Transformation of metals speciation in a combined landfill leachate treatment

Landfill leachate was treated by a combined sequential batch reactor (SBR), coagulation, Fenton oxidation and biological aerated filter (BAF) technology. The metals in treatment process were fractionated into three fractions: particulate and colloidal (size charge filtration), free ion/labile (cation exchange) and non-labile fractions. Fifty percent to 66% Cu, Ni, Zn, Mn, Pb and Cd were present as particulate/colloidal matter in raw leachate, whereas Cr was present 94.9% as non-labile complexes. The free ion/labile fractions of Ni, Zn, Mg, Mn, Pb and Cd increased significantly after treatment except Cr. Fifty-nine percent to 100% of Al was present mainly as particulate/colloidal matter > 0.45 μm and the remaining portions were predicted as non-labile complexes except in coagulation effluent. The speciation of Fe varied significantly in various individual processes. Visual MINTEQ simulation showed that 95-100% colloidal species for Cu, Cd and Pb were present as metal-humic complexes even with the lower dissolved organic carbon. Optimum agreements for the free ion/labile species were within acidic solution, whereas under-estimated in alkaline effluents. Overestimated particulate/colloidal fraction consisted with the hypothesis that a portion of colloids in fraction < 0.45 μm were considered as dissolved.     

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.     

Distribution of species of Cu, Pb, Zn and Cd in a water profile of the Yarra river estuary

The behaviour of Cu, Pb, Zn and Cd in a highly stratified estuary was examined. The distribution of ionic and ‘organically bound” forms of the metals was determined by differential pulse anodic stripping voltammetry (dpasv) before and after u.v. irradiation. The two forms of the metals were compared with the water characteristics of salinity, temperature, turbidity, flow, and inorganic and organic carbon.Irradiation increased the concentration of all four elements detectable by dpasv. The greatest increase was for Cu in the 1 m depth river water which yielded 7.5 μg l⁻¹ before irradiation and 29 μg l⁻¹ after irradiation. Cu and Cd showed minimum concentrations in the seawater layer at 4 m depth, corresponding to the fresh seawater flowing upstream below the halocline. The concentrations of Cu and Cd were higher in the river water than in the underlying seawater. Zn concentration in the river water was lower than in the seawater. Relationships between the trace metal concentrations and the characteristics of the water column are not clear, but the direction of water movement is a major influence.     

Physico-chemical speciation of selected metals in the treated effluent of a lead-acid battery manufacturer and in the receiving river

A scheme for the speciation of metals in freshwaters has been applied to the metals Pb, Cd, Cu, Fe and Mn in the treated effluent of a lead-acid battery manufacturer and the receiving river upstream and downstream of the effluent outfall. The speciation is inferred from measurements of the size-associations of the metals, the lability with respect to anodic stripping voltammetry and Chelex resin and by u.v. irradiation to destroy organic complexing agents. The results are related to chemical and physical interactions within the waters and are discussed in terms of the impact of the effluent discharge upon the receiving river.     

Determination and speciation of copper and lead in sediments of a Mediterranean river (River Tenes, Catalonia, Spain)

Total concentrations of Cu and Pb and the speciation of these metals in sediments of the River Tenes are studied in order to establish the extent to which they are polluted and their capacity of remobilization. Five samples taken along the river were analyzed, major components of the sediments were studied using XRF and total Pb and Cu content were determined by AAS. In order to test the accuracy of the digestion methods used (triacid attack with nitric, perchloric and hydrofluoric acids or diacic attack with nitric and hydrochloric acids) for the determination of total trace metal, a standard reference material was also analyzed. Triacid attack is proposed to obtain good results. The results show a highly polluted area (1556 mg kg⁻¹ Cu and 1555 mg kg⁻¹ Pb) in the last sampling site analyzed. For metal speciation, the sequential scheme of Tessier et al. was used. From the results obtained, it can be concluded that Cu content in non-residual fraction is bonded mainly to organic matter, whereas non-residual Pb is mainly associated to iron and manganese oxides.     

