Comparative and competitive adsorption of Cu(II), Cd(II) and Pb(II) onto Sepia pharaonis endoskeleton biomass from aqueous solutions

In this research, the possibility of simultaneous removal of lead, cadmium and copper divalent ions from water samples through the use of Sepia pharaonis endoskeleton powder (SPEB) as bio‐material, was investigated. The bio‐sorbent was characterised by Fourier transform infrared spectrum (FT‐IR), atomic force microscopy (AFM) and X‐ray fluorescence (XRF). The different factors affecting the bio‐sorption process were studied. Langmuir and Freundlich isotherm models were applied to analyse the experimental data. The kinetic studies showed that the pseudo‐second order model kinetics were compatible with the investigated systems. It was found that under optimal conditions, this bio‐sorbent was efficient in the uptake of these heavy metal ions from both mono and multi‐metal solutions, and high removal percentages were achieved. This study verified the potential ability of SPEB as an efficient natural adsorbent for removal of Pb(II), Cd(II) and Cu(II) ions from river, tap and mineral water samples.     

Removal of Co(II), Ni(II) and Cd(II) from Aqueous Solutions by Magnetic Sorbents

The possibility of using magnetic sorbents for the removal of Co(II), Ni(II) and Cd(II) from water media is shown. It was established that magnetite is more effective compared with magnetic potassium–zinc hexacyanoferrate(II). The pH (> 4) and the dose of sorbents were defined for obtaining maximum possible degree of removing ions of specified metals from water media.     

Sorption of Zn(II), Pb(II), and Co(II) using natural sorbents: equilibrium and kinetic studies

Natural Jordanian sorbent (consisting of primary minerals, i.e., quartz and aluminosilicates and secondary minerals, i.e., calcite and dolomite) was shown to be effective for removing Zn(II), Pb(II) and Co(II) from aqueous solution. The major mineral constitutions of the sorbent are calcite and quartz. Dolomite was present as minor mineral and palygorskite was present as trace mineral. The sorbent has microporous structure with a modest surface area of 14.4 m(2)g(-1). pH(zpc) (pH of zero point charge) of the sorbent was estimated by alkaline-titration methods and a value of 9.5 was obtained. The sorption capacities of the metals were: 2.860, 0.320, 0.076 mmol cation g(-1) for Zn(II), Pb(II) and Co(II) at pH 6.5, 4.5 and 7.0, respectively. The shape of the experimental isotherm of Zn(II) was of a "L2" type, while that of Pb(II) and Co(II) was of a "L1" type according to Giles classification for isotherms. Sorption data of metals were described by Langmuir and Freundlich models over the entire concentration range. It was found that the mechanism of metal sorption was mainly due to precipitation of metal carbonate complexes. The overall sorption capacity decreased after acid treatment, as this decreased the extent of precipitation on calcite and dolomite. The effect of Zn(II) ions concentration on sorption kinetics was investigated. Kinetic data were accurately fitted to pseudo-first order and external diffusion models which indicated that sorption of Zn(II) occurred on the exterior surface of the sorbent and the contribution of internal diffusion mechanism was insignificant. Furthermore, the sorption rate of Zn(II) was found to be slow, where only 10-20% of the maximum capacity was utilized in the first 30 min of interaction.     

Removal of free and complexed heavy-metal ions by sorbents produced from fly (Musca domestica) larva shells

Fly larva shells (FLS) are formed as a side product in the biological treatment of organic wastes, and chitin and chitosan produced from the FLS have been used as sorbents for heavy-metal ions. Sorbents are characterised by FT-IR measurements and pH-potentiometric titration and by determination of their surface area, and the content of main elements (C, N, P, S) and ashes. Free metal ions are sorbed best (up to 0.5-0.8 mmol g(-1)) onto chitin and chitosan. The sorption ability for free metal ions of chitin decreases in the order Fe(III) > Cu(II) (Pb(II) > Zn(II). > Ni(II) > Mn(II) and that of chitosan decreases in the order Cu(II) > Mn(II) > Ni(II) > Zn(II) > Pb(II) > Fe(III). The complexed metal ions are sorbed by the FLS up to 0.2-0.4mmol g(-1). The sorption ability for metal ions and ligands depends on pH, concentration of complexed metal ions and the ligand species in the solution. Glycine has the retarding effect on the sorption of Ni(II) and Cu(II) ions, and EDTA enhances the Cu(II) ion sorption. Ni(II) and glycine sorption obeyed the Langmuir isotherm. The observed sorption data show the promising potentialities of the FLS for the heavy-metal removal from the solutions, containing strong complexing agents. Mechanisms for the removal of free and complexed metal ions by chitin, chitosan and the FLS have been discussed.     

