The effect of surfactants on the extraction-atomic absorption spectrophotometric determination of copper, iron, manganese, lead, nickel, zinc cadmium and cobalt

Nine surfactants representing pure cationic, anionic and non-ionic detergents, three industrially prepared detergents. sodium pyrophosphate. sodium tripolyphosphate, and a soap were investigated for their effect on the extraction-atomic absorption spectrophotometric determination of copper. iron, manganese and lead. Some results are also given for nickel, zinc, cadmium and cobalt. Cations were extracted into 10 ml of MIBK as APDC chelates. To Avoid emulsion formation, maximum concentration of LAS was 1 mg 1⁻¹, and for formulated and non-ionic detergents and washing powders it was 5 mg 1⁻¹.A standard addition procedure was used to obtain correct results for copper and nickel. Two extractions of iron, cobalt and lead, and one extraction of manganese, zinc and cadmium gave a recovery of 100 ± 5%. Soap gave high recoveries for iron and copper. NTA in concentrations up to 25 mg l⁻¹ did not interfere. EDTA in concentrations up to 25 mg l⁻¹ interfered with iron and nickel determinations, but the addition of 3 mg of aluminium removed the EDTA interference in the determination of copper, manganese, lead, zinc, cadmium and cobalt.For the determination of trace metals in polluted natural waters the amount of 4% APDC was increased to 10 ml and for manganese to 25 ml. An addition of 3 mg aluminium as nitrate after the addition of buffer with subsequent 20 min reaction time is required for the determination of all eight metals by the recommended procedures. The effect of humic acid was also investigated.     

Heavy metal removal in anaerobic semi-continuous stirred tank reactors by a consortium of sulfate-reducing bacteria

Removal of heavy metals by an enriched consortium of sulfate-reducing bacteria (SRB) was evaluated through the abundance of SRB, sulfate reduction, sulfide production and heavy metal precipitation. Five parallel anaerobic semi-continuous stirred tank reactors (CSTR, V = 2 L) (referred as R1-R5) were fed with synthetic wastewater containing mixtures of Cu²⁺, Zn²⁺, Ni²⁺, and Cr⁶⁺ in the concentrations of 30, 60, 90, 120, and 150 mg L⁻¹ of each metal and operated with a hydraulic retention time of 20 days for 12 weeks. The loading rates of each metal in R1-R5 were 1.5, 3, 4.5, 6, and 7.5 mg L⁻¹ d⁻¹, respectively. The results showed that there was no inhibition of SRB growth and that heavy metal removal efficiencies of 94-100% for Cu²⁺, Zn²⁺, Ni²⁺, and Cr⁶⁺ were achieved in R1-R3 throughout the experiment and in R4 during the first 8 weeks. The toxic effect of heavy metals on the SRB consortium was revealed in R5, in which no SRB could survive and almost no heavy metal precipitation was detected after four weeks of operation.     

Electrodeposition of six heavy metals on reticulated vitreous carbon electrode

Six heavy metals, copper, cadmium, chromium, lead, uranium and zinc were deposited on cathodes made of a newly developed form of carbon, Reticulated Vitreous Carbon, in a laboratory scale electrochemical reactor. Different metals varied in the extent of their removal with copper depositing 100% at a flow rate of 0.24 cm min⁻¹ in a single pass while it would require a maximum of 20 passes for 100% chromium deposition at a flow rate of 1.8 cm min⁻¹, initial concentrations for both metals being 50 μmol 1⁻¹.Experiments conducted using 0.5 × 10⁻³ M CuSO₄ in 0.5 M Na₂SO₄ supporting electrolyte resulted in a mass transfer coefficient of the order of 10⁻³ cm s⁻¹ and a current efficiency of 64% for the electrodeposition of copper at a cell voltage of 4.0V. Because of very high porosity, 97%, high specific surface area, up to 66 cm² cm⁻³ for RVC grade 100, and useful electrochemical characteristics, RVC can be advantageously used as electrode material for heavy metal removal from dilute industrial effluents.     

