Efficient removal of heavy metals from electroplating wastewater using polymer ligands

Poly(hydroxamic acid)-poly(amidoxime) chelating ligands were synthesized from poly(methyl acrylate-co-acrylonitrile) grafted acacia cellulose for removing toxic metal ions from industrial wastewaters. These ligands showed higher adsorption capacity to copper (2.80 mmol?g⁻¹) at pH 6. In addition, sorption capacities to other metal ions such as iron, zinc, chromium, and nickel were also found high at pH 6. The metal ions sorption rate (t_1/2) was very fast. The rate of adsorption of copper, iron, zinc, chromium, nickel, cobalt, cadmium and lead were 4, 5, 7, 5, 5, 8, 9 and 11 min, respectively. Therefore, these ligands have an advantage to the metal ions removal using the column technique. We have successfully investigated the known concentration of metal ions using various parameters, which is essential for designing a fixed bed column with ligands. The wastewater from electroplating plants used in this study, having chromium, zinc, nickel, copper and iron, etc. For chromium wastewater, ICP analysis showed that the Cr removal was 99.8% and other metal ions such as Cu, Ni, Fe, Zn, Cd, Pb, Co and Mn removal were 94.7%, 99.2%, 99.9%, 99.9%, 99.5%, 99.9%, 95.6% and 97.6%, respectively. In case of cyanide wastewater, the metal removal, especially Ni and Zn removal were 96.5 and 95.2% at higher initial concentration. For acid/alkali wastewater, metal ions removing for Cd, Cr and Fe were 99.2%, 99.5% and 99.9%, respectively. Overall, these ligands are useful for metal removal by column method from industrial wastewater especially plating wastewater.     

Environmental and technological studies on the interaction of wool with some metal ions

The technical feasibility of using a suitable sorbent for the removal of some heavy metal ions from their aqueous solutions was investigated. The scope of the work covers the use of low-class native wool or wool wastes from industrial processes or from recycled woolen textiles for the removal of copper, nickel, cobalt, chromium, and zinc ions from their effluents. The sorption efficiency of the aforementioned metals by wool is in the following order: copper?>?cobalt?=?nickel?>?zinc?>?chromium.

The effect of time of sorption, temperature of the effluent, and concentration of metal ions on the rate of sorption was examined. The effect of oxidation or reduction of wool on its sorption power of copper ions is studied. The reduced wool was found to be better than native or oxidised wool in the sorption of copper metal from its effluents. The reuse of wool as metal sorber after elution of the metal, using hydrochloric acid, was also studied. It was found that wool can be reused for sorption after elution of copper up to 25 times of elution; a very limited amount of permanently fixed copper was observed. The use of sufficient woolen layers displays the best way of obtaining an effluent of zero copper content.     

Metal survey of the marine clam Pitar morrhuana collected near a Rhode Island (USA) electroplating plant

Benthic fauna were collected from 17 stations in mid-Narragansett Bay, Rhode Island, during September 1973 from the vicinity of the recently-closed Quonset Point electroplating facility. Despite repeated sampling, most of the 14 species of molluscs taken, including the widgeon clam Pitar morrhuana, were absent from stations in the immediate vicinity of plant outfalls. In general, P. morrhuana captured near outfall sites exhibited high moisture content and elevated body burdens of silver, cadmium, cobalt, chromium, copper, iron, manganese, nickel, lead, and zinc compared to clams of similar size from more distant stations. Observed changes in metal concentrations and moisture content of P. morrhuana were probably attributable to plant operations during the preceding 30 years.     

