Studies on electrochemical recovery of silver from simulated waste water from Ag(II)/Ag(I) based mediated electrochemical oxidation process

In the Ag(II)/Ag(I) based mediated electrochemical oxidation (MEO) process, the spent waste from the electrochemical cell, which is integrated with the scrubber columns, contains high concentrations of precious silver as dissolved ions in both the anolyte and the catholyte. This work presents an electrochemical developmental study for the recovery of silver from simulated waste water from Ag(II)/Ag(I) based MEO process. Galvanostatic method of silver deposition on Ti cathode in an undivided cell was used, and the silver recovery rate kinetics of silver deposition was followed. Various experimental parameters, which have a direct bearing on the metal recovery efficiency, were optimized. These included studies with the nitric acid concentration (0.75-6M), the solution stirring rate (0-1400 rpm), the inter-electrode distance between the anode and the cathode (2-8 cm), the applied current density (29.4-88.2 mA cm(-2)), and the initial Ag(I) ion concentration (0.01-0.2M). The silver recovered by the present electrodeposition method was re-dissolved in 6M nitric acid and subjected to electrooxidation of Ag(I) to Ag(II) to ascertain its activity towards Ag(II) electrogeneration from Ag(I), which is a key factor for the efficient working of MEO process. Our studies showed that the silver metal recovered by the present electrochemical deposition method could be reused repeatedly for MEO process with no loss in its electrochemical activity. Some work on silver deposition from sulfuric acid solution of different concentrations was also done because of its promising features as the catholyte in the Ag(II) generating electrochemical cell used in MEO process, which include: (i) complete elimination of poisonous NO(x) gas liberation in the cathode compartment, (ii) reduced Ag(+) ion migration across Nafion membrane from anolyte to catholyte thereby diminished catholyte contamination, and (iii) lower cell voltage and hence lesser power consumption.     

Molten salt oxidation: a versatile and promising technology for the destruction of organic-containing wastes

Molten salt oxidation (MSO), a robust thermal but non-flame process, has the inherent capability of destroying organic constituents in wastes, while retaining inorganic and radioactive materials in situ. It has been considered as an alternative to incineration and may be a solution to many waste disposal problems. The present review first describes the history and development of MSO, as well as design and engineering details, and then focuses on reaction mechanisms and its potential applications in various wastes, including hazardous wastes, medical wastes, mixed wastes, and energetic materials. Finally, the current status of and prospects for the MSO process and directions for future research are considered.     

Arabica-coffee and teobroma-cocoa agro-industrial waste biosorbents,for Pb(II) removal in aqueous solutions

Environmental Science and Pollution Research - Agro-industrial waste biosorbents of arabica–coffee (WCA) and theobroma–cocoa (WCT) have been characterized and tested to remove Pb(II)...     

Destruction of EDTA using Ce(IV) mediated electrochemical oxidation: a simple modeling study and experimental verification

Mediated electrochemical oxidation (MEO) is a recent development in the environmental research field for the complete destruction of organic pollutants. This study presents the destruction of EDTA by cerium(IV) MEO process in nitric acid medium. The destruction reaction was carried out in a continuous stirred tank reactor under various conditions. A simple kinetic model was developed to analyze and simulate the organic destruction in the MEO process. The model was based on the calculation of the total mass balance, the component mass balance, and the energy balance in the reactor and also in the heating jacket. The sensitivity to key operating conditions such as the initial EDTA concentration (50-200 mM), EDTA feeding time (30-180 min), reaction temperature (323-363 K), and the rate laws corresponding to zero-, first-, second-, and third-order reaction were analyzed. It was found that the model simulated agreed well with the experimental data for EDTA oxidation. The results obtained showed the suitability of the MEO process for the effective mineralization of high concentrations of EDTA.     

Peroxymonosulfate-Co(II) oxidation system for the removal of the non-ionic surfactant Brij 35 from aqueous solution

The non-ionic surfactant Brij 35 was effectively removed from concentrated aqueous solution by the peroxymonosulfate/Co(II) system, using oxone (2KHSO₅·KHSO₄·K₂SO₄) as a source of peroxymonosulfate. At pH = 2.3 and initial Brij 35 concentration in the range 680-2410 mg L⁻¹, 86-94% removal was achieved after 24 h, using Co(II) = 15 μM and oxone = 5.9 mM. The effectiveness of removal did not change when initial pH was in the range 2.3-8.2. After five subsequent additions of Co(II) and oxone to the solution, COD and TOC removals increased up to 64% and 33%, respectively. Radical quenching tests confirmed that sulfate radical was the dominant radical species in the system. The main identified by-products from surfactant degradation were: (a) low molecular weight organic acids; (b) aldehydes and formates with shorter ethoxy chain than Brij 35; (c) alcohol ethoxylates carrying hydroxyl groups bonded to ethoxy chain. By-products identification allowed to hypothesize the pathways of Brij 35 degradation.     