Particulate and dissolved trace metals in Lake Ontario

Particulate metal concentrations in the nearshore waters of Lake Ontario have been determined to be 690 ng l⁻¹ for Cu; 40 ng l⁻¹ for Cd; 180 ng l⁻¹ for Ni; 1690 ng l⁻¹ for Zn; 2100 ng l⁻¹ for Mn; and 700 μg l⁻¹ for Fe. These values are considerably higher than the particulate metal concentrations in the offshore waters: 130, 8, 34, 230, 110, 260 and 9000 ng l⁻¹ for Cu, Cd, Ni, Zn, Pb, Mn and Fe respectively. In general, 50–80% of the Cu, 10–40% of the Ni, 20–60% of the Cd and >60% of the Pb in the lake water were bound to the suspended particulates. From the standing crop of the particulate metals and the estimated rates of their deposition on the lake bottom, the residence times of the particulate metals in the lake water column have been estimated to be about 0.5 yr. on the average. The suggestion is made that particulate organic matter may be an important vehicle for metal transport to the Lake Ontario sediments.     

Effects of manganese, copper and lead on Selenastrum capricornutum and Chlorella stigmatophora

Algal assays were conducted to observe the responses of Selenastrum capricornutum and Chlorella stigmatophora to the metals manganese, copper and lead, added singly or in combination to both artificial media and natural waters. A 50% reduction in the total algal cell volume of Selenastrum in standard algal assay medium (SAAM) occurred by the addition of either 3.1 mg manganese 1⁻¹ 85 μg copper 1⁻², or 140 μg lead 1⁻¹. For Chlorella grown in 28 ppt artificial seawater plus full SAAM nutrients, the corresponding numbers were 50mg manganese 1⁻¹, 70 μg copper 1⁻¹ or 700 μg lead 1⁻¹. Of the metals tested, only lead was found in higher concentrations in urban and agricultural runoff than at least one of these levels.Theoretical considerations show that a product model is a more reasonable reference for no-interaction than an additive model for experiments in which toxic metals are added in combination. Combination experiments, in which any combination of the three metals act at the same time, indicate (1) synergism between manganese and copper, (2) antagonism between manganese and lead, and (3) antagonism between copper and lead. As to the manganese-lead interaction, it is shown that the lead-induced inhibition of cell division is offset, partially for Selenastrum and completely for Chlorella by the addition of manganese.     

Accumulation de quelques metaux lourds (Cd, Cu, Pb et Zn) chez l'eperlan (Osmerus mordax) preleve sur la rive Nord de l'Estuaire du Saint-Laurent

Heavy metals in trace amounts are normal constituents of marine organisms. At sufficiently high concentrations, heavy metals are toxic to living organisms and so it is important to know by how much their concentration may be increased before effects on marine or estuarine populations can be detected or commercial species become unsuitable as food. A method of removing metals is by storage in a particular tissue. Several different sites for storing metals were investigated and concentrations of Cd, Cu, Pb and Zn were examined in muscle, liver and gonads of the smelt (Osmerus mordax) from the North shore of the St Lawrence estuary. Copper and zinc are constituents of several enzymes and are absolutely essential for normal growth and development, while cadmium and lead are not known to have necessary physiological function. A modified wet digestion procedure was used to prepare biological samples for the determination of trace elements by flameless atomic absorption spectrophotometry procedure, using calibration standards made up in a matrix of similar acidity (Table 1). NBS reference material bovine liver was analyzed along with the samples and the results were within the specified tolerance (Table 2). Analyses were reported on a dry weight basis (Table 3) and the correlations with total body weight were determined by regression analysis. Copper (range 0.3–3.3 μg g⁻¹) and zinc (range 19–38 μg g⁻¹) in muscle fillets were found to be negatively correlated with total body weight (Fig. 1). Apparent decreasing concentrations in these two metal levels in muscle sample with increasing body weight were possibly due to factor such as dilution with growth. Growth may dilute metal concentrations in an organism if tissue is added faster than metal. Livers and gonads contained greater levels of the four metals than somatic muscle. Liver metal concentrations of Zn (range 29–108 μg g⁻¹) and Cd (range 0.06–0.37 μg g⁻¹) increased with total body weight. All equations fit data at P < 0.01 (Fig. 2). Positive correlations between size and metal concentrations suggest that net uptake may occur. Inessential, slowly exchanging metals such as Cd appear to reflect an uptake which tend to become a cumulative process (age dependence of concentrations). The occurrence of insignificant correlation between liver concentrations of Cu (mean value: 4 μg g⁻¹) and environmental concentrations of this metal was consistent with equilibration. Since fish are known to possess the metal binding protein metallothionein, a sequestering agent, detoxification of these metals in fish liver may be by sequestration rather than elimination. Increasing metal concentrations in liver may represent storage of sequestered products in that organ. In the gonads, no significant relationship exists between total body weight and trace metal contents. Results of t-test indicated that females had significantly greater Cu and Zn concentrations, but no significant difference existed between males and females for Cd concentrations (Figs 3 and 4). Thus, the relation between concentration and total body weight appears to be specific as to the species, tissues analyzed and environmental conditions. The comparison of metal concentrations in fish to assess variations in contamination levels requires understanding the relationship between metal concentration and body size within each population.     

