Technical and environmental long-term properties of industrial residues--summary of field and laboratory investigations

In Sweden, use of industrial residues is still hindered by concern for their long-term properties. A three-year research project was therefore initiated aiming to (1) identify the crucial processes of ageing related to the usefulness of residues in roads; (2) investigate the consequences of these processes for technical and environmental properties of the residues, and (3) propose a method for accelerated ageing to predict the long-term properties. This paper gives an overview of the project methodology, a summary of the test results and references to papers where further details are given.The project, running through 2006-2008, compared naturally aged samples of two residues used as sub-bases in existing asphalt paved roads with samples of fresh residues from producers’ piles. Steel slag of electric arc furnace (EAF) type and municipal solid waste incinerator (MSWI) bottom ash were chosen. The samples were thoroughly characterised in order to identify which ageing processes had been crucial.The results showed that:

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Bottom ash from the pavement edge was more aged than bottom ash from the road centre. However, no difference in pH was found, instead the differences were caused by differences in water exposure.

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Steel slag from the pavement edge showed traces of carbonation and leaching processes, whereas slag from the road centre was identical to fresh slag.

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Water exposure to the subbase materials after ten years in an asphalt paved road was calculated to less than 0.1-0.5 litres per kg.

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Ageing reactions in steel slag and MSWI bottom ash, ready for use, were too small to be verified by laboratory measurement of deformation properties under loaded conditions.

An accelerated ageing test for steel slag was set up to achieve the carbonation (decrease in pH) and leaching that was observed in the pavement edge material.An accelerated ageing test for bottom ash was set up to achieve the pozzolan reactions that were observed in SEM analyses of in situ specimens.It is recommended to use uncrushed particles when properties of aged material are studied, in order to preserve the original particle surfaces.     

Reclaiming the spent alkaline zinc manganese dioxide batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi0.5Mn1.5O4 materials

A process for reclaiming the materials in spent alkaline zinc manganese dioxide (Zn–Mn) batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi_0.5Mn_1.5O₄ materials is presented. After dismantling battery cans, the iron cans, covers, electric rods, organic separator, label, sealing materials, and electrolyte are separated through the washing, magnetic separation, filtrating, and sieving operations. Then, the powder residues react with H₂SO₄ (2 mol L^?1) solution to dissolve zinc under a liquid/solid ratio of 3:1 at room temperature, and subsequently, the electrolytic Zn with purity of ?99.8% is recovered in an electrolytic cell with a cathode efficiency of ?85% under the conditions of 37–40 °C and 300 A m^?2. The most of MnO₂ and a small quantity of electrolytic MnO₂ are recovered from the filtration residue and the electrodeposit on the anode of electrolytic cell, respectively. The recovered manganese oxides are used to synthesize LiNi_0.5Mn_1.5O₄ material of lithium-ion battery. The as-synthesized LiNi_0.5Mn_1.5O₄ discharges 118.3 mAh g^?1 capacity and 4.7 V voltage plateau, which is comparable to the sample synthesized using commercial electrolytic MnO₂. This process can recover the substances in the spent Zn–Mn batteries and innocuously treat the wastewaters, indicating that it is environmentally acceptable and applicable.     

Recovery of manganese oxides from spent alkaline and zinc–carbon batteries. An application as catalysts for VOCs elimination

Manganese, in the form of oxide, was recovered from spent alkaline and zinc–carbon batteries employing a biohydrometallurgy process, using a pilot plant consisting in: an air-lift bioreactor (containing an acid-reducing medium produced by an Acidithiobacillus thiooxidans bacteria immobilized on elemental sulfur); a leaching reactor (were battery powder is mixed with the acid-reducing medium) and a recovery reactor. Two different manganese oxides were recovered from the leachate liquor: one of them by electrolysis (EMO) and the other by a chemical precipitation with KMnO₄ solution (CMO). The non-leached solid residue was also studied (RMO). The solids were compared with a MnO_x synthesized in our laboratory.The characterization by XRD, FTIR and XPS reveal the presence of Mn₂O₃ in the EMO and the CMO samples, together with some Mn⁴⁺ cations. In the solid not extracted by acidic leaching (RMO) the main phase detected was Mn₃O₄.The catalytic performance of the oxides was studied in the complete oxidation of ethanol and heptane. Complete conversion of ethanol occurs at 200 °C, while heptane requires more than 400 °C. The CMO has the highest oxide selectivity to CO₂.The results show that manganese oxides obtained using spent alkaline and zinc–carbon batteries as raw materials, have an interesting performance as catalysts for elimination of VOCs.     