Sorption of cadmium(II) and zinc(II) ions from aqueous solutions by cassava waste biomass (Manihot sculenta Cranz)

The sorption of two divalent metal ions, Cd(II) and Zn(II), onto untreated and differentially acid-treated cassava waste biomass over a wide range of reaction conditions was studied at 30°C. The metal ion removal from the spent biomass was also measured. The batch experiments show that pH 4.5–5.5 was the best range for the sorption of the metal ions for untreated and acid-treated biomass. Time-dependent experiments for the metal ions showed that for the two metals examined, binding to the cassava waste biomass was rapid and occurred within 30 min and completed within 1 h. High sorption capacities were observed for the two metals. The binding capacity experiments revealed the following amounts of metal ions bound per gram of biomass: 86.68 mg/g Cd, 55.82 mg/g Zn and 647.48 mg/g Cd, 559.74 mg/g Zn for untreated and acid-treated biomass, respectively. It was further found that the rate of sorption was particle-diffusion controlled, and the sorption rate coefficients were determined to be 2.30×10⁻¹ min⁻¹ (Cd²⁺), 4.0×10⁻³ min⁻¹ (Zn²⁺) and 1.09×10⁻¹ min⁻¹ (Cd²⁺), 3.67×10⁻² min⁻¹ (Zn²⁺) for 0.5 and 1.00 M differential acid treatment, respectively. Desorption studies showed that acid treatment inhibited effective recovery of metal ions already bound to the biomass as a result of stronger sulfhydryl-metal bonds formed. Less than 25% of both metals were desorbed as concentration of acid treating reagent increases. However, over 60% Cd and 40% Zn were recovered from untreated biomass during the desorption study. The results from these studies indicated that both untreated and acid-treated cassava waste biomass could be employed in the removal of toxic and valuable metals from industrial effluents.     

Modeling the sorption kinetics of divalent metal ions to hematite

The sorption kinetics of the divalent metals Zn, Co, Ni, and Cd to hematite were studied in single sorbate systems with high sorbate/sorbent ratios (from 1.67 to 3.33mol sorbate/mol sorption sites) in 10mM Na-piperazine N,N'-bis 2-ethane sulfonic acid (Na-PIPES) solution at pH 6.8. The experimental data showed a rapid initial sorption (half-time about 1min) followed by slower sorption that continued for 1-5 days. The sequence of fast to slow sorption kinetics was modeled by slow inner-sphere (IS) complexation in equilibrium with outer-sphere (OS) complexes. Although the OS reaction was fast and considered to be in equilibrium, the extent of OS complexation changed over time due to increased surface potential from the IS complexes. For example, the model showed that the dimensionless OS complexation function, K(os), decreased from 0.014 initially to 0.0016 at steady state due to sorption of 4x10(-5)M Zn(II) to 2gL(-1) hematite. Sorption rate constants, k(ads), for the various divalent metals ranged from 6.1 to 82.5M(-1)s(-1). Desorption rate constants, k(des), ranged from 5.2x10(-7) to 6.7x10(-5)s(-1). This study suggests that the conversion from OS to IS complex was the rate-determining step for the sorption of divalent metals on crystalline adsorbents.     

Concentrations of heavy metals and plant nutrients in water, sediments and aquatic macrophytes of anthropogenic lakes (former open cut brown coal mines) differing in stage of acidification.