Heavy metals,occurrence and toxicity for plants: a review

Metal contamination issues are becoming increasingly common in India and elsewhere, with many documented cases of metal toxicity in mining industries, foundries, smelters, coal-burning power plants and agriculture. Heavy metals, such as cadmium, copper, lead, chromium and mercury are major environmental pollutants, particularly in areas with high anthropogenic pressure. Heavy metal accumulation in soils is of concern in agricultural production due to the adverse effects on food safety and marketability, crop growth due to phytotoxicity, and environmental health of soil organisms. The influence of plants and their metabolic activities affects the geological and biological redistribution of heavy metals through pollution of the air, water and soil. This article details the range of heavy metals, their occurrence and toxicity for plants. Metal toxicity has high impact and relevance to plants and consequently it affects the ecosystem, where the plants form an integral component. Plants growing in metal-polluted sites exhibit altered metabolism, growth reduction, lower biomass production and metal accumulation. Various physiological and biochemical processes in plants are affected by metals. The contemporary investigations into toxicity and tolerance in metal-stressed plants are prompted by the growing metal pollution in the environment. A few metals, including copper, manganese, cobalt, zinc and chromium are, however, essential to plant metabolism in trace amounts. It is only when metals are present in bioavailable forms and at excessive levels, they have the potential to become toxic to plants. This review focuses mainly on zinc, cadmium, copper, mercury, chromium, lead, arsenic, cobalt, nickel, manganese and iron.     

Spread of metals through an invertebrate food chain as influenced by a plant that hyperaccumulates nickel

Summary. Hyperaccumulation of metals in the shoot system of plants is uncommon, yet taxonomically and geographically widespread. It may have a variety of functions, including defense against herbivores. This study investigated the effects of hyperaccumulation on metal concentrations across trophic levels. We collected plant material, soil, and invertebrates from Portuguese serpentine outcrops whose vegetation is dominated by the nickel hyperaccumulator Alyssum pintodasilvae. Samples were analyzed for nickel, chromium, and cobalt. Grasshoppers, spiders, and other invertebrates collected from sites where A. pintodasilvae was common had significantly elevated concentrations of nickel, compared to nearby sites where this hyperaccumulator was not found. Chromium and cobalt, occurring in high concentrations in the serpentine soil but not accumulated by A. pintodasilvae, were not elevated in the invertebrates. Therefore, it appears likely that a flux of nickel to herbivore and carnivore trophic levels is specifically facilitated by the presence of plants that hyperaccumulate this metal. The results may be relevant to the development of phytoremediation and phytomining technologies, which use plants to extract metals from the soil. Reveived 22 August 2002; accepted 2 April 2003. R1D=" Correspondence to: A. J. Pollard, e-mail:joe.pollard@furman.edu     

Health hazards from exposure to cobalt with special reference to carcinogenic,mutagenic and teratogenic effects†

Occupational exposure to cobalt‐containing dust may cause a severe type of pneumoconiosis as well as obstructive lung disease. Peroral exposure to cobalt chloride may under certain circumstances precipitate cardiomyopathy.

There are only a limited number of experimental studies available which deal with the carcinogenic, mutagenic and teratogenic effects of cobalt and its salts. Single or repeated injections of cobalt powder or cobalt chloride have been shown to induce malignant tumours at the site of injection in rats, but not in mice. In vitro studies have shown that cobalt chloride has mutagenic and teratogenic properties. There are no data available on cancer incidence among workers occupationally exposed to cobalt. Thus the possible role of cobalt in human carcinogenesis is still an open question.     

Heavy metal action on transintegumentary absorption of glycine in two annelid species

Absorption of ¹⁴C-glycine from ambient sea water across the body surface of the oligochaete Enchytraeus albidus Henle was, after 6 h preincubation, significantly reduced in the presence of 0.1 to 0.15 ppm mercury, 0.25 ppm copper, 1.5 ppm silver, and 2 ppm cadmium. Addition of heavy metal salts reduced maximum uptake rates (V _max ), without affecting transport constants (K _t ). Influx of ¹⁴C-glycine remained unchanged in the presence of up to 10 ppm aluminium, chromium, iron, lead, molybdenum, vanadium, and zinc. Effects of up to 150 ppm nickel, manganese, cobalt and selenium were negligible. Inhibition of glycine absorption by mercury and cadmium in the polychaete Nereis diversicolor Müller is almost identical with results presented for E. albidus. Transintegumentary solute absorption in soft-bodied marine invertebrates obviously represents a suitable biological function for studies on heavy metal toxicity. The close relationship between rates of heavy metal absorption, inhibition of transintegumentary glycine uptake, and acute toxicity is discussed.     