Preparation and Characterization of Polyaniline and Ag/ Polyaniline Composite Nanoporous Particles and Their Antimicrobial Activities

Polyaniline (PANI) and Ag/PANI nanoporous composite were prepared by an oxidative polymerization method. The oxidation process of PANI nanoparticles was occurred using (NH₄)₂S₂O₈ while the oxidation process of Ag/PANI nanoporous composite was occurred using AgNO₃ under the effect of artificial radiation. The structural, morphological, and optical properties of the PANI and Ag/PANI nanoporous structures were studied using different characterization tools. The results confirm the formation of polycrystalline nanoporous PANI and spherical nanoporous composite of Ag/PANI particles. Antibacterial activity tests against gram-positive bacteria, Bacillus subtilis and Staphylococcus aureus, and gram-negative bacteria, Escherichia coli, and Salmonella species were carried out using different concentrations of PANI nanoparticles and Ag/PANI nanoporous composites. PANI has not antibacterial effect against all studied pathogens. In contrast, Ag/PANI nanoporous composites possessed antibacterial activity that is identified by the zone of inhibition. The inhibition zones of bacteria are in order; Salmonella species?>?S. aureus?>?B. subtilis?>?E. coli. The inhibition zones of all bacteria increased with increasing concentrations of Ag/PANI nanoporous composites from 200 to 400 ppm then decreased with further increasing of the dose concentrations to 600 ppm. Finally, a simplified mechanism based on the electrostatic attraction is presented to describe the antimicrobial activity of Ag/PANI nanoporous composite.     

Kinetic Analysis of the Temperature Effect on Polyhydroxyalkanoate Production by <Emphasis Type="Italic">Haloferax mediterranei</Emphasis> in Synthetic Molasses Wastewater

Haloferax mediterranei is an extremely halophilic archaeon that is able to synthesize polyhydroxyalkanoate (PHA) in high salt environment with low sterility demand. In this study, a mathematical model was validated and calibrated for describing the kinetic behavior of H. mediterranei at 15, 20, 25, and 35 °C in synthetic molasses wastewater. Results showed that the production of PHA by H. mediterranei, ranging from 390 to 620 mg h^?1 L^?1, was strongly dependent on the temperature. The specific growth rate (µ _max), specific substrate utilization rate (q _max), and specific decay rate (k _d) of H. mediterranei increased with temperature following Arrhenius equation prediction. The estimated activation energy was 58.31, 25.59, and 22.38 kJ mol^?1 for the process of cell growth, substrate utilization, and cell decay of H. mediterranei, respectively. The high temperature triggered the increased PHA storage even without nitrogen limitation. Thus, working at high temperatures seems a good strategy for improving the PHA productivity of H. mediterranei.     

Dynamic studies on lead volatilization from CaO–SiO2–Al2O3 molten slag under N2–CO–CO2, N2–HCl and N2–H2S gas atmospheres

