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Purification of metal electroplating waste waters using zeolites.

The sorption behaviour of natural (clinoptilolite) and synthetic (NaP1) zeolites has been studied with respect to Cr(III), Ni(II), Zn(II), Cu(II) and Cd(II) in order to consider its application to purify metal finishing waste waters. The batch method has been employed using metal concentrations in solution ranged from 10 to 200 mg/l and solid/liquid ratios ranged from 2.5 to 10 g/l. The Langmuir model was found to describe well all sorption processes, allowing to establish metal sorption sequences from which the main retention mechanism involved for each metal has been inferred. Synthetic zeolite exhibited about 10 times greater sorption capacities (b(Cr)=0.838 mmol/g, b(Ni)=0.342 mmol/g, b(Zn)=0.499 mmol/g, b(Cu)=0.795 mmol/g, b(Cd)=0.452 mmol/g) than natural zeolite (b(Cr)=0.079 mmol/g, b(Ni)=0.034 mmol/g, b(Zn)=0.053 mmol/g, b(Cu)=0.093 mmol/g, b(Cd)=0.041 mmol/g), appearing, therefore, as most suitable to perform metal waste water purification processes. This mineral showed the same high sorption capacity values when used in the purification of metal electroplating waste waters.

Adsorption↗

Role of cell surface components on Cu2+ adsorption by Pseudomonas putida 5-x isolated from electroplating effluent.

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

Adsorption↗

Removal of Cu, Cr, Ni, Zn, and Cd from electroplating wastes and synthetic solutions by vermicompost of cattle manure.

This study was undertaken to evaluate the retention of Cu, Cr, Ni, Zn, and Cd under laboratory conditions from synthetic solution and electroplating wastes by vermicompost. A glass column was loaded with vermicompost, and metal solutions were passed through it. Metal concentrations were then measured in the eluate in order to evaluate the amounts retained by the vermicompost. Measurements of pH, metal concentrations, moistness, organic matter and ash contents, and infrared and XRD spectroscopy were used for vermicompost characterisation. Vermicompost residues obtained from this process were used for plant nutrition in eroded soil collected from a talus near a highway. Metal retention (in g of metal/kg of vermicompost) from effluents ranged from 2 for Cr and Zn to 4 in the case of Ni. In synthetic solutions, the values for metal retention were 4 for Cd and Zn, 6 for Cu and Ni, and 9 for Cr. The results also showed that metal concentrations in the purified effluents were below the maximum values established for waste discharges into rivers by the Brazilian Environmental Standards. The relatively high available Cd concentration of the vermicompost residue resulted in plant damage. This effect was attributed to the presence of Cd in the synthetic solution passed through the vermicompost. The data obtained do not give a complete picture of using vermicompost in cultivated lands, but such values as are determined do show that it can be suitable to remove heavy metals from industrial effluents.

Animals↗

Bacterial biosorbent for removing and recovering copper from electroplating effluents.

Investigations were carried out to study the removal and recovery of Cu(II) ions from wastewater by Micrococcus sp. The Langmuir isotherm model described very well the equilibrium behavior of copper biosorption, with maximum biosorption capacity (q(max)) reaching 52.1 mg Cu2+/g dry cell at pH 6. Biomass prewashed with sulfuric acid (0.05 mol 1(-1)) and sodium sulfate (1 mol l(-1)) solutions were shown to increase the copper removal capabilities up to 27% and 16%, respectively. Copper uptake by cells was negligible at pH 2.0 and then increased quickly with increasing pH until 6.0. Cells of Micrococcus sp. were immobilized in 2% calcium alginate and 10% polyacrylamide gel beads. A counter-current process comprising a series of immobilized cell reactors was developed for removing and recovering copper from electroplating effluents. This process was capable of producing an effluent at low copper concentration, with only a minimum amount of desorbing agent used. The technique of scanning electron microscopy coupled with X-ray dispersion analysis shows that Cu2+ exchanged with K+ and Ca2+ on the cell wall of Micrococcus sp., thereby suggesting ion exchange as one of the dominant mechanisms of metal biosorption for this bacterial strain.

Adsorption↗

[Spectrophotometric determination of trace copper in electroplating wastewater].