Zinc, cadmium and lead in water, sediments and submerged plants of the Derwent Reservoir, Northern England

A partial budget is presented of the zinc, cadmium and lead entering the Derwent Reservoir. The mean levels in the water column upstream of the site of inflow are: Zn, 0.216 mg 1⁻¹ ; Cd, 0.003 mg 1⁻¹; Pb, 0.065 mg 1⁻¹; the levels after passage through the 4.1 km² reservoir fall by: Zn, 70.3%; Cd, 98.3%; Pb, 89.2%. Most of these metals are deposited in sediments, the mean values for which are: Zn, 1035 μg⁻¹; Cd, 13μg⁻¹; Pb, 827μg⁻¹. Lead, a higher percentage of which occurs as particulate material, is deposited more rapidly than zinc; this effect is especially obvious when streaming of colder water along the bottom of the reservoir takes place at the time of floods. Macroscopic plants are only occasional in this reservoir, due perhaps in part to heavy metal toxicity. Of the two most common submerged species, Nitella flexilis probably accumulates almost all of its metal content directly from the water, but the data suggest that sediments are a source of some of the heavy metals accumulated by Glyceria fluitans.     

Current and historic mercury deposition to New Haven Harbor (CT, USA): Implications for industrial coastal environments

This study quantifies historic and current mercury contamination in New Haven Harbor (New Haven, Connecticut, USA) through the analysis of sediment cores. The mercury concentration measured in surface sediment ranged from 320 to 1640 μg kg^− 1 with an average of 530 μg kg^− 1. The harbor is relatively small in area (6.6 km²) but displays a large range in concentrations, illustrating the important methodological issue that a large number of samples may be necessary to capture the variability in even a small area. Depth profiles of mercury reflect sedimentation over a range of 20 to 200 years and indicate a complex history of contamination. Mercury depth profiles were compared with lead, copper, cadmium, and silver concentrations and the metals generally covary. This trend indicates that the sources of mercury and heavy metals are linked and that regionally specific sources dominate the historic input of metals rather than large-scale atmospheric deposition patterns. Results also show there are large differences in absolute concentrations of metals among sites in the harbor. Differences in the abundance of Fe-rich, fine-grained sediment likely control the level of metals in various parts of the harbor. Proximity to current sources and the long, diverse industrial history of the harbor also influence the distribution pattern. All of the cores can be modeled as mixing between pre-industrial sediments and either one or two pollution endmembers. This study demonstrates the importance of riverine sources in the mass balance of mercury delivered to coastal areas and of watershed management to preserve coastal ecosystems.     

Influence of toxic metals on the repression of carbonaceous oxygen demand

Toxic metals like lead, bismuth, mercury and zinc-aranyl have been found to repress the carbonaceous oxygen demand. The biological seed was developed from trade waste of Glaxo Laboratories. Three concentrations: 5, 10 and 15 mg 1⁻¹ of the metals were used to observe repression of carbonaceous oxygen demand of amino acid, methionine, used as substrate. Rate constants, ratios of (t/y)^1.3 and COD: BOD were computed.     