Dynamic studies on the volatilization of lead from CaO–SiO₂–Al₂O₃ molten slags were conducted in a lab-scale melting furnace from 1623 to 1773 K under different mixed gas atmospheres of CO 0.05–0.3 atm to CO₂ 0–0.3 atm to N₂ (balance), HCl 1.7 × 10^?3–6.7 × 10^?3 atm to N₂ (balance), and H₂S 3.0 × 10^?4 to 1.7 × 10^?3 atm to N₂ (balance). The slag samples consisted of the mixed powders of 20–50 wt% CaO, 30–60 wt% SiO₂, and 10–40 wt% Al₂O₃, containing 2000 ppm PbO.Results showed that the rates of volatilization of lead from the CaO–SiO₂–Al₂O₃ molten slags under the N₂–CO–CO₂, N₂–HCl, and N₂–H₂S gas atmospheres were higher than those under the simulated air (N₂–O₂), which increased with CO, HCl, and H₂S partial pressures. At \(p_{{HCl}}\)  =  \(p_{H_{2}S}\)  = 1.7 × 10^?3 atm, the apparent rate constants for the volatilization of lead under the N₂–H₂S and N₂–HCl gas atmospheres were nearly equal, which increased with a rise in temperature. Results also showed that the rate of volatilization of lead from the molten slag decreased drastically with the increasing viscosity of the molten slag, in the viscosity range lower than 3 Pa s. Consequently, the volatilization of lead from the CaO–SiO₂–Al₂O₃ molten slag was significantly influenced by CO, HCl, and H₂S partial pressures and by the viscosity of the molten slag.     

Comparison of three ornamental plants for phytoextraction potential of chromium removal from tannery sludge

Based on pre-experimentation, three ornamental plants, Mirabilis jalapa, Impatiens Balsamin (I. Balsamin) and Tagetes erecta L., were selected as target plants to study the phytoextraction of chromium (Cr) in tannery sludge irrigated with four treatments according to Cr concentration gradient [Control (CK); 20.50 × 10³ mg kg^?1 (T1); 51.25 × 10³ mg kg^?1 (T2); 102.50 × 10³ mg kg^?1 (T3)]. Results of pot experiments showed that the biomass of Mirabilis jalapa and Tagetes erecta L. had no significant differences among the four treatments, while I. Balsamin showed a decline trend in the biomass with the increase of Cr concentration, probably due to some extent to the poisoning effect of Cr under treatment T2 or T3. Mirabilis jalapa accumulated Cr concentration, with 408.97, 124.97, 630.16 and 57.30 mg kg^?1 in its roots, stems, leaves and inflorescence, respectively. The translocation factor and the bioaccumulation coefficient of Mirabilis jalapa are each greater than 1, indicating that Mirabilis jalapa has the strong ability to tolerate and enrich Cr by biological processes. Comparing accumulation properties of the three ornamental plants, in the amount and allocation, Mirabilis jalapa showed the highest phytoextraction efficiency and could grow well at the high Cr concentration. Our experiments suggest that Mirabilis jalapa is the expected flower species for Cr removal from tannery sludge.     

Selective Lead(II) Adsorption and Flocculation Characteristics of the Grafted Sodium Alginate: A Comparative Study

Synthesis of sodium alginate-g-poly(acrylamide-co-N-methylacrylamide) [S-III], sodium alginate-g-poly(N-methylacrylamide-co-N,N-dimethylacrylamide) [S-II], sodium alginate-g-poly(acrylamide-co-N,N-dimethylacrylamide) [S-I]. Sodium alginate-g-poly(N,N-dimethylacrylamide) [SAG-g-PDMA] and sodium alginate-g-poly(acrylamide) [SAG-g-PAM] were prepared by solution polymerization technique using potassium peroxydisulfate as the initiator at 70?°C in water medium. The graft copolymers were characterized by FTIR and NMR (¹H and ¹³C) spectroscopy, SEM and XRD studies. All the five graft copolymers were used to remove Pb(II) ions from the aqueous solution and also in flocculation studies of kaolin clay (1.0 wt%), silica (1.0 wt%) and iron ore slime (0.25 wt%) suspensions. A comparative studies of all the five graft copolymers were also made in both the two cases. The Pb(II) ion removal capacity of all the graft copolymers follows the order S-III?>?SAG-g-PAM?>?S-II?>?SAG-g-PDMA?>?S-I. But the flocculation performance of the graft copolymers follows the order S-II?>?S-I?>?S-III?>?SAG-g-PDMA?>?SAG-g-PAM. S-III was also used for the competitive metal ion removal with Hg(II), Cd(II), Cu(II) and Zn(II). Pb(II) adsorption of S-III (the best Pb(II) ion adsorber) follows pseudo second order rate equation and Langmuir adsorption isotherm.     