Distribution and transport of sediment-bound metal contaminants in the rio grande de tarcoles, costa rica (Central America)

A reconnaissance survey of the extent of metal contamination in the Rio Grande de Tarcoles river system of Costa Rica indicated high levels of chromium (Cr) in the fine-grain bed sediments (<60 μm) of tributaries downstream from leather tanneries (50–83 times Cr background or 3000–5000 μg/g). In the main channel of the river downstream of the San Jose urban area, Cr contamination in sediments was 4–6 times background and remained relatively constant over 50 km to the mouth of the river. Sediments from a mangrove swamp at the river mouth had Cr levels 2–3 times above background. Similar patterns of dilution were observed for lead (Pb) and zinc (Zn) sediment contamination, although the contamination levels were lower. The high affinity of Cr towards particulate phases, probably as Cr(III), allows the use of Cr contamination levels for delineating regions of deposition of fine-grained sediments and dilution of particle associated contaminants during transport and deposition.     

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.     

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.     

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.     

Behavior of Fe, Mn, Cu and Cd in the duwamish river estuary downstream of a sewage treatment plant

The behavior of dissolved Fe, Mn, Cu and Cd in the Duwamish River downstream of a sewage treatment plant located near Seattle, Washington, was investigated in three distinct zones: (1) immediately downstream of the effluent outfall, (2) further downstream in the freshwater portion of the river and (3) in the estuarine mixing zone. A three-end-member tracer model utilizing salinity and dissolved inorganic nitrogen was developed to distinguish physical mixing processes from biogeochemical reactions. The results of this investigation indicate that Fe was removed from the dissolved phase onto particulates near the plant. Although no additional reactions controlled the distribution of dissolved Fe, Mn and Cu in the freshwater portion of the river, Cd was removed from the dissolved phase. In the estuarine mixing zone, a significant fraction of the dissolved Fe and Cu was removed from solution, while Mn and Cd desorbed from particulates. The chemical forms of the trace metals rather than their sources appear to determine their participation in these reactions.     

Effects of naturally occurring aquatic organic fractions on cadmium toxicity to Simocephalus serrulatus (daphnidae) and Gambusia affinis (poeciliidae)

Cadmium toxicity to Simocephalus serrulatus and Gambusia affinis in soft well water, highly organic pond water and well water containing various sized organic fractions isolated from pond water was determined and compared to Cd binding capacity of each water type. Pond organics were separated into three nomial molecular diameter fractions (> 0.0183 μm; 0.0183 < > 0.0032 μm; 0.0032 < > 0.0009 μm) using ultrafiltration. Cadmium binding capacity was determined using selective ion electrodes. Pond water and organic fractions bound Cd. reducing the amount of free Cd²⁺ as determined by Cd selective ion electrode. Whole pond water reduced Cd toxicity to S. serrulatus but had little effect on Cd toxicity to G. affinis. The three larger molecular diameter organic fractions reduced Cd toxicity to S. serrulatus, while the smallest fraction slightly increased Cd toxicity. Cadmium 96 h LC₃₀ values cannot be predicted from Cd binding capacities determined by selective ion electrode.     

Seasonal changes in the forms and species of iron and manganese in a seasonally-inundated floodplain swamp

The forms and species in which Fe and Mn occurred in a seasonally-inundated Southeastern United States floodplain swamp were examined. The analytical scheme provided operational estimates of the concentrations of Fe(II), Fe(III) and Mn in particulate (> 0.45 μm), colloidal (0.45-0.0032 μm) and ultrafilterable (<0.0032 μm) size fractions. The procedure also provided a differentiation between forms of Fe that were readily reactive to bathophenanthroline (BPN) and those forms that were unreactive to BPN until undergoing acid extraction. Further, the concentrations of Fe and Mn associated with suspended particulate matter in ion-exchangeable, reducible, and oxidizable forms and as inert mineral were determined using an operational classification scheme.The ferric species predominated due to the oxygenated conditions of the swamp water. Concentrations of colloidal-sized, readily-reducible Fe and of ultrafilterable Fe(II) and Fe(III) were low (<0.25 mg 1⁻¹) and fairly constant throughout the study; more Fe occurred in the colloidal than ultrafilterable size range. The majority of the colloidal-sized Fe was in an acid-extracted form. Almost all ultrafilterable Fe was ferric, although high Fe(II) concentrations occurred in floodplain soil pore water. Total Fe, mainly particulate-associated, varied with periods of flooding and intense bioturbation. Manganese occurred in low concentrations, primarily in the ultrafilterable fraction, although colloidal-sized Mn forms were important at times. Most of the Fe and Mn associated with suspended particulates occurred in the inert mineral form and to a lesser extent in a reducible form. Ion-exchangeable and oxidizable particulate Fe and Mn were relatively unimportant.     