Concentration of heavy metals (Al, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V and Zn) as well as macronutrients (N, P, K, Ca, Mg, S) were measured in water, bottom sediments and plants from anthropogenic lakes in West Poland. The collected plants were: Phragmites australis, Potamogeton natans, Iris pseudoacorus, Juncus effusus, Drepanocladus aduncus, Juncus bulbosus, Phalaris arundinacea, Carex remota and Calamagrostis epigeios. Two reference lakes were sampled for Nymphaea alba, Phragmites australis, Schoenoplectus lacustris, Typha angustifolia and Polygonum hydropiper. These plants contained elevated levels of Cd, Co, Cr, Cu and Mn, and part of the plants contained in addition elevated levels of Mn, Fe, Pb, Ni and Zn. Analyses of water indicated pollution with sulfates, Cd, Co, Ni. Zn, Pb and Cu, and bottom sediments indicated that some of the examined lakes were polluted with Cd, Co and Cr. Strong positive correlations were found between concentrations of Co in water and in plants and between Zn in sediments and plants, indicating the potential of plants for pollution monitoring for this metal. Heavy metal accumulation seemed to be directly associated with the exclusion of Ca and Mg.     

Modeling heavy metal uptake by sludge particulates in the presence of dissolved organic matter

The uptake of the seven heavy metal ions Cd(II), Co(II), Cr(III), Cu(II), Ni(II), Pb(II), and Zn(II) by sludge particulates in single-metal systems was investigated. Results showed that under acidic and neutral pH conditions, the uptake of all heavy metals by sludge particulates increases with the increase of pH. However, in the alkaline pH region, the uptake of Cu(II), Ni(II), and Co(II) decreases with the increase of pH, primarily due to the high dissolved organic matter (DOM) concentration in high pH conditions. Based on chemical reactions among heavy metal, sludge solids, and DOM, a mathematical model describing metal uptake as functions of DOM and pH was developed. The stability constants of metal–sludge and metal–DOM complexes can be determined using this model in conjunction with experimental metal uptake data. Results showed that, for the secondary sludge sample collected from Baltimore Back River Wastewater Treatment plant on March 1997, the stability constants of Cu(II)–sludge complex (log K_S) and Cu(II)–DOM complex (log K_L) are 5.3±0.2 and 4.7±0.3, respectively; for Ni(II), they are 4.0±0.2 and 3.9±0.2, respectively. Results also showed that under neutral and low pH conditions (pH<8), the DOM effects on metal uptake for all heavy metals are insignificant. Therefore, the DOM term in the model can be ignored. Results showed that, for the secondary sludge sample collected from Baltimore Back River Wastewater Treatment plant on December 1996, the estimated log K_S values of metal–sludge complexes for Cd(II), Co(II), Cr(III), Cu(II), Ni(II), Pb(II), and Zn(II) are, respectively, 3.6±0.2, 3.0±0.1, 5.5±0.1, 4.8±0.1, 3.1±0.1, 5.1±0.1, and 4.4±0.3.     

The acute lethal toxicity of heavy metals to peracarid crustaceans (with particular reference to fresh-water asellids and gammarids)

In static tests on the acute toxicity of metal salts to two fresh-water peracarids, Asellus aquaticus (L.) (Isopoda) and Crangonyx pseudogracilis Bousfield (Amphipoda), 48 and 96 h LC₅₀ values were determined for Al(III), Cd(II), Cr(III), Cu(II), Fe(III), Hg(II), Mn(II), Ni (II), Pb(II) and Zn(II). Additional metals tested upon Crangonyx alone were Ag(I), Co(II), Cr(VI), Fe(II), Mn(VII), Mo(VI), Sn(II) and V(V). Of the metal salts tested on both species, Asellus was more sensitive to Al(III) and Mn(II) than Crangonyx, similarly sensitive to Cd(II), Fe(III) and Zn(II), and less sensitive to the remainder. Toxicity of metal salts which are unstable with respect to reduction or oxidation was found to be higher than that of the corresponding stable salts of the same metal.Previously published data on the acute toxicity of heavy metal salts to fresh-water, estuarine and marine amphipods and isopods are tabulated and discussed. Brief comparisons are also made between the relative tolerances of peracarids, Daphnia and fresh-water fish. Crangonyx pseudogracilis is recommended as worthy of further research, due to its widespread distribution and ease of culture.     