Application of ameliorated wood pulp to recover Cd(II), Pb(II), and Ni(II) from e-waste

In this study, dl-malic acid and hydrogen peroxide were used as leaching agents to remove metals from e-waste (printed-circuit boards) and itaconic acid-grafted poly(vinyl alcohol)-encapsulated wood pulp (IA-g-PVA-en-WP) to uptake metals from leachate with high proficiency [11.63 mg g^?1; 93.03 % for Cd(II), 11.90 mg g^?1; 95.18 % for Pb(II), and 12.14 mg g^?1; 97.08 % for Ni(II)]. Metals were recovered from the loaded biosorbent by desorption studies. The standard analytical techniques, such as elemental analysis, Fourier-transform-infrared spectroscopy, scanning electron microscopy, atomic force microscopy, and thermogravimetric analysis, were used to characterize the recovering agent (biosorbent). At equilibrium, the metal uptake data were fitted to Langmuir and D–R isotherms (R ² > 0.99) significantly, revealing, the homogeneous distribution of active sites on biosorbent’s backbone. The possible mechanism appeared to be ion exchanges of metal ions with H⁺ together with binding over functionalities (COO^?). Dimensionless equilibrium parameter (R _L) showed the favourability of metal uptake at lower concentration, while mean adsorption energy (E) certified the physical binding of metal on functionalities which was further confirmed by sticking probability and activation energy parameters. Reusability studies were also conducted to state the performance of biosorbent.     

BMP estimation of landfilled municipal solid waste by multivariate statistical methods using specific waste parameters: case study of a sanitary landfill in Turkey

The main objective of this study was to determine whether methane potential of waste could be estimated more easily by a limited number of waste characterization variables. 36 samples were collected from 12 locations and 3 waste depths in order to represent almost all waste ages at the landfill. Actual remaining methane potential of all samples was determined by the biochemical methane potential (BMP) tests. The cumulative methane production of closed landfill (cLF) samples reached 75–125 mL at the end of experiment duration, while the samples from active landfill (aLF) produced in average 216–266 mL methane. The average experimental k and L ₀ values of cLF and aLF were determined by non-linear regression using BMP data with first-order kinetic equation as 0.0269 day^?1–30.38 mL/g dry MSW and 0.0125 day^?1–102.1 mL/g dry MSW, respectively. The principal component analysis (PCA) was applied to analyze the results for cLF and aLF along with BMP results. Three PCs for the data set were extracted explaining 72.34 % variability. The best MLR model for BMP prediction was determined for seven variables (pH–Cl–TKN–NH4–TOC–LOI–Ca). R ² and Adj. R ² values of this best model were determined as 80.4 and 75.3 %, respectively.     

Distribution of inorganic bromine and metals during co-combustion of polycarbonate (BrPC) and high-impact polystyrene (BrHIPS) wastes containing brominated flame retardants (BFRs) with metallurgical dust

This study focused on the thermal degradation of polycarbonate (BrPC) and high-impact polystyrene (BrHIPS), containing different brominated flame retardants. The evolved inorganic bromine was utilized for the separation of metals present in electric arc furnace dust (EAFD). The thermal degradation of BrPC generated inorganic gaseous HBr (69%) and condensable Br₂ (31%). The bromine evolved from BrHIPS was detected almost entirely in a condensed phase as SbBr₃. When mixed with EAFD, the evolved inorganic bromine reacted immediately with the metallic components of zinc and lead, but not with iron. The best bromination efficiencies were obtained during the isothermal heating (80 min at 550 °C) of the mixtures at mass ratios of 6:1 and 9:1 w/w under oxidizing conditions. The achieved brominating rates reached 78 and 81% for zinc and 90 and 94% for lead in 6:1 and 9:1 BrPC:EAFD, respectively, and 47 and 65% for zinc and 67 and 63% for lead in 6:1 and 9:1 BrHIPS:EAFD, respectively. The oxidizing condition favored complete vaporization of the formed bromides.     