Chromium recovery from solid leather waste by chemical treatment and optimisation by response surface methodology

The leather industry uses conventional tanning methods which cause environmental pollution due mainly to the presence of chromium. This study suggests a treatment for solid leather waste containing chromium as an ecological alternative to the pollution generated by tanneries. The study uses an original approach to the optimisation of chromium recovery by mathematical and statistical treatment of the experimental data. Several factors that influence recovery, such as temperature, concentration, time and solid/liquid ratio through acid and basic hydrolysis were analysed with the aid of experimental design. Tanning liquor was obtained by adjusting pH, alkalinity and concentration when hydrolysis finished. An appropriate response surface model was constructed using alkaline hydrolysis experiments with sodium hydroxide, leading to conditions for maximum recovery of Cr₂O₃. The optimal NaOH concentration (1.58%), temperature (63.7 °C), time (3 h) and solid/liquid ratio (1/70 g·mL^?1) were established. The results indicate that sodium hydroxide as an hydrolysis agent is a highly efficient means of recovering chromium from solid leather waste in order to produce tanning liquor.     

Influence of iron,nickel and cobalt on biogas production during the anaerobic fermentation of fresh residual biomass

We have investigated the dependence of the rate of the production of biogas upon the concentration of nickel, cobalt and iron at sub-toxic concentration and monitored its composition as amount of hydrogen, methane and carbon dioxide. The distribution of the added metals between the liquid and solid phase has also been monitored.

The results of our investigations show that the addition of any of the listed metals to the sludge may cause the production of a higher amount of biogas and influence the methane or carbon dioxide percentage. Conversely, the effect on the hydrogen production depends upon the metal added, the age of the active sludge used, and its adaptation to the susbtrate. As a general feature, during the acidogenesis phase, nickel reduces, while iron increases, the percentage of dihydrogen in the biogas, while cobalt has no influence.     

Simultaneous removal of Co,Cu, and Cr from water by electrocoagulation

This study provides an electrocoagulation process for the removal of metals such as cobalt, copper, and chromium from water using magnesium as anode and galvanized iron as cathode. The various parameters like pH, current density, temperature, and inter electrode distance on the removal efficiency of metals were studied. The results showed that maximum removal efficiency was achieved for cobalt, copper, and chromium with magnesium as anode and galvanized iron as cathode at a current density of 0.025?A?dm^?2 at pH 7.0. First- and second-order rate equations were applied to study adsorption kinetics. The adsorption process follows second-order kinetics model with good correlation. The Langmuir and Freundlich adsorption isotherm models were studied using the experimental data. The Langmuir adsorption isotherm favors monolayer coverage of adsorbed molecules for the adsorption of cobalt, copper, and chromium. Temperature studies showed that adsorption was endothermic and spontaneous in nature.     

Research of usability of tree leaves and soil in determining the contribution of industry and traffic to air pollution in Bozüyük (Turkey) region

In industrialized regions like Bozüyük, generally density of settlement and traffic is also observed. As a result of this density, the metal pollution that results from either industrial activities or traffic shall affect the air quality negatively. In determining this effect and sources thereof inspection of the depositing of heavy metals, which cause pollution, on the tree leaves and in the soil, and making comments by comparing with the values in the same kinds of plants and soil in the clean region has been aimed. For this purpose, zinc, copper, chromium, cadmium, iron, nickel, lead analysis have been carried out in order to determine the accumulation of pollution in plants and soils resulting from heavy industry and vehicles around Bozüyük (Turkey) region which is close to highway. These analyses have been carried out on washed and unwashed tree leave samples and surface soil from ten locations. Data used in the results were the average values of a series of data obtained from the experimental studies.     

Influence of iron, nickel and cobalt on biogas production during the anaerobic fermentation of fresh residual biomass

We have investigated the dependence of the rate of the production of biogas upon the concentration of nickel, cobalt and iron at sub-toxic concentration and monitored its composition as amount of hydrogen, methane and carbon dioxide. The distribution of the added metals between the liquid and solid phase has also been monitored.

The results of our investigations show that the addition of any of the listed metals to the sludge may cause the production of a higher amount of biogas and influence the methane or carbon dioxide percentage. Conversely, the effect on the hydrogen production depends upon the metal added, the age of the active sludge used, and its adaptation to the susbtrate. As a general feature, during the acidogenesis phase, nickel reduces, while iron increases, the percentage of dihydrogen in the biogas, while cobalt has no influence.     