Pb(II)、Cu(II)、Cd(II)在黄土上二元竞争吸附特性研究

铅、铜、镉是3种具有代表性的重金属污染物,可用于模拟多重离子复合污染情况。研究了离子浓度、土水比等因素对3种元素在黄土上二元竞争吸附特性的影响。等温吸附模型Langmuir、Freundlich和D-R模型都能在一定程度上解释Pb(II)-Cu(II)、Pb(II)-Cd(II)、Cu(II)-Cd(II)在黄土上的竞争吸附性能。黄土对Pb(II)、Cu(II)、Cd(II)的选择顺序为Pb(II)>Cu(II)>Cd(II)。相比单一吸附,黄土对每种离子的吸附容量均有不同程度的下降。溶液的初始浓度越大,3种离子在单位黄土上的最大吸附量也随之增大,吸附效率随之降低;适当增大土水比可提高离子的去除效率。试验结果为黄土作为防污屏障和污水处理材料提供了依据。     

Geochemistry of trace metals in a fresh water sediment: field results and diagenetic modeling

Concentrations of Fe, Mn, Cd, Co, Ni, Pb, and Zn were determined in pore water and sediment of a coastal fresh water lake (Haringvliet Lake, The Netherlands). Elevated sediment trace metal concentrations reflect anthropogenic inputs from the Rhine and Meuse Rivers. Pore water and sediment analyses, together with thermodynamic calculations, indicate a shift in trace metal speciation from oxide-bound to sulfide-bound over the upper 20 cm of the sediment. Concentrations of reducible Fe and Mn decline with increasing depth, but do not reach zero values at 20 cm depth. The reducible phases are relatively more important for the binding of Co, Ni, and Zn than for Pb and Cd. Pore waters exhibit supersaturation with respect to Zn, Pb, Co, and Cd monosulfides, while significant fractions of Ni and Co are bound to pyrite. A multi-component, diagenetic model developed for organic matter degradation was expanded to include Zn and Ni dynamics. Pore water transport of trace metals is primarily diffusive, with a lesser contribution of bioirrigation. Reactions affecting trace metal mobility near the sediment-water interface, especially sulfide oxidation and sorption to newly formed oxides, strongly influence the modeled estimates of the diffusive effluxes to the overlying water. Model results imply less efficient sediment retention of Ni than Zn. Sensitivity analyses show that increased bioturbation and sulfate availability, which are expected upon restoration of estuarine conditions in the lake, should increase the sulfide bound fractions of Zn and Ni in the sediments.     

Application of sub-critical water technology for recovery of heavy metal ions from the wastes of Japanese scallop Patinopecten yessoensis

Sub-critical water (sub-CW) technology was used as a new technology with environmental and financial benefits for the recovery of harmful heavy metal ions Cd (II), Zn (II), Cu (II), Fe (II), Mn (II) and Ni (II) in the waste of Japanese scallop Patinopecten yessoensis. The metals are responsible for environmental problems owing to the large amount of the waste. This study proposes a new method using sub-CW treatment to recover the metal ions from scallop waste and simultaneously produce harmless and valuable materials. Reactions were conducted in a temperature range of 473-653 K and for reaction times of 1-60 min. After the sub-CW reaction, four phases existed: an oil phase, metal-soap phase, aqueous phase and solid residual. Some oil was hydrolyzed by the sub-CW reaction and converted to free fatty acids and glycerin. Free fatty acids reacted with metal ions and became metal-soap phase. Both the metal-soap phase and oil phase caught almost all metal ions at low and medium reaction temperatures (473-573 K) from original wastes, although the concentrations of the metal ions in the metal-soap phase were much higher than those in the oil phase. With increasing temperature, these two phases decomposed and the metal ions concentrated in solid residual (un-reacted waste). The binding mechanisms in the oil and metal-soap phases are discussed including the key functional groups involved. The maximum concentrations of metal ions in metal-soap phase were 7225 ppm (Fe), 862 ppm (Zn), and 800 ppm (Cd) at 573 K. The aqueous phase showed the lowest concentration of metal ions especially at temperatures above 550 K (~1.5 ppm).     

