalis antipyretica L. Ex Hedw.--was experimentally studied in laboratory exposing the plants to different zinc concentrations in the range, 1.0-5.0 mg 1(-1), for a 144 h contamination period, and then exposed to metal-free water for a 120 h decontamination period. The experiments were carried out in perfectly mixed contactors at controlled illumination, using mosses picked out in February 1997, with a background initial zinc concentration of 263 mg g(-1) (dry wt.). A first-order mass transfer kinetic model was fitted to the experimental data to determine the uptake and release constants, k1 and k2, the zinc concentration in mosses at the end of the uptake period, C(mu), and at the equilibrium, for the contamination and decontamination stages, C(me) and C(mr), respectively. A bioconcentration factor, BCF = k1 /k2 (zinc concentration in the plant, dry wt./zinc concentration in the water) was determined. A biological elimination factor defined as BEF = 1 - C(mr)/C(mu) was also calculated. BCF decreases from about 4500 to 2950 as Zn concentration in water increases from 1.05 to 3.80mg 1(-1). BEF is approximately constant and equal to 0.80. Comparing Zn and Cu accumulation by Fontinalis antipyretica, it was concluded that the uptake rate for Zn (145 h(-1)) is much lower than for Cu (628 h(-1)) and the amount retained by the plant decreased by a factor of about seven.

The trophic transfer of metals along the food chain has been recognized as an important issue in the study of water quality in recent years. Feeding experiments were conducted to examine the assimilation of three metals (Cd, Cr and Zn) by the zebrafish Danio reiro feeding on the freshwater zooplankton Daphnia magna. The zooplankton were exposed to radiotracers from both the aqueous and dietary phases for different duration, and then pulse-fed to the zebrafish for measurements of metal assimilation efficiency (AE). The calculated AEs were 3-8% for Cd, 2-39% for Cr, and 17-36% for Zn in the zebrafish. For Cd and Zn, there was no statistically significant difference between the two different radiolabeling routes (aqueous and dietary exposure). For Cr, the AEs were higher when it was accumulated by D. magna from the dietary source than when it was accumulated from the aqueous phase. The gut passage time (GPT) was 6-10 h for all metals, with less variation for Zn among the different treatments. There was no obvious relationship between metal GPT and metal AE, presumably due to the narrow range of variation of metal gut passage. About 5-36%, 20-31%, and 8-30% of the total Cd, Cr and Zn was found in the soft tissue of D. magna after the radiolabeling. A much higher fraction of Cd and Zn was found in the soft tissue of D. magna when the metals were accumulated from the dietary phase. No significant relationship between the metal AE and the metal distribution in the soft tissue of D. magna was however documented in this study. Our results demonstrated that there was major difference in metal AE in freshwater fish among different metals. Metal localization in prey organisms and GPT appear to have little influence on metal assimilation by the zebrafish.

Crushed crab shells were chemically treated to transform the chitin present into chitosan. Three particle sizes with average diameters of 0.65, 1.43 and 3.38 mm, average pore diameters ranging from approximately 300 to 540 A, and a specific surface area of approximately 30 m2/g were obtained. Batch experiments were performed to study the uptake equilibrium and kinetics of cadmium by chitosan. Adsorption equilibrium followed a Freundlich relationship and was found to be independent of particle size indicating that adsorption takes place largely in the pore space. A high initial rate of cadmium uptake was followed by a slower uptake rate suggesting intraparticle diffusion as the rate-limiting step. The kinetic uptake data were successfully modeled using a pore diffusion model incorporating nonlinear adsorption. The effect of boundary layer resistance was modeled through inclusion of a mass transfer expression at the outside boundary. Two fitting parameters, the tortuosity factor (tau) and the mass transfer coefficient at the outside boundary (k(c)) were used. These parameters were unique for all solute and sorbent concentrations. The tortuosity factors varied from 1.5 for large particles to 5.1 for small particles. The mass transfer coefficient varied from 2 x 10(-7) m/s at 50 rpm to 2 x 10(-3) m/s at 200 rpm. At agitation rates below 100 rpm, boundary layer resistance reduced the uptake rate significantly. Its very high sorption capacity and relatively low production cost make chitosan an attractive sorbent for the removal of heavy metals from waste streams.

An equilibrium model for describing the relationships between important parameters for heavy metal sorption by algae was derived through a thermodynamics approach. In this model, both the removal efficiency of heavy metal and metal adsorption per unit algal biomass are considered to be simple functions of the ratio of algal biomass concentration to the initial metal concentration for selected conditions, i.e. as at constant pH and temperature. The model was found to fit the experimental results well (judged by the correlation-regression coefficient, R2), for the adsorption of cadmium, copper, lead and zinc by two algal species, Oocystis sp. (both living and non-living) and Chlorococcum sp. The applicability of the model was also supported by the reprocessed results of experimental data given in the literature, i.e. for the metal species, Cd, Pb, Cu and Ag, the algal species, Chlorella vulgaris, Scenedesmus quadricauda and Cladophora crispata, and both batch and continuous fixed-bed reactors. It was also demonstrated that the model could be applied over a broad range of pH for cadmium and copper adsorption by Oocystis sp. However, the model was not applicable at very low and high pH levels, due to negligible adsorption and precipitation, respectively.

Acid volatile sulfides (AVS) in sediments are available for binding with divalent cationic metals through the formation of insoluble metal-sulfide complexes, thereby controlling the metal bioavailability and subsequent toxicity to benthic biocommunities. However, when the molar concentrations of simultaneously extracted metals (SEM) were greater than AVS, the unexpectedly low or nondetectable levels of metal in pore water could also be found. Thus, except AVS, additional binding phases in sediments were supposed to provide the binding sites for SEM. The aims of this study are to realize the spatial distribution of AVS, SEM, and other binding phases of heavy metals in anoxic sediments of the Ell-Ren river and to elucidate what may be the main additional binding phases except AVS in the anoxic river sediments. By comparing the spatial distributions of SEM/ AVS ratio with various binding phases in extremely anoxic sediments (redox potential was between -115 and -208 mV), both organic matter and carbonates could be considered to be the main additional binding phases of SEM other than AVS. In addition, AVS appeared to have the priority to bind with SEM. By comparing the binding phases of heavy metals before and after AVS extraction, it could be found that Fe-oxides could also be considered to be the main additional binding phase associated with Zn in slightly anoxic sediments (redox potential was between -50 and -130mV), while organic matter with Cu being the next.