Use of seaweeds for monitoring trace elements in coastal waters

Concentrations of a wide range of trace elements: arsenic, cadmium, cobalt, chromium, hafnium, nickel, thorium, uranium, zinc and the rare earth elements, cerium, europium, samarium, terbium and ytterbium were determined by instrumental neutron activation analysis in the brown alga,Fucus vesiculosus from Eckwarder Hörne, North Sea and from Rügen, Baltic Sea. Another brown alga,Sargassum filipendula from Sri Lanka, Indian ocean (representing an unpolluted control station) was similarly investigated. Cobalt, chromium and nickel concentrations were highest inF. vesiculosus from the North Sea while zinc was highest in samples from the Baltic Sea, reflecting high levels of these elements in coastal waters of the North and the Baltic sea. Cadmium, cobalt, nickel and zinc levels were lowest inS. filipendula from Sri Lanka, probably demonstrating lower levels of those elements in coastal waters. Concentration levels of hafnium, thorium, uranium, and the rare earth elements were highest inS. filipendula. Two years later in 1994,S. filipendula along withUlva sp. (green alga) was resampled from the same sampling site, and in addition to the above elements, six other trace elements (Ag, Ba, Br, Rb, Se and Sr) were determined.Sargassium filipendula showed a particular affinity for Ag, As, Br and Sr. For the other elements, marginal concentration differences were observed betweenS. filipendula andUlva sp., probably reflecting the regional background levels. Substantially higher concentrations of Hf, Th, U, and the rare earths were found again in the 1994Sargassum andUlva samples, reflecting the effect of a substrate rich in rare earth elements. The brown algae used in this study may be used to monitor trace elements in coastal waters.     

Heavy metals in three commercially valuable cyprinids in the river Panjkora,district Lower Dir,Khyber Pakhtunkhwa,Pakistan

This study was conducted in river Panjkora (Khall, upstream; Timergara, downstream) and its tributary (Konhaye stream, reference site) at district Lower Dir. The study was aimed to assess heavy metal load in gills, liver, kidneys, and muscles of three fish species, namely Schizothorax esocinus, Racoma labiata, and Crossocheilus diplocheilus. The heavy metals, including nickel, cadmium, lead, copper, zinc, chromium, iron, and manganese were determined using an atomic absorption spect-rophotometer. Nickel and cadmium were not detected in any of the collected specimens at all sampling sites. Concentration of the detected metals varied significantly depending upon fish species and tissue type. Crossocheilus diplocheilus showed higher accumulated concentration of heavy metals while R. labiata contained the least. Schizothorax esocinus and R. labiata displayed significant differences in their concentrations of metals. The order of accumulation of heavy metals in different tissues was liver>kidneys>muscles>gills. Data demonstrated that heavy metal levels in the studied species were within permissible limits and thus, apparently suitable for human consumption. Currently, the river contains a sewage burden, and continued heavy pollution may ultimately lead to serious problems in the future.     

Total and bioavailable metals in two contrasting mining regions (Sudbury in Canada and Lubumbashi in DR-Congo): relation to genetic variation in plant populations

Knowledge of total and bioavailable metal contents in soil is important for regional risk assessment and management. The main objective of the present study was to analyse the concentrations of metals in soils in two contrasting mining regions (Sudbury in Canada and Lubumbashi in DR-Congo). Genetic variation of plant populations was investigated to assess the potential impact of metal contamination on forest sustainability. The levels of copper, cobalt, zinc, arsenic, and lead were significantly higher (up to 200-fold) in mining sites in the Lubumbashi compared to the most highly contaminated Sudbury sites. The nickel content in soil samples from Lubumbashi was much lower compared to Sudbury region samples. Only 3.5% and 4 % of total copper and nickel, respectively, were phytoavailable, with values of 6%, 5.7%, 3.6%, and 5.4% for cobalt, magnesium, manganese, and zinc, respectively. There were significant positive correlations between total metal and phytoavailable metal concentrations for copper (r=0.99), nickel (r=0.86), cobalt (r=0.72), strontium (r=0.71), and zinc (r=0.66). Although genetic variation was high in Picea glauca populations from the Sudbury region, no association was found between metal contamination levels and genetic variation within and among the P. glauca populations.     