Biosorption of Cr(VI) and Zn(II) ions from aqueous solution onto the solid biodiesel waste residue: mechanistic, kinetic and thermodynamic studies

In this present study, the biosorption of Cr(VI) and Zn(II) ions from synthetic aqueous solution on defatted J atropha oil cake (DJOC) was investigated. The effect of various process parameters such as the initial pH, adsorbent dosage, initial metal ion concentration and contact time has been studied in batch-stirred experiments. Maximum removal of Cr(VI) and Zn(II) ions in aqueous solution was observed at pH 2.0 and pH. 5.0, respectively. The removal efficiency of Cr(VI) and Zn(II) ions from the aqueous solution was found to be 72.56 and 79.81 %, respectively, for initial metal ion concentration of 500 mg/L at 6 g/L dosage concentration. The biosorbent was characterized by Fourier transform infrared, scanning electron microscopy and zero point charge. Equilibrium data were fitted to the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich isotherm models and the best fit is found to be with the Freundlich isotherm for both Cr(VI) and Zn(II) metal ions. The kinetic data obtained at different metal ion concentration have been analysed using the pseudo-first-order, pseudo-second-order and intraparticle diffusion models and were found to follow the pseudo-second-order kinetic model. The values of mass transfer diffusion coefficients (D _e) were determined by Boyd model and compared with literature values. Various thermodynamic parameters, such as ΔG°, ΔH° and ΔS°, were analysed using the equilibrium constant values (K _e) obtained from experimental data at different temperatures. The results showed that biosorption of Cr(VI) and Zn(II) ions onto the DJOC system is more spontaneous and exothermic in nature. The results indicate that DJOC was shown to be a promising adsorbent for the removal of Cr(VI) and Zn(II) ions from aqueous solution.     

Sorption of native polyaromatic hydrocarbons (PAH) to black carbon and amended activated carbon in soil

Organic pollutants (e.g. polyaromatic hydrocarbons (PAH)) strongly sorb to carbonaceous sorbents such as black carbon and activated carbon (BC and AC, respectively). For a creosote-contaminated soil (Sigma15PAH 5500 mg kg(dry weight(dw))(-1)) and an urban soil with moderate PAH content (Sigma15PAH 38 mg kg(dw)(-1)), total organic carbon-water distribution coefficients (K(TOC)) were up to a factor of 100 above values for amorphous (humic) organic carbon obtained by a frequently used Linear-Free-Energy Relationship. This increase could be explained by inclusion of BC (urban soil) or oil (creosote-contaminated soil) into the sorption model. AC is a manufactured sorbent for organic pollutants with similar strong sorption properties as the combustion by-product BC. AC has the potential to be used for in situ remediation of contaminated soils and sediments. The addition of small amounts of powdered AC (2%) to the moderately contaminated urban soil reduced the freely dissolved aqueous concentration of native PAH in soil/water suspensions up to 99%. For granulated AC amended to the urban soil, the reduction in freely dissolved concentrations was not as strong (median 64%), especially for the heavier PAH. This is probably due to blockage of the pore system of granulated AC resulting in AC deactivation by soil components. For powdered and granulated AC amended to the heavily contaminated creosote soil, median reductions were 63% and 4%, respectively, probably due to saturation of AC sorption sites by the high PAH concentrations and/or blockage of sorption sites and pores by oil.     

Biosorption characteristics of Bacillus gibsonii S-2 waste biomass for removal of lead (II) from aqueous solution