In the presence of CPB and OP, the chromogenic reaction of DBH-PF with Cu(II) was studied. The results show that the purple micelle reaction has high sensitivity in the medium of (CH2)6N4-HCl(pH = 5.4) buffered solution, the molar absorptivity is 1.8 x 10(5) L.mol-1.cm-1, and Beer's law is obeyed for Cu(II) in the range of 0.0-9.0 micrograms.25 mL-1 at 540 nm. Combined with solvent extraction separation, the method has been applied to the determination of trace Cu in electroplating wastewater with satisfactory results.

Copper↗

[An increased mortality from lung cancer among workers of a bright electroplating factory].

OBJECTIVE: to evaluate cancer mortality especially from lung tumours, in a cohort of workers of a bright electroplating factory, an industrial activity suspected of increasing the risk of cancer because of exposure to hexavalent chromium. Workers of this and other similar factories have been the target of a health surveillance program in the early '80s. DESIGN: the cohort members have been selected from the roster of employees as workers or technical clerks with at least 6 month of presence between the beginning of the activity (January 1968) until December 1994. Vital status has been updated to December 2003. The mortality rates of both the Italian and regional population have been used as standards. RESULTS: mortality from lung cancer was strongly increased among workers (based on 7 deaths among males, and one among females). Among males, lung cancer mortality was stratified by duration of work, latency and period of entry: the excess is evident in all categories and appeared higher among the workers recruited in more recent years. CONCLUSION: we suggest that the results are in agreement with the hypothesis of an occupational exposure to a carcinogenic hazard, as observed in other studies, and correlates with the increase of chromosomal aberrations observed in the past among these workers. This type of industrial activity deserves more epidemiological studies and close attention on the side of industrial hygiene.

Chromium↗

[Nose disease caused by occupational exposure to chromium in the electroplating industry: cytomorphological aspects].

Twenty-six workers were studied (9 chrome-platers exposed to chromium dioxide and 17 workers exposed to metallic chromium dust) in order to investigate the macroscopic and cytological changes of the nasal mucosa due to exposure to water-soluble hexavalent chromium or to metallic chromium dust in the electroplating industry and the role of different valencies in the onset of nasal disease. Experimental and epidemiological data have shown that hexavalent chromium, which has strong oxidative power, induces more noticeable toxic effects on tissues and mucous membranes than other compounds. The correlation between the degree of local toxic effects and the chemical state of chromium was demonstrated in both the macro- and the microscopic investigations and in particular in the cytological examinations: cases of atypia were found only in workers exposed to hexavalent chromium. Evidence of atypia raises the question of whether hexavalent chromium may act as a carcinogenic agent on the rhinosinusal mucosa. For this reason, the introduction of cytological nasal examination in health surveillance programmes for this category of workers acquires considerable importance. Sample collection from the nasal mucosa by brushing is the method of choice since it is simple, non-invasive and gives good diagnostic results.

Adult↗

Effect of three variables on the accuracy and variability of electroplated copper dies.

This investigation compared the accuracy of electroplated copper and stone dies. Sixty copper die replicas of a stainless steel master die were fabricated using different current settings, plating times, and backing materials. Die accuracy was assessed by measuring the misfit of a stainless steel ring machined to fit the master die. All the copper dies were more accurate than the 10 stone dies. The variability of the copper/stone dies was less than that of the stone dies (P = .011) and copper-resin dies (P < .001). There was no significant difference between the variability of the 40-mA, 48-hour copper-resin dies and the stone dies. The variability of the copper-resin dies was related to the thickness of the electrodeposit, which was a function of plating time, current, and plated surface area.

Analysis of Variance↗

A biocompatible needle-type glucose sensor based on platinum-electroplated carbon electrode.

A biocompatible needle-type glucose sensor with a 3-electrode configuration was constructed. A platinum-electroplated carbon stick was used as the working electrode, Ag/AgCl as the reference electrode, and a disposable hypodermic needle made of stainless steel as the counter electrode. A Nafion membrane, an immobilized glucose oxidase (GOD) membrane, and a biocompatible membrane with diffusion-limiting effect were coated successively onto the working electrode. The sensor showed a rapid response (< 120 s in batch operation), good reproducibility (RE < 3%), good stability (over 36 h in control serum), a wide dynamic range (5-600 mg/dL glucose), and superior biocompatibility. It was used to determine glucose in serum. The data obtained from the sensor showed good agreement with that from a clinical autoanalyzer (R > 0.95).