Comparative fertilizer properties of digestates from mesophilic and thermophilic anaerobic digestion of dairy manure: focusing on plant growth promoting bacteria (PGPB) and environmental risk

The fertilizer properties of anaerobic digestate depend on the feedstock and operating conditions of digestion. In this study, the comparative fertilizer properties of mesophilic and thermophilic digestates from dairy manure were evaluated for plant nutrient contents, and special attention was paid to plant growth promoting bacteria (PGPB). Two digestates contained similar plant nutrient contents, while the thermophilic digestate contained higher contents of NH₄⁺–N. The quantity of Bacillus and Pseudomonas in the mesophilic digestate was significantly higher than in the thermophilic digestate. Furthermore, Bacillus showed siderophore production and antifungal activity (43.5–75.3%), and Pseudomonas showed siderophore and phytohormone production (4.2–75.2 µg ml^?1). One phosphate solubilizing isolate was also detected in the mesophilic digestate. These results indicated that two digestates showed different fertilizer properties with respect to nutrient contents and PGPB, and digestates had the potential to increase the availability of phosphorus and iron in the soil, both to provide phytohormones to plant roots and protect plants from fungal phytopathogens. The contents of indicator bacteria and heavy metals were analyzed to determine their environmental risk, and the results showed a high reduction in indicator bacteria and lower levels of heavy metals than in other feedstocks.     

Adsorption of Crystal Violet Dye from Aqueous Solution by Poly(Acrylamide-<Emphasis Type="Italic">co</Emphasis>-Maleic Acid)/Montmorillonite Nanocomposite

Poly(acrylamide-co-maleic acid)/montmorillonite nanocomposites, were synthesized via in situ polymerization with different maleic acid and MMT content. The capability of the hydrogel for adsorption of crystal violet (CV) was investigated in aqueous solutions at different pH values and temperatures. The pseudo-second-order kinetics model could fit successfully the adsorption kinetic data. The effects of maleic acid to acrylamide molar ratio (MA_R), weight percent of MMT (MMT%), the pH of medium and the solution temperature (T) on the CV adsorption capacity (q _e ) of adsorbents were studied by Taguchi experimental design approach. The results indicated that increasing the MMT% leads to a greater q _e . The q _e value of adsorbents increased also with increasing both MA_R and pH, while reduced when the temperature of medium increased. The relatively optimum conditions to achieve a maximum CV adsorption capacity for P(AAm/MA)/MMT adsorbents were found as: 0.06 for MA_R and 5 % of MMT%, medium pH = 7 and T = 20 °C.     

Water Absorption Kinetics and Hygrothermal Aging of Poly(lactic acid) Containing Halloysite Nanoclay and Maleated Rubber

Poly(lactic acid)/halloysite nanoclay composites (PLA/HNC) containing maleic anhydride grafted styrene-ethylene/butylene-styrene (SEBS-g-MAH) were produced using melt compounding followed by compression molding. The effects of hygrothermal aging on the thermal properties and functional groups changes of the HNC reinforced PLA (with and without SEBS-g-MAH) at three different temperatures (i.e., 30, 40 and 50 °C) were analyzed using differential scanning calorimetry and Fourier transform infrared spectroscopy techniques. The diffusion coefficient (D) of PLA was decreased by the incorporation of HNC and SEBS-g-MAH. The activation energy of water diffusion (E _a ) of PLA/HNC/SEBS-g-MAH nanocomposites was higher than that of pure PLA. The glass transition temperature (T _g ), cold-crystallization temperature (T _cc ) and melting temperature (T _m ) of the PLA sample were shifted to lower temperature and the effect was more pronounced at 50 °C. The carbonyl index values of all PLA samples increased after immersed in 40 and 50 °C, which is due to the formation of higher amount of carboxyl groups during the hydrolysis process.     