Lead (II) has been as one of the most toxic heavy metals because it is associated with many health hazards. Therefore, people are increasingly interested in discovering new methods for effectively and economically scavenging lead (II) from the aquatic system. Recent studies demonstrate biosorption is a promising technology for the treatment of pollutant streams. To apply these techniques, suitable adsorbents with high efficiency and low cost are demanded. The waste biomass of Bacillus gibsonii S-2 biosorbent was used as low-cost biosorbent to remove metallic cations lead (II) from aqueous solution. To optimize the maximum removal efficiency, the effect of pH and temperature on the adsorption process was studied. The isotherm models, kinetic models and thermodynamic parameters were analysed to describe the adsorptive behaviour of B. gibsonii S-2 biosorbent. The mechanisms of lead (II) biosorption were also analysed by FTIR and EDX. The results showed that the optimum pH values for the biosorption at three different temperatures, i.e. 20, 30 and 40 °C, were determined as 4. The equilibrium data were well fitted to Langmuir model, with the maximum lead (II) uptake capacities of 333.3 mg?g^?1. The kinetics for lead (II) biosorption followed the pseudo-second-order kinetic equation. The thermodynamic data showed that the biosorption process were endothermic (?G?<?0), spontaneous (?H?>?0) and irreversible (?S?>?0). The mechanism of lead (II) biosorption by the waste biomass of B. gibsonii S-2 biosorbent could be a combination of ion exchange and complexation with the functional groups present on the biosorbent surface. The application of the waste biomass of B. gibsonii S-2 for lead (II) adsorption, characterized with higher lead (II) sorption capacity and lower cost, may find potential application in industrial wastewater treatment.     

Scavenging of SO4− radical anions by mono- and dicarboxylic acids in the Mn(II)-catalyzed S(IV) oxidation in aqueous solution

The rate constants for reactions of the SO₄⁻ radical anion with some low molecular weight monocarboxylic acids (MCAs) and dicarboxylic acids (DCAs) and their anions using the laser flash photolysis-long path laser absorption (LFP-LPLA) technique were determined. The present study contains the first measured rate constants for SO₄⁻ reactions with glycolic, lactic, malic and malonic acid. The rate constants are found to be in the range from 10⁵ to 10⁷ M⁻¹ s⁻¹, with the lower values found for acids and higher values for their respective anions. In addition, the rate constants for scavenging of SO₄⁻ by all investigated organics in the Mn(II)-catalyzed S(IV) autoxidation at pH 4.5 and T=25 °C were determined by means of the reversed rate method. The comparison between these rate constants and the rate constants obtained by direct measurements confirms the proposed inhibiting mechanism for the Mn(II)-catalyzed S(IV) autoxidation in the presence of monocarboxylic acids. In the case of formic acid, which causes the highest inhibition, this mechanism can explain the second part of kinetic traces (i.e. after the induction period). Surprisingly, although dicarboxylic acids are reactive toward SO₄⁻ they do not contribute to the inhibition of S(IV) oxidation (especially malic and malonic acids).     

Characterisation of polymer fractions from waste electrical and electronic equipment (WEEE) and implications for waste management

There is an increasing interest in the end-of-life management of polymers present in waste electrical and electronic equipment (WEEE). This is mainly due to high recycling and recovery quotas set by the European WEEE directive, which can only be fulfilled by including the plastic fraction in recycling and recovery approaches. Previous studies identified a high material diversity and various contaminants in WEEE plastics, including heavy metals, polybrominated biphenyls (PBB), diphenyl ethers (PBDE), as well as polybrominated dibenzodioxins and dibenzofurans (PBDD/F). These substances are regulated by European directives that limit their levels in marketable products. Consequently, both material diversity and contaminants are strong arguments against material recycling and point to hazardous waste treatment. However, recent developments in the production of flame retardants and electrical and electronic goods aimed to reduce contaminants and material diversity. Thus, the present study summarises updated contaminant levels of plastic fractions of European WEEE, as well as data on materials in waste housing polymers. Material characterisation revealed housing fractions to be interesting sources for polymer recycling, which however has to implement potent material separation and/or bromine elimination techniques. With respect to contaminants, our data indicate an effective phase-out of PBB, but still high levels of PBDE and PBDD/F are found. Sources and implications for the material recycling and thermal recovery approaches are discussed in detail.     

Kinetics of oxidation of chlorobenzenes and phenyl-ureas by Fe(II)/H2O2 and Fe(III)/H2O2. Evidence of reduction and oxidation reactions of intermediates by Fe(II) or Fe(III)

The rates of degradation of 1,2,4-trichlorobenzene (TCB), 2,5-dichloronitrobenzene (DCNB), diuron and isoproturon by Fe(II)/H2O2 and Fe(III)/H2O2 have been investigated in dilute aqueous solution ([Organic compound]0 approximately 1 microM, at 25.0 +/- 0.2 degrees C and pH < or = 3). Using the relative rate method with atrazine as the reference compound, and the Fe(II)/H2O2 (with an excess of Fe(II)) and Fe(III)/H2O2 systems as sources of OH radicals, the rate constants for the reaction of OH* with TCB and DCNB were determined as (6.0 +/- 0.3)10(9) and (1.1 +/- 0.2)10(9) M(-1) s(-1). Relative rates of degradation of diuron and isoproturon by Fe(II)/H2O2 were about two times smaller in the absence of dissolved oxygen than in the presence of oxygen. These data indicate that radical intermediates are reduced back to the parent compound by Fe(II) in the absence of oxygen. Oxidation experiments with Fe(III)/H2O2 showed that the rate of decomposition of atrazine markedly increased in the presence of TCB and this increase has been attributed to a regeneration of Fe(II) by oxidation reactions of intermediates (radical species and dihydroxybenzenes) by Fe(III).     