Biocompatible Materials↗

Interaction between components of electroplating industry wastes. Influence of the receiving water on the toxicity of the effluent.

A copper-cadmium-nickel-zinc mixture was assessed in seven different river waters to study metal toxicity to the ciliate protozoan Colpidium campylum, the interactions occurring between metals, and the influence of the receiving water on toxicity. In the range of concentrations tested, which are representative of electroplating industry wastes, the main part of the toxicity can be attributed to copper and to cadmium-copper synergy. A classification of waters, based on a principal component analysis (PCA), was used to examine the main parameters of the water, which can affect the toxicity of metal mixtures. It appears that the mineralization of the water, more than the total organic carbon (TOC), is an important parameter for the expression of toxicity. A strategy for the estimation of ecotoxicological hazard assessment, based on a simplified factorial experiment is proposed. It enables one to study, in a two-step bioassay, the toxicity of an effluent, the influence of river water on its toxicity, and the effects of contact time and dilution. By applying PCA to data from very different waters, it may be possible to estimate the ecotoxicological risk associated with the discharge of an effluent, on the basis of the chemistry of the receiving water.

Journal Article↗

Influence of copper content on NO removal of the activated carbon fibers produced by electroplating.

In this study, the activated carbon fibers (ACFs) on which copper metal was deposited by electroplating were used to remove nitric oxide (NO). N(2)/77 K adsorption isotherm characteristics, including the specific surface area and micropore volume, were investigated by BET and T-plot methods. NO removal efficiency was confirmed by gas chromatographic technique. From the experimental results, the copper content supported on ACFs led to an increase in the NO conversion, in spite of the decrease of the specific surface area or the micropore volume of ACFs. Consequently, the presence of Cu on ACFs played an important role in improving the NO reduction into O(2) and N(2), which was mainly attributed to the catalytic reactions of Cz-NO-Cu.

Journal Article↗

Biodetoxification of silver-cyanide from electroplating industry wastewater.

A bacterial consortium capable of utilizing metal-cyanides as a source of nitrogen was used to develop a microbiological process for the detoxification of silver-cyanide from electroplating wastewater. When the treatment was carried out in a 27-l rotating biological contactor (R3C) in continuous mode, the system could achieve > 99.5% removal of 0.1 mmol l(-1) silver-cyanide (approximately 5 mg l(-1) cyanide and 10 mg l(-1) silver) in 10 h with sugarcane molasses (0.1 ml l(-1)) as carbon source. The silver ions set free during biodegradation were efficiently adsorbed by the bacterial biomass. The RBC-treated effluent was found to be safe for discharge into the environment, as confirmed by chemical analysis and fish bioassay studies.

Animals↗

Cytotoxicity and mutagenicity study of waste and purified water samples from electroplating industries prepared by use of ferrous sulfate and wood fly ash.

Toxicological safety of the new purification method for electroplating wastewaters (EWW) has been assessed. Method utilizes waste by-product ferrous sulfate and wood fly ash to scavenge heavy metals from EWW. Energy dispersive X-ray fluorescence (EDXRF) analysis of all samples met the law requirements for safe depositing of waste into the environment. The toxicity study consisted of determination of frequency of bacterial and human cell lines survival and the Ames assay (plate incorporation assay and the preincubation assay). Unexpectedly, data obtained indicate cytotoxicity and slight mutagenic potential of purified water. Ames assay showed that combination of alkalis and heavy metals present in the water purified with original fly ash and eluates of fly and waste ash were metabolically activated and conjugated with glutathione, resulting in new metabolites active and toxic for the cell. In order to reduce this effect pretreatment of fly ash (partial removal of highly soluble compounds) are necessary prior to its usage for neutralization /coagulation/flocculation processes.

Carbon↗

Zinc blocks acetylcholine release but not vesicle fusion at the Torpedo nerve-electroplate junction.