Modeling metal bioaccumulation in a deposit-feeding polychaete from labile sediment fractions and from pore water

Estuarine sediments are often highly enriched in particle-reactive metal contaminants and because aquatic animals have often been shown to acquire metals predominantly from their diet, benthic animals feeding on deposited or resuspended sediments may also accumulate metals through this uptake pathway. Laboratory experiments were performed in which the surface deposit-feeding polychaete, Nereis succinea, was exposed to As(+ 5), Cd, and Cr(+ 3) in pore water or in estuarine sediments with and without enrichment with algal debris. These experiments generated metal uptake parameters (assimilation efficiency of ingested metal [AE], uptake rate constant of dissolved metal, efflux rate constants following dietary or aqueous metal exposures) used in a kinetic model of metal bioaccumulation. The model showed that > 97% of the body burden of these metals is accumulated through ingested sediment. The kinetic model was further modified to consider the geochemical fractionation of the metals in the sediments because metals bound to some fractions were shown to be unavailable to these polychaetes. The modified model substituted the AE term for each metal by the percentage of metal extracted in neutral and weak acid exchangeable fractions (termed “carbonex” fraction) multiplied by the slope of the regression between the metal AE and its fractionation in carbonex. The modified model generated predictions of As, Cd, and Cr body burdens in polychaetes at three different estuarine sites that matched independent field observations at these sites (r² = 0.84 for sediments without organic enrichment, r² = 0.87 with organic enrichment). Model predictions that relied on total metal concentrations showed weaker relationships (r² = 0.11-0.50). This study adds to the evidence for the dominance of dietary uptake of metals in aquatic animals and identifies a key sedimentary fraction of metals that can account for bioavailability of sediment-bound metals.     

Accumulation de quelques metaux lourds (Cd,Cu, Pb et Zn) chez l'eperlan (Osmerus mordax) preleve sur la rive Nord de l'Estuaire du Saint-LaurentHeavy metal accumulation (Cd,Cu, Pb and Zn) by smelt (Osmerus mordax) from the North shore of the St Lawrence estuary

Heavy metals in trace amounts are normal constituents of marine organisms. At sufficiently high concentrations, heavy metals are toxic to living organisms and so it is important to know by how much their concentration may be increased before effects on marine or estuarine populations can be detected or commercial species become unsuitable as food. A method of removing metals is by storage in a particular tissue. Several different sites for storing metals were investigated and concentrations of Cd, Cu, Pb and Zn were examined in muscle, liver and gonads of the smelt (Osmerus mordax) from the North shore of the St Lawrence estuary. Copper and zinc are constituents of several enzymes and are absolutely essential for normal growth and development, while cadmium and lead are not known to have necessary physiological function. A modified wet digestion procedure was used to prepare biological samples for the determination of trace elements by flameless atomic absorption spectrophotometry procedure, using calibration standards made up in a matrix of similar acidity (Table 1). NBS reference material bovine liver was analyzed along with the samples and the results were within the specified tolerance (Table 2). Analyses were reported on a dry weight basis (Table 3) and the correlations with total body weight were determined by regression analysis. Copper (range 0.3–3.3 μg g^?1) and zinc (range 19–38 μg g^?1) in muscle fillets were found to be negatively correlated with total body weight (Fig. 1). Apparent decreasing concentrations in these two metal levels in muscle sample with increasing body weight were possibly due to factor such as dilution with growth. Growth may dilute metal concentrations in an organism if tissue is added faster than metal. Livers and gonads contained greater levels of the four metals than somatic muscle. Liver metal concentrations of Zn (range 29–108 μg g^?1) and Cd (range 0.06–0.37 μg g^?1) increased with total body weight. All equations fit data at P < 0.01 (Fig. 2). Positive correlations between size and metal concentrations suggest that net uptake may occur. Inessential, slowly exchanging metals such as Cd appear to reflect an uptake which tend to become a cumulative process (age dependence of concentrations). The occurrence of insignificant correlation between liver concentrations of Cu (mean value: 4 μg g^?1) and environmental concentrations of this metal was consistent with equilibration. Since fish are known to possess the metal binding protein metallothionein, a sequestering agent, detoxification of these metals in fish liver may be by sequestration rather than elimination. Increasing metal concentrations in liver may represent storage of sequestered products in that organ. In the gonads, no significant relationship exists between total body weight and trace metal contents. Results of t-test indicated that females had significantly greater Cu and Zn concentrations, but no significant difference existed between males and females for Cd concentrations (Figs 3 and 4). Thus, the relation between concentration and total body weight appears to be specific as to the species, tissues analyzed and environmental conditions. The comparison of metal concentrations in fish to assess variations in contamination levels requires understanding the relationship between metal concentration and body size within each population.     