Ecological treatment of El Kriymat boiler ash for recovering vanadium,nickel and zinc from sulfate leach liquor

The primary goal of this work is to develop a technology that allows for the recovery of metal values from waste products, thereby promoting the wise and efficient use of our nation's resources. To achieve this goal, an industrial waste of El Kriymat boiler fly Ash was used for recovering its content of vanadium, nickel and zinc. About 97, 95 and 99% respectively of these economic elements were first dissolved from boiler fly ash magnetic concentrate (after physical concentration). Leaching experiments using optimum conditions include: 180 g/L sulfuric acid concentration and 4% solid/solid proportion manganese dioxide acts as an oxidant at 80 °C. The recovery of vanadium (V) metal ions was carried out using 3% Alamine 336 in kerosene at an equilibrium pH value of 0.9. Subsequently, 15% sodium sulfide solution was used for co-precipitation of nickel and zinc metal ions in the raffinate solution at pH value of 3.5.

Graphical Abstract

     

Microbial Degradation of UV-Pretreated Low-Density Polyethylene Films by Novel Polyethylene-Degrading Bacteria Isolated from Plastic-Dump Soil

Eleven effective low-density polyethylene (LDPE)-degrading bacterial strains were isolated and identified from landfill soil containing large amounts of plastic materials. The isolates belonged to 8 genera, and included Pseudomonas (areroginosa and putida), Sphingobacterium (moltivorum), Delftia (tsuruhatansis), Stentrophomonas (humi and maltophilia), Ochrobacterum (oryzeae and humi), Micrococcus (luteus), Acinetobacter (pitti), and Citrobacter (amalonaticus). Abiotic degradation of LDPE films by artificial and natural ultraviolet (UV)-exposure was analyzed by FT-IR spectroscopy. LDPE films treated with UV-radiation were also inoculated with the isolates and biofilm production and LDPE degradation were measured. Surface changes to the LDPE induced by bacterial biofilm formation were visualized by Scanning Electron Microscopy. The most active bacterial isolate, IRN19, was able to degrade polyethylene film by 26.8?±?3.04% gravimetric weight over 4 weeks. Analysis of 16S rRNA sequence of this isolate revealed 96.97% similarity in sequence to Acinetobacter pitti, which has not previously been identified as a polyethylene-degrading bacterium. Also, most the effective biofilm forming isolate, IRN11, displayed the highest cell mass production (6.29?±?0.06 log cfu/cm²) after growth on LDPE films, showed 98.74% similarity to Sphingobacterium moltivourum.     

Nitrate and phosphate leaching in a Phaeozem soil treated with biosolids,composted biosolids and inorganic fertilizers

The use of organic wastes in agriculture may increase the production of crops by incorporating organic matter and nutrients into the soil, and by improving its physical characteristics; however, this use may cause environmental problems such as the leaching of certain ions. The objective of this study was to establish possible nitrogen and phosphorus leaching under real field conditions in Phaeozem soils. The experimental work was performed in a corn (Zea mays L.) field where three plots were conditioned with inorganic fertilizer, three plots with 4.5 Mg ha^?1 of biosolids on dry basis, and three plots with the same amount of composted biosolids. The quality of biosolids and composted biosolids complied with the Mexican Official Standards. Soil water samples were collected with suction cups during two agricultural cycles and were analysed. Soil samples were also taken and analysed.The N–NO₃ concentrations in soil water fluctuated between 0.9 and 98 mg L^?1 in the composted biosolid treatment, between 0.7 and 64 mg L^?1 in the biosolid treatment, and between 1 and 61 mg L^?1 in the inorganic fertilizer treatment. The maximum concentration of N–NO₂ and N–NH₃ in soil water was 1.02 and 2.65 mg L^?1, respectively. The greatest percentage of nitrogen leached is produced when inorganic fertilizer is used (37.4% and 24.0% N leached in the first and second years, respectively), followed by composted biosolids (17.1% and 13.5% N leached in the first and second years, respectively) and last by biosolids (11% for both years). This difference could be related to the form in which nitrogen is present in the fertilizers, while commercial fertilizer is as inorganic nitrogen, organic wastes are basically presented as organic nitrogen. The maximum ${\text{PO}}_4^{3-}$ concentration in soil water was 1.9 mg L^?1 in the composted biosolid treatment, 1.7 mg L^?1 in the biosolid treatment and 0.9 mg L^?1 in the inorganic fertilizer treatment. The estimated percentage of leached phosphorus was less than 1% for all treatments. The minimum leaching that occurred seemed to be due to a sorption–precipitation process.