The combined effects of Zn2+ treatment and nerve stimulation were studied on cholinergic synapses of the Torpedo marmorata electric organ. Incubation of small pieces of electric tissue in 250 microM ZnCl2 for 2 h irreversibly blocked synaptic transmission by inhibiting the release of acetylcholine. This treatment, however, did not cause any significant fine structural alteration in the nerve-electroplate junctions. Preparations treated with Zn2+ were submitted to electrical stimulation. In spite of the fact that no transmitter was released, stimulation resulted in the accumulation of calcium in the tissue, and in marked ultrastructural changes. The density of synaptic vesicles was significantly reduced and many of the remaining vesicles were found in close proximity to the presynaptic membrane. Images of vesicles fused with the plasmalemma were abundant, indicating that numerous vesicles were caught in different phases of exocytosis or endocytosis. Freeze-fracture replicas made from quick-frozen or chemically fixed material showed a high number of vesicle openings (pits) in the presynaptic plasmalemma. No recovery occurred even after a prolonged period of rest, indicating that retrieval was impaired by zinc treatment. In conclusion, the present experimental paradigm created an unusual situation where fusion of synaptic vesicles to the plasma membrane could be activated independently from the release of transmitter.

Acetates↗

Properties of miniature post-synaptic currents at the Torpedo marmorata nerve-electroplate junction.

The post-synaptic conductance changes induced by spontaneous release of neurotransmitter on the Torpedo marmorata electroplates were studied by focal extracellular recording methods. It was found that miniature post-synaptic currents (m.p.s.c.s) recorded on the innervated and non-innervated faces of the electrocyte are opposite in sense and the distribution of amplitudes is bimodal. The bimodal distribution could reflect the presence of two populations of m.p.s.c.s (smaller and giant m.p.s.c.s). In the smaller m.p.s.c.s the distribution of the ratio (amplitude/decay time constant) shows two populations that probably represent areas with different receptor densities. The value of the mean open-channel lifetime estimated from the decay time constant of the m.p.s.c. is 0.92 +/- 0.67 ms (n = 319, temperature 20 +/- 1 degree C). Prostigmine (10 microM) increases the amplitude, decay time constant and time to peak of the m.p.s.c. A decrease of temperature increases m.p.s.c. decay time, the activation energies found ranging from 8.0 to 12.6 kcal x mol-1. Increasing the external K+ concentration produces a decrease in the decay time constant. High concentrations of divalent ions, particularly Ca2+, increase the decay time constant of the m.p.s.c. Alkaline or acid bathing solution produces a decrease in the decay time constant. An almost total substitution of external Cl- by non-permeant SO42- does not modify the time course of the m.p.s.c.

Animals↗

Urinary and plasma concentrations of nickel as indicators of exposure to nickel in an electroplating shop.

The relationship between atmospheric exposure to nickel and urine and plasma nickel concentrations was studied by following four workers from an electroplating shop for one work week by daily measurements of the nickel concentration in workroom air with personal samplers and nickel concentrations in blood and urine samples collected before and after the work shift. The workroom air concentrations ranged from 0.03 to 0.16 mg/m3. The urinary and plasma nickel concentrations were higher in the samples taken after than before the work shift and a close positive correlation was found between the air nickel concentrations and the urine and plasma nickel concentrations, respectively. There was also a close correlation between urinary and plasma nickel concentrations. A slight accumulation of nickel occurred as judged from the increasing concentrations of nickel in the urine and plasma morning samples during the study week. This study indicates that both plasma and urine nickel concentrations may be used as biological indicators of exposure to soluble nickel compounds.

Adult↗

Mortality among workers in a die-casting and electroplating plant.

A proportional mortality and case-referent analysis of 238 deaths among hourly employees in an automobile hardware manufacturing plant was conducted. The major operations of the plant were zinc die casting and electroplating. Chemical exposure included die-casting emissions and mists from chrome and nickel plating. The chief proportional mortality finding was a significant excess of lung cancer among both white men and women. A case-referent analysis indicated a possible association between lung cancer and work in certain departments. The findings support the hypothesis of a work-related carcinogenic risk. Follow-up recommendations have been made.

Adult↗

Cancer mortality in United States counties with metal electroplating industries.

A survey of cancer mortality from 1950 to 1969 was conducted in U.S. counties where greater than 0.1% of the county's population was employed in the metal electroplating and coating industry. The mortality rates for several cancers, particularly of the esophagus and larynx, in these counties were higher than rates for a group of control counties with comparable demographic characteristics. Further study is needed to determine if these patterns result for worker exposures to substances such as caustic acids and alkalies, metals, and organic solvents commonly used in this industry.

Adult↗