Characterization and treatment of condensates from high efficiency appliances

In order to characterize the condensate waste stream from experimental high efficiency heaters and a pulse combustion furnace, samples were analyzed for total solids, pH, acidity, alkalinity, nitrate, nitrite, sulfate and selected metals, and were screened for semivolatile organic priority pollutants, including phenols and polynuclear aromatic hydrocarbons. A typical condensate has a pH of approx. 4, contains quantities of nitrites (1–8 mg l^?1 as N), nitrates (0.4–15 mg l^?1 as N), sulfates (3–10 mg l^?1) and may contain metals dissolved from the condensing surfaces of the appliance. No priority pollutant compounds were found in the condensate samples. Calcium carbonate (calcite) was used in testing the potential of a lab-scale column and a prototype treatment unit to neutralize acidity and precipitate metals in condensates from the pulse combustion furnace prior to disposal of the waste product to the residential wastewater system. Limestone neutralization effectively reduces condensate acidity and increases alkalinity and pH. The effectiveness of the test column and prototype treatment unit for precipitation and removal of high levels of metals from the condensate will require additional testing.     

On the potential of combining neutron activation analysis and particle induced X-ray emission (PIXE) for micro- and microdistribution analysis of hard metals in human tissues

Tungsten carbide and cobalt are the main components of hard metal alloy while other metals such as chromium, niobium, tantalum, titanium and vanadium are sometimes added in smaller amounts. Exposure to hard metal dusts can induce a lung fibrosis with cobalt playing a major role. In order to provide information on the role that each metal may have in causing this disease, determination of the total content and the distribution of inhaled metals in lung tissue of hard metal workers is of paramount importance. However, samples such as transbronchial biopsy and bronchoalveolar lavage (BAL), often used in the medical diagnosis of pneumoconiosis, only allow for a small amount of material. This calls for sensitive and accurate analytical procedures for microdetermination and distribution of metals in pulmonary tissue and cellular material, such as macrophages. This work proposes a combination of sophisticated analytical techniques such as neutron activation analysis (NAA), currently applied to the determination of the total concentration of more than 30 elements in biological specimens, and PIXE analysis, particularly microPIXE, which has a great potential for microdistribution analysis in small biological samples. Principles and perspectives for the combined use of these techniques for the analysis of human tissue are outlined and discussed. NAA: determination of hard metals in lung tissue are carried out by neutron irradiation (2 × 10¹⁴ neutrons cm⁻² s⁻¹) in the HFR reactor of Petten. After neutron activation, radiochemical separations of ⁶⁰Co, ¹⁸⁷W, ¹⁸²Ta, ⁵¹Cr followed by computer-based high resolution gamma ray spectrometry allow the measurement of these elements in pulmonary tissues with sensitivities ranging from 10⁻⁴ μg (Cr) to 10⁻⁶ μg (W). PIXE: this technique is multielemental and of relatively high sensitivity (μg/g) even in small total sample masses of from 10 to 100 μg, thus allowing the analysis of parts of needle biopsies. Whereas PIXE has been successfully applied to many medical problems, its usefulness is limited in the total samples analysis for cobalt-related hard metal disease, due to the low levels of cobalt in tissue combined with severe element interferences from the generally more abundant metal, iron. Nevertheless, microPIXE, a special variety of the method scanning over the sample with a focussed ion beam of about 2 × 2 μm², could complement the NAA findings in total samples in the sense of achieving a microdistribution analysis of hard metals (including cobalt) in suitable thin tissue sections.The availability of specialized facilities at the JRC such as the powerful HFR reactor (Petten), the NAA laboratories (Ispra) and the microPIXE facility (Geel) could represent a European ‘reference pole’ for the study of metals in tissues of hard metal diseased subjects.     