Aspects of the aquatic chemistry of cadmium and zinc in a heavy metal contaminated lake

Concentrations of the heavy metals cadmium (Cd) and zinc (Zn) were determined at several sites in Palestine Lake, Indiana, and in the stream (Williamson Ditch) which transports metal-bearing wastes to the lake. Average dissolved Cd and Zn concentrations in the lake were as high as 17.3 μg 1^-1 and 293 μg 1^-1, respectively, while corresponding suspended levels were 30.3 μg Cd 1^-1 and 270 μg Zn 1^-1. Average levels of both Cd and Zn in the dissolved fraction exceeded those in the suspended fraction, except at one site in the lake where suspended Cd was higher. During anaerobic conditions occurring in lake's hypolimnion, a marked decrease in the dissolved fraction and concomitant increase in the suspended fraction of both Cd and Zn were noted. A cadmium-specific ion electrode was used to determine the chemical forms of dissolved Cd present in the lake. Free Cd²⁺ was the dominant form; however, Cd-organic complexes sometimes comprised a significant portion of the total dissolved Cd.     

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.     

Bioleaching of metals from sewage sludge: Microorganisms and growth kinetics

Microbial leaching is one of the advantageous methods of removing heavy metals from sewage sludge, however, the microbiological aspects of this technology have not been studied. This study presents the characterization of the naturally occurring microorganisms, responsible for the metal leaching activity, in 21 different sewage sludges. The results obtained indicate that the bioleaching of metals is carried out by successive growth of less-acidophilic and acidophilic thiobacilli. Several species of less-acidophilic thiobacilli participate in the sludge acidification, but Thiobacillus thioparus is the most important species. In contrast, Thiobacillus thiooxidans seems to be the only species involved in the acidophilic group of thiobacilli. The growth kinetics of the two groups of thiobaciili was followed in five different sewage sludges. After 5 days of incubation in shake flasks, the pH of the sludge was decreased to about 2.0 and this pH decrease solubilized the toxic metals (Cd: 83–90%; Cr: 19–41%; Cu: 69–92%; Mn: 88–99%; Ni: 77–88%; Pb: 10–54%; Zn: 88–97%). The maximum specific growth rate (μ_max) for the less-acidophilic thiobacilli varied between 0.079 and 0.104 h⁻¹ and that for the acidophilic thiobacilli varied between 0.067 and 0.079 h⁻¹.     

Lead and cadmium composition in indoor dust

Pb and Cd levels in different size fractions of indoor dust have been analyzed by differential pulse anodic stripping voltammetry (DPASV) after digestion with HNO₃ and HF using a microwave oven. The relationship between Pb and Cd levels with dust size have been investigated and the metal levels in different sources of indoor dust are compared. In addition, the Pb and Cd composition in different size fractions of dust have been investigated by a sequential extraction method. Dusts are dominated by particulate matter < 500 μm. Pb levels in office dust in the particulate fraction > 75 μm are clearly shown to be higher than that in domestic dust. Generally, for domestic premises, Pb and Cd levels increase with a decrease in the particle size and with an increase in house age, while for office dust, the Pb level increases with an increase of particle size. For domestic houses, most of the metals are bound to carbonate and FeMn oxides in fine dust. For office dust, the situation is more complicated, with a clear increase in Pb in the organic and residue fractions in coarse dust.     

Influence of pH and TOC concentration on Cu,Zn, Cd,and Al speciation in rivers

Dissolved ( < approximately 4 nm, dialysis in situ), colloidal ( < 0.45 microm filtered, minus dissolved) and particulate (total, minus < 0.45 microm filtered) concentrations of Cu, Zn, Cd, (Al) in eight (three) mining polluted rivers were determined by atomic absorption spectrometry (flame and graphite furnace). The metal size distribution in the rivers was compared to pH, Ca concentration, alkalinity, conductivity, and total organic carbon (TOC). Data plots based on the present and other studies also yielded information about the interrelations between TOC, pH and metal adsorption in rivers and lakes. Less than 10% of Cu, Zn, and Cd were sorbed on particles or colloids in two rivers with average pH at 3.1 and 5.1, whereas 46%, 21%, and 21% of Cu, Zn, and Cd, respectively, occurred in sorbed form in six pH neutral rivers. In three pH neutral rivers, on average 55% of Al was in colloidal form, whereas the dissolved and particulate fractions were 21% and 23%, respectively. Our data combined with data from similar studies support conclusions from other research suggesting that the percent fraction of metals adsorbed on particles rises steeply from almost zero to nearly 100% within a narrow and element specific pH range. Changes in TOC concentration seem capable of shifting the pH to % metal absorption curves in the order of one pH unit.     