Heavy metals in wheat grain: assessment of potential health risk for inhabitants in Kunshan, China

Heavy metals (HMs) may cause deleterious effects on human health due to the ingestion of food grain grown in contaminated soils. Concentrations of HMs (Hg, As, Cr, Cu, Ni, Pb, Zn and Cd) in wheat grains were investigated in different areas of a developed industry city in Southeast China (Kunshan city), and their potential risk to health of inhabitants was estimated. The results showed that concentrations of HMs in the top soil (0-15 cm) were in this order: Zn>Cr>Ni>Pb>Cu>As>Hg>Cd. The Zn, Cr, Ni Cd and Hg concentrations of several soil samples exceeded the permissible limits of China standard. In addition, concentrations of HMs in wheat grain decreased in the order of Zn>Cu>Pb>Cr>Ni>Cd>As>Hg. There were 1, 6 and 10 wheat samples whose Zn, Pb and Cd concentrations were above the permissible limits of China standard, respectively. In relation to non-carcinogenic risks, Hazard Quotient (HQ) of individual metal presented values inside the safe interval. However, health risk due to the added effects of eight HMs was significant for rural children and rural adults, but not for urban adults and urban children. HQ (individual risk) and HI (Hazard Index of aggregate risk) to different inhabitants due to HMs followed the same sequence of: country children>country adults>urban children>urban adults. Amongst the HMs, potential health hazards due to As, Cu, Cd and Pb were great, and that due to Cr was the minimum. It was suggested to pay more attention on the potential added threat of HMs to the health of country inhabitants (both children and adults) through consumption of wheat in Kunshan.     

Divalent metal accumulation in freshwater bivalves: an inverse relationship with metal phosphate solubility

Whole soft tissue concentrations of Mn, Co, Ni, Cu, Zn, Pb, Cd and U were measured in two species of freshwater (unionid) bivalves (Hyridella depressa and Velesunio ambiguus) from a minimally polluted site in the Hawkesbury-Nepean River, south-eastern Australia. Although the mean concentrations of metals in the tissue were similar for each bivalve species, their patterns of accumulation were dissimilar. For each metal, positive linear relationships between tissue concentration and shell length (r2 = 0.37-0.77; P < or = 0.001) and tissue dry weight (r2 = 0.29-0.51; P < or = 0.01) were found in H. depressa, but not in V. ambiguus. However, for both species, positive linear relationships were found between the tissue concentration of each divalent metal and Ca tissue concentration (r2 = 0.59-0.97; P < or = 0.001). For both bivalve species, the normalised rates of accumulation of the metals relative to increasing Ca concentration and/or size, were U approximately = Cd > or = Pb > or = Mn > Co > or = Zn > Cu > Ni. The differential rates of accumulation of divalent metals are interpreted as being predominantly governed by their varying loss rates, which are controlled by the differing solubilities (log Ksp values) of the metals in the phosphatic extracellular granules, the demonstrated major sites of metal deposition in the tissue of H. depressa and V. ambiguus. The rates of accumulation of Mn, Co, Zn, Cu and Ni were linearly and inversely related (r2 = 0.91-0.97; P < or = 0.001) to their solubilities as hydrogen phosphates, a finding consistent with the bioaccumulation model previously developed for the alkaline-earth metals. However, for U, Cd and Pb, this linear inverse relationship did not continue to hold, i.e. their rates of accumulation did not increase with decreasing solubility. However, these results are still consistent with the model if U, Cd and Pb are so insoluble in the granules of H. depressa and V. ambiguus over their lifetime (up to approx. 50 years) that there is effectively no loss of these metals, and hence, no differential between their rates of accumulation. The present results reaffirm the use of Ca tissue concentration to predict the tissue concentrations of other divalent metals by explaining up to 94 and 97% of the variability between individual bivalves of H. depressa and V. ambiguus, respectively. The use of Ca tissue concentration to effectively minimise the inherent variability between individuals in their metal tissue improves the ability of an investigator to discern smaller spatial and/or temporal differences in the metal tissue concentrations of these bivalves, and thus to detect metal pollution.     