The effect of triethylene tetramine upon the selective removal of nickel (II), iron (II), manganese (II) and tin (II) in rats

The distribution of Nickel-63, Iron-59, Manganese-54 and Tin-113 in plasma was studied in rats which received single intravenous (i.v.) injection of aqueous solutions of their salts alone, and in rats which also received single intramuscular (im) injection of triethylene tetramine (TETA). TETA was extremely effective in reducing the plasma concentration of Nickel-63 followed by that of Iron-59, Manganese-54 and Tin-113.     

The marine macroalga Cystoseira baccata as biosorbent for cadmium(II) and lead(II) removal: kinetic and equilibrium studies

This work reports kinetic and equilibrium studies of cadmium(II) and lead(II) adsorption by the brown seaweed Cystoseira baccata. Kinetic experiments demonstrated rapid metal uptake. Kinetic data were satisfactorily described by a pseudo-second order chemical sorption process. Temperature change from 15 to 45 degrees C showed small variation on kinetic parameters. Langmuir-Freundlich equation was selected to describe the metal isotherms and the proton binding in acid-base titrations. The maximum metal uptake values were around 0.9 mmol g(-1) (101 and 186 mg g(-1) for cadmium(II) and lead(II), respectively) at pH 4.5 (raw biomass), while the number of weak acid groups were 2.2 mmol g(-1) and their proton binding constant, K(H), 10(3.67) (protonated biomass). FTIR analysis confirmed the participation of carboxyl groups in metal uptake. The metal sorption was found to increase with the solution pH reaching a plateau above pH 4. Calcium and sodium nitrate salts in solution were found to affect considerably the metal biosorption.     

Biomass-derived materials in the remediation of heavy-metal contaminated water: removal of Cadmium(II) and copper(II) from aqueous solutions

Manganese-coated activated carbon (MCAC) and activated carbon were used in batch experiments for the removal of cadmium(II) and copper(II). Results showed that uptake of Cd(II) and Cu(II) was unaffected by increases in pH (3.0 to 8.5) or concentration (1 to 20 mg/L). Increased ionic strength (from 0.001 to 1 M NaNO3), however, significantly affected the uptake of Cd(II); adsorption of Cu(II) was not affected. Freundlich adsorption isotherm results indicated that MCAC possessed higher sorption capacity than activated carbon. Second-order rate constants were found to be 0.0386 for activated carbon and 0.0633 g/mg x min for MCAC for Cd(II) and 0.0774 for AC and 0.1223 g/mg x min for MCAC for Cu(II). Column experiments showed that maximum sorption capacity of MCAC was 39.48 mg/g for Cu(II) and 12.21 mg/g for Cd(II).     

Binding characteristics of Hg(II) with extracellular polymeric substances: implications for Hg(II) reactivity within periphyton

Environmental Science and Pollution Research - Periphyton contains extracellular polymeric substances (EPS), yet little is known about how periphyton EPS affect the speciation and mobility of...     

Biogeochemical dynamics of perfluorinated alkyl acids and sulfonates in the River Seine (Paris, France) under contrasting hydrological conditions

The biogeochemical dynamics of 15 perfluorinated compounds (PFCs) were investigated in a heavily urbanised river (River Seine, Paris, France). The target compounds included C4-C10 sulfonates and C5-C14 acids; eleven PFCs were detected and ∑PFCs ranged between 31 and 91 ng L⁻¹ (median: 47 ng L⁻¹). The molecular pattern was dominated by the perfluoroalkyl sulfonates PFHxS and PFOS (>54% of ∑PFCs), which were the only PFCs quantified in both the dissolved and particulate phases. For these PFCs, the sorbed fraction positively correlated with suspended sediment levels. Total PFC levels negatively correlated with river flow rate, which varied between 150 and 640 m³ s⁻¹. This suggests the predominance of point sources (likely WWTP effluent discharge), but a contribution of non-point sources such as combined sewer overflow could not be excluded. The annual PFC mass flow was estimated at 500 kg, which is less than observed for other large European rivers.