Effect of electronic waste on E. coli genomic integrity: a possible role for metal induced carcinogenesis

Electronic waste (e-waste) poses a major public health threat for developing countries’ populations. The hazards of e-waste are exacerbated by crude recycling methods. In this study, the presence of metals in e-waste samples obtained from Lagos, Nigeria, was assessed using atomic absorption spectrometry. The effect of e-waste on Escherichia coli (E. coli) PQ-37 genomic integrity was evaluated using the SOS chromotest. The means of metal concentrations in the evaluated samples were 16 (cadmium), 7.3 (nickel), 11 (chromium), 20 (lead), 3100 (iron), 90 (zinc), and 2000 (copper) μg_L^?1. Damage to E. coli deoxyribonucleic acid (DNA) increased proportionally to the metal concentrations. Significant amounts of DNA damaging agents from inadequately processed e-waste are present in the studied environment, which will have implications for adverse effects on public and ecological health. Existing policies against dumping of toxic materials in susceptible communities should be enforced.     

The importance of solid-phase distribution on the oral bioaccessibility of Ni and Cr in soils overlying Palaeogene basalt lavas, Northern Ireland

Potentially toxic elements (PTEs) including nickel and chromium are often present in soils overlying basalt at concentrations above regulatory guidance values due to the presence of these elements in underlying geology. Oral bioaccessibility testing allows the risk posed by PTEs to human health to be assessed; however, bioaccessibility is controlled by factors including mineralogy, particle size, solid-phase speciation and encapsulation. X-ray diffraction was used to characterise the mineralogy of 12 soil samples overlying Palaeogene basalt lavas in Northern Ireland, and non-specific sequential extraction coupled with chemometric analysis was used to determine the distribution of elements amongst soil components in 3 of these samples. The data obtained were related to total concentration and oral bioaccessible concentration to determine whether a relationship exists between the overall concentrations of PTEs, their bioaccessibility and the soils mineralogy and geochemistry. Gastric phase bioaccessible fraction (BAF %) ranged from 0.4 to 5.4 % for chromium in soils overlying basalt and bioaccessible and total chromium concentrations are positively correlated. In contrast, the range of gastric phase BAF for nickel was greater (1.4–43.8 %), while no significant correlation was observed between bioaccessible and total nickel concentrations. However, nickel BAF was inversely correlated with total concentration. Solid-phase fractionation information showed that bioaccessible nickel was associated with calcium carbonate, aluminium oxide, iron oxide and clay-related components, while bioaccessible chromium was associated with clay-related components. This suggests that weathering significantly affects nickel bioaccessibility, but does not have the same effect on the bioaccessibility of chromium.     

Spatial analysis of chromium in southwestern part of Iran: probabilistic health risk and multivariate global sensitivity analysis

This study was concerned with chromium as a potential carcinogenic contaminant in 64 wells located in five aquifers, southwest of Iran. A probabilistic health risk assessment indicated a high risk to the local residents including adults and children in the study area. A sequential sensitivity analysis and a novel approach known as multivariate global sensitivity analysis using both principal component analysis and B-spline were applied to investigate the behavior of health risk model along time considering four independent input parameters in the risk equation. In this context, based on the results of sensitivity analysis, concentration of chromium in drinking water (C_w) and body weight (W) were the most influential parameters. Random forest (RF) was used as a variable selection method to choose the most influential parameters for the prediction of chromium. Five parameters, among 13 water quality variables, including phosphate, nitrate, fluoride, manganese and iron were selected by RF as the most important parameters for spatial prediction. Hybrid methods of RF and ordinary kriging (RFOK) and RF and inverse distance weighting (RFIDW) were then applied for spatial prediction of Cr using the secondary variables. The RFOK and RFIDW were more efficient than that of ordinary kriging (OK) with respect to a cross-validation algorithm. For instance, in terms of relative root mean squared error, the performance of OK was improved from 31.72 to 23.21 and 23.61 for RFOK and RFIDW, respectively.