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.     

Distribution of remaining Cd in MSWI fly ash washed with nitric acid

Municipal solid waste incineration (MSWI) fly ash is by-product and hazardous waste produced from MSWI plant. In the MSWI fly ash there are high contents heavy metals, among which cadmium (Cd) is more active and toxic. Although inorganic acid leaching is an effective way to remove heavy metals out from the MSWI fly ash and nitric acid has great efficiency for Cd removal, little literature reported the redistribution of remaining Cd in the MSWI fly ash. This investigation focused on the change of different factions (exchangeable, bound to carbonates, bound to Fe–Mn oxides, bound to organic matter and residual) of Cd in treated (i.e. washed with nitric acid) MSWI fly ash. Sequence extraction procedures (SEP) have been used to derive different fractions of Cd, results indicated that fractions of Cd have changed significantly after nitric acid washing procedures. Due to the changes of main compounds and microstructures stable Cd (bound to organic matter and residual) had opportunity to leach out, which resulted in a higher potential risk (or higher bioavailability index) for living creatures, although the total amount of Cd decreased. X-ray diffraction (XRD) and images of scanning electron microscope (SEM) proved these changes in washed MSWI fly ash.     

Zinc removal from synthetic waters using magnetite/graphene oxide composites

The removal of heavy metals from wastewater has become a global challenge, which demands the continuous study of efficient and low-cost treatment alternatives such as adsorption. In this research, the removal of zinc was evaluated using batch adsorption processes with nonconventional materials such as graphene oxide (GO), magnetite (MG), and their composites (GO:MG), formulated with three weight ratios (2:1, 1:1, and 1:2). Graphene was synthesized by the modified Marcano method, using pencil lead graphite as a precursor. MG and the composites were synthesized by chemical coprecipitation of ferrous sulfate and ferric chloride. The materials were characterized by Raman and Fourier transform infrared spectroscopies, scanning electron microscopy, X-ray diffraction, and the Brunauer–Emmett–Teller method to determine the functional groups, microstructural and morphological characteristics, and specific surface area. Batch adsorption tests were carried out to optimize the adsorbent dose and contact time with zinc solutions of 10 ppm. Zinc adsorption reached equilibrium at 2 h, with an optimal dose between 0.25 and 1.0 g/L. The maximum zinc removal efficiencies/