The determination of cadmium. lead, copper and zinc in ground water, estuarine water, sewage and sewage effluent by anodic stripping voltammetry

Anodic stripping voltammetry (ASV) using the thin-film mercury electrode was shown to be a successful technique for the determination of total (free plus complexed) trace metal concentrations in various types of aqueous sample. The method developed involved the minimum of sample treatment and required only simple and inexpensive equipment. The practical limit of sensitivity was about 0·1 μg I⁻¹ for cadmium, lead and copper. The determination of zinc was found to be complicated by the formation of an intermetallic compound with copper. Interference by other trace metals and by complexing agents was investigated. Photochemical oxidation for the decomposition of complexes of the metals with organic ligands in filtered sewage and sewage effluent was found to be successful, although the process is slower for cadmium than for the other metals. Good agreement with atomic absorption spectroscopy was obtained for all the types of aqueous sample investigated. Possible improvements of the ASV technique are discussed.     

Role of bacterial extracellular polymers in metal uptake in pure bacterial culture and activated sludge—I. Effects of metal concentration

A gel filtration technique afforded a good separation between metal complexed with bacterial extracellular polymers and free metal ions. The complexation of polymers extracted from cultures of Klehsiella aerogenes and activated sludge with cadmium, nickel, manganese and cobalt was demonstrated. The extraction of extracellular polymers from cultures of K. aerogenes and activated sludge reduced the capacity of the cells and flocs to adsorb metal. Adsorption and complexation of metals by cells of K. aerogenes and extracellular polymers extracted from activated sludge were fitted to Freundlich equilibrium isotherms. Saturation of activated sludge polymer binding sites occurred at 10 mg 1^?1 metal additions for all the metals studied except manganese which was complexed to a very limited extent. Cells of K. aerogenes exhibited no saturation effects in the range of metal concentrations studied.Precipitation of metals below a concentration of 1 mg 1^?1 was minimal, with the exception of cadmium precipitation. At a concentration of 10 mg 1^?1, precipitation of cadmium, cobalt and manganese may have been the major mechanism of metal removal. The more soluble metals generally displayed the lowest removals. Concentrations of extracellular polymers and soluble chelating agents may be important in controlling removals of metals which are largely soluble in activated sludge.     

Assessment of heavy metals contamination and its effects on oyster (Saccostrea cucullata) biometry parameters in the Asaluyeh port coasts,Persian Gulf,Iran

The current study examines biometric parameters and concentration of some heavy metals in soft tissues of Saccostrea cucullata in the Asaluyeh coast, Persian Gulf, Iran. The metals concentration in the soft tissue of the Saccostrea cucullata ranged as: Zn: 765–3411 mg kg^?1, Cu: 120.3–580.6 mg kg^?1, Cd: 0.13–3.5 mg kg^?1, As: 0.39–3.3 mg kg^?1, Pb: 0.05–1.64 mg kg^?1, Ni: 0.02–0.44 mg kg^?1, V: 0.06–0.32 mg kg^?1, Cr: 0.02–0.16 mg kg^?1 and Hg: 0.002–0.068 mg kg^?1. The results showed that the concentration of total heavy metals in oysters of the control station (CA) is usually lower. The results also indicated lack of correlation between oyster biometric parameters and bioaccumulated heavy metals, except between Cu and longitudinal diameter (R = 0.77). The concentration of heavy metals is higher than limits recommended by the World Health Organization, except for Cd and Pb.     

Behavior of Mn, Fe, Cu, Zn, Cd and Pb discharged from a wastewater treatment plant into an estuarine environment

To obtain information on the fate of trace metals discharged to an estuarine environment, analyses have been made on water and sediment samples from Back River, MD., and on effluent from the large wastewater treatment plant that discharges there. Within 2–3 km of the outfall, the concentration (in μg 1⁻¹) of all metals decreases as follows: Mn, > 120-90; Fe, > 570-300; Cu, 53-7; Zn, 280-9; Cd, 3.5-0.5 and Pb, 31-<4. Except possibly for Mn and Fe, these decreases are much greater than can be ascribed to simple dilution, so physical, chemical or biological processes must be removing metals to the sediments. Correspondingly, sediment concentrations of Cu, Zn, Cd and Pb are approximately one order of magnitude higher than normally found in uncontaminated areas. After the initial decrease, concentrations of Mn and Cd in the water begin to rise again, suggesting remobilization from the sediments. Comparison of the estimated annual discharge of 8 trace metals to the Chesapeake Bay from wastewater treatment plants and from rivers suggests that the wastewater input may be within one order of magnitude of the fluvial input for Cr, Cu, Zn, Cd and Pb. Of the metals studied, Cd presents the greatest potential for serious pollution because its input from wastewater probably exceeds fluvial input, it appears to be readily remobilized from sediments, and it is known to be toxic to many organisms.     