Assessment of metal mobility in dredged harbour sediments from Barcelona, Spain

In order to assess heavy metal mobility in dredged harbour sediments, six superficial sediment samples covering a range of pollution levels and environments were collected in Barcelona Harbour. Samples were characterised in terms of major compounds (Al, Ca, Fe, Mn, Si, Ti, Mg, K and Na); total C, N and S contents; organic matter; and water content. Pseudo-total trace metal contents were assessed after aqua regia digestion (ISO 11466:1995). The modified BCR three-step sequential extraction procedure (BCR-SEP) was applied, and both major compounds (Al, Ca, Fe and Mn) and trace metals (Cd, Cr, Cu, Ni, Pb and Zn) were determined in the different extracts. Both the pseudo-total digestion method and the BCR-SEP were validated using two sediment certified materials from lakes (BCR CRM 701 and BCR CRM 601). The highest metal concentrations were observed in one of the sampling points which receives an urban discharge. The observed mobility order (percentage of metal extracted in the first step) of the six trace metals studied was Cd>Zn>Pb>Cu>Ni>Cr. The good agreement observed with the results obtained as the sum of the four steps (extractable+residue) and the pseudo-total content shows that laboratory working conditions were under control.     

Concentrations of selected metals in honey consumed in Nigeria

The concentration of metals, cadmium (Cd), lead (Pb), nickel (Ni), chromium (Cr), copper (Cu), cobalt (Co), iron (Fe), manganese (Mn), and zinc (Zn) was measured in selected samples of honey in Nigeria with a view to providing information on the regional concentration profile of metals in these honeys. The honey samples were digested with a mixture of acids and analysed for metal concentrations using atomic absorption spectrophotometry. The concentrations of metals (mg kg^?1) in these honeys ranged from < 0.3 for Cd,<0.50–39.75 for Pb,<0.25–6.98 for Ni,<0.25–55.25 for Cr,<0.25–71.25 for Cu,<0.25–3.50 for Co,<5.0–163.15 for Fe,<11.0–31.75 for Mn and 1.0–31.0 for Zn. The concentrations of metals were relatively high but lower than their respective permissible limits in food except for Pb and Cu in some samples. The regional distribution patterns of metals indicated that honey samples from the Niger Delta region of Nigeria had higher mean concentrations of Ni, Cr, Co, Fe and Zn than honey samples from other regions. The honey samples from the northern region had higher mean concentrations of Pb and Cu.     

Removal of toxic metal ions with magnetic hydrogels

Hydrogels, based on 2-acrylamido-2-methyl-1-propansulfonic acid (AMPS) were synthesized via photopolymerization technique and used for the preparation of magnetic responsive composite hydrogels. These composite hydrogels with magnetic properties were further utilized for the removal of toxic metal ions such as Cd(II), Co(II), Fe(II), Pb(II), Ni(II), Cu(II) and Cr(III) from aqueous environments. It was revealed that hydrogel networks with magnetic properties can effectively be utilized in the removal of pollutants. The results verified that magnetic iron particle containing p(AMPS) hydrogel networks provide advantageous over conventional techniques. Langmuir and Freundlich adsorption isotherms were applied for toxic metal removal and both isotherms were fit reasonably well for the metal ion absorptions.     

A pilot study on the content and the release of Ni and other allergenic metals from cheap earrings available on the Italian market

The capability of alloys used in cheap jewellery to release metal ions on contact with the skin causing allergic contact dermatitis (ACD) is generally acknowledged. To reduce the diffusion of the Ni-induced ACD the Council Directive 94/27/EC [Council Directive 94/27/EC of 30 June 1994. Official Journal L 188, 22/07/1994, 1.] limited the total Ni content in alloys and its release rate in artificial sweat. In this work, three different aspects were explored: i) the frequency of skin sensitization to Ni-containing earrings in patients before and after the introduction of the Directive's limit; ii) metal composition of alloys by X-ray analysis; iii) metal leaching in artificial sweat followed by Sector Field Inductively Coupled Plasma Mass Spectrometry (SF-ICP-MS) quantification. Well-known allergenic metals, as Ni, Cr and Co, and possible emergent allergens, as Al, Ag, Au, Cd, Cu, Fe, Ir, Mn, Pb, Pd, Pt, Rh, Sn, V and Zn, were studied. Results showed that the frequency of allergy due to earrings did not decrease after the introduction of the Ni limit: in 1994 and in 2005 patients positive to Ni patch tests were 54.3% and 53.5%, respectively. The earring components analyzed were Fe-based or alloys of Cu/Zn or Fe/Cr/Ni, plated with a thin film of precious metal (Ag, Au) which, in several cases, was combined with a Ni layer beneath. Five out of 10 items were not in compliance with the Ni Directive 94/27/EC having a total Ni content >0.05%. In three cases the release of Ni concentrations was higher than the safe sensitizing limit given by the above mentioned Regulation (i.e., <0.5 microg/cm(2)/week). The release of Cu and Zn was very variable among the different pieces (Cu: 0.134-30.9 microg/cm(2)/week; Zn: 0.141-160 microg/cm(2)/week); two objects released high amounts of Fe (358 and 586 microg/cm(2)/week) and one released considerable Mn (21 microg/cm(2)/week). Lead was released from 70% of the objects, while Ag, Al, Cd, Co, Cr and Sn from ca. 30% of the items and concentrations of these elements were well below 0.5 microg/cm(2)/week. Vanadium was released by only one item whereas Au, Ir, Pd, Pt and Rh were never leached.     

Removal of some divalent cations from water by membrane-filtration assisted with alginate

The removal of divalent metal ions from hard waters or galvanic wastewater by polymer-assisted membrane filtration using alginate was investigated. The ability of this natural polymer to form aggregates and gels in presence of metal ions was studied, in order to carry out metal removal by ultra or micro-filtration. Alginate titrations have shown the presence of amine groups in addition to carboxylates onto the polymer backbone. The binding properties of alginate with divalent cations have been studied, showing an increasing affinity for Ca2+ over Mg2+ as polymer concentration increases, and the relative affinity Pb2+ > or = Cu2+ > Zn2+ > Ni2+. The softening of hard natural waters was achieved successfully and easily, but needs an optimal alginate concentration approximately 4 x 10(-2) M. The alginate powder can be directly added to hard waters. Except for Ni2+, metal-removal was efficient. Polymer regeneration has shown that Cu2+-complexes are labiles.     

Heavy metals in the tissues of common dolphins (Delphinus delphis) stranded on the Portuguese coast.

The concentrations of Hg, Sn, Cr, Zn, Ni, Co, Cd, Mn, Fe and Cu were determined in the liver, kidney and muscle of 24 common dolphins stranded on the Portuguese coast between 1995 and 1998. Nitric acid was used to extract the metals from the tissues for analysis by inductively-coupled plasma/atomic emission spectroscopy (ICP/AES). Those metals with relatively higher concentrations included Fe, Zn and Hg, particularly in liver. Other metals including Cr, Ni and Cd tended to show much lower levels, or were even undetected (e.g. Co). Different metals seemed to show different temporal trends, although due to substantial variations of the mean concentrations for each year obtained, such temporal pattern has to be studied further. Total Hg concentration in the kidney, muscle and particularly liver, were higher in females than in males. Total Hg concentrations in all the organs increased with body length of dolphins, whilst those of Zn and Cu in muscle decreased with dolphin length. A strong correlation was found between essential metals Zn and Cu in muscle, possibly resulting from sequestration of these metals by metallothionein. In addition, significant co-associations existed between the same metal (e.g. Hg, Sn and Zn) in different organs.