Total metal concentrations and partitioning of Cd, Cr, Cu, Fe, Ni and Zn in sewage sludge

Application of the BCR three-step sequential extraction procedure to sewage sludge samples collected at an urban wastewater treatment plant (Dom ale, Slovenia) is reported. The total concentrations of Cd, Cr, Cu, Fe, Ni and Zn and their concentrations in fractions after extraction were determined by flame or electrothermal atomic absorption spectrometry (FAAS, ETAAS) under optimised measurement conditions. Total acid digestion including hydrofluoric acid (HF) treatment and aqua regia extraction were compared in order to estimate the efficiency of aqua regia extraction for determination of total metal concentrations in sewage sludge. It was found experimentally that aqua regia quantitatively leached these heavy metals from the sewage sludge and could therefore be applied in analysis of total heavy metal concentrations. The total concentrations of 856 mg kg⁻¹ Cr, 621 mg kg⁻¹ Ni and 2032 mg kg⁻¹ Zn were higher than those set by Slovenian legislation for sludge to be used in agriculture. Total concentrations of 2.78 mg kg⁻¹ Cd, 433 mg kg⁻¹ Cu and 126 mg kg⁻¹ Pb were below those permitted in the relevant legislation. CRM 146R reference material was used to follow the quality of the analytical process. The results of the BCR three-step sequential extraction procedure indicate high Ni and Zn mobility in the sludge analysed. The other heavy metals were primarily in sparingly soluble fractions and hence poorly mobile. Due to the high total Ni concentration and its high mobility the investigated sewage sludge could not be used in agriculture.     

A study of the sorptive properties of surface sediments in a landfill project region

Surface sediment samples were collected from 3 regions of a river island (a landfill area, a foreshore zone and a swamp segment) and the adsorptive properties of the - 180 μm and “clay” fractions were examined by studying the effects of concentration, pH and complex formation on the uptake of copper or zinc ions. The fine sand fraction contained basic material which raised the pH of aqueous suspensions to 8, at which value near total precipitation of added metal ions occurred. Uptake by the clay fractions (at pH 5) conformed to a Langmuir type adsorption isotherm, yielding parameters of similar order to values reported for soil clays and clay minerals. Using constant initial concentrations the amount of Cu or Zn adsorbed increased with pH until the threshold for precipitation (7) was exceeded. Both uptake and precipitation were inhibited in the presence of ligands which formed stable anionic complexes (e.g. NTA, EDTA, citric acid). The foreshore and swamp samples contained organic matter which retained part of the added metal ion as a solute in alkaline media. Treatment of these clay fractions with hydrogen peroxide did not destroy all the organic content, but it did change adsorptive behaviour.Extraction studies with 0.01 M nitric acid, 0.1 M oxalic acid, 0.1 M ammonium acetate, and 0.01 M EDTA showed that both the clay fractions and fine sands contained measurable amounts (0.05–40 mmol kg⁻¹) of the metal ions Pb, Cd, Cu and Zn, but because of the basic nature of the sediments, adjacent waters had solution levels which remain well within acceptable limits.The overall results have been used to predict factors likely to promote formation of high leachate levels.     

Heavy metal behaviour during the activated sludge process I. Extent of soluble and insoluble metal removal

The extent of removal of Ag, Bi, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Tl and Zn and their distribution between the soluble and insoluble phases in the influent, and effluent of the activated sludge process has been studied using a pilot-scale plant operated at sludge ages of 3, 6, 9 and 12 days. Molybdenum, Tl, Co, Mn and Ni were >50% soluble in the influent settled sewage. The mean removals of the former two metals were <3% and the latter three were 35 and 50%. Silver, Bi, Cd, Cr, Cu, Pb and Zn were all <35% soluble in the influent and had substantial removals of >75%. Solubilities were greater in the effluent than the influent with the exception of Mn. The observed overall removals of Ag, Bi, Co, Ni, Pb, Tl and Zn were almost entirely due to insoluble metal removal; Cd, Cr and Cu removals had a significant contribution from soluble metal removal. Overall Mn removal appeared to be solely due to soluble metal removal.