Removing metals from waste solutions with low rank coals and related materials

Ion exchange media were produced by contacting brown coal, peat or wood sawdust with a solution of calcium hydroxide, preferably as an aqueous slurry of lime. The resultant calcium loading on the media, which ranged up to 8% for sawdust, 12% for peat and to 19% for brown coal, was exchanged for many metals in solution.Preliminary work showed the method to be amenable to extraction of copper, nickel, chromium, cadmium, lead, zinc, mercury, cobalt, silver, iron, manganese, vanadium, germanium, gallium, aluminium, antimony and uranium. For most of the metals more than 99% was removed from I g 1⁻¹ solutions.In more detailed work, confined to calcium loaded brown coal and solutions having metal concentrations more typical of industrial operations, minimum residual metal concentrations of 0.0005 mg l⁻¹ mercury; 0.02 mg 1⁻¹ copper; 0.02 mg 1⁻¹ zinc; <0.05 mg l⁻¹ cadmium; 0.1 mg 1⁻¹ lead and 0.2 mg l⁻¹ manganese were obtained. These results compare favourably with those reported for other relevant processes and there might be operational advantages in the method.The method can be applied either by agitating the calcium loaded media in the solution and then filtering, or by passing the solution through packed beds of the media. Where appropriate, dilute solutions can be up-graded for re-use by stripping the metals from the media which can also be re-used. Alternatively, the loaded media can be combusted and the metals recovered from the residues.The method might be applicable to mine drainage and to effluents from metallurgical processing and electroplating, but more work is required to assess costs.It is suggested that the method is environmentally preferable to other common effluent treatment procedures because it enables collection and recycling of heavy metal pollutants.     

Speciation (including adsorbed species) of copper, lead, nickel and zinc in the Meuse River: Observed results compared to values calculated with a chemical equilibrium computer program

The adsorption of trace metals on sediments of the Meuse River was interpreted in terms of competition between metals and protons for surface sites. Surface constants (^*β₁^surf) were determined for Cu, Zn and Cd (10^−1.8, 10^−3.6 and 10^−3.7). The constants for Pb, Ni, Ca and Mg (10^−1.7, 10^−3.8, 10^−6.5 and 10^−5.2) were estimated using a correlation between hydrolysis and surface constants. A chemical equilibrium computer program in which surface sites (for adsorption reactions) are treated as conventional ligands was used to calculate the speciation of Cu, Pb, Ni and Zn in the Meuse River. Calculated values of the adsorbed/dissolved distribution agreed well with observed values, after some realistic data manipulation. This work indicates that dissolved trace metal concentrations in the Meuse River are controlled by adsorption and not by precipitation mechanisms. The relationship between organic matter and suspended matter greatly influences the adsorption of metals like Cu and Pb.     

Role of bacterial extracellular polymers in metal uptake in pure bacterial culture and activated sludge—II Effects of mean cell retention time

A gel filtration technique afforded a good separation between metal complexed with bacterial extracellular polymers and free metal ions. The complexation of polymers extracted from cultures of Klehsiella aerogenes and activated sludge with cadmium, nickel, manganese and cobalt was demonstrated. The extraction of extracellular polymers from cultures of K. aerogenes and activated sludge reduced the capacity of the cells and flocs to adsorb metal. Adsorption and complexation of metals by cells of K. aerogenes and extracellular polymers extracted from activated sludge were fitted to Freundlich equilibrium isotherms. Saturation of activated sludge polymer binding sites occurred at 10 mg 1⁻¹ metal additions for all the metals studied except manganese which was complexed to a very limited extent. Cells of K. aerogenes exhibited no saturation effects in the range of metal concentrations studied.Precipitation of metals below a concentration of 1 mg 1⁻¹ was minimal, with the exception of cadmium precipitation. At a concentration of 10 mg 1⁻¹, precipitation of cadmium, cobalt and manganese may have been the major mechanism of metal removal. The more soluble metals generally displayed the lowest removals. Concentrations of extracellular polymers and soluble chelating agents may be important in controlling removals of metals which are largely soluble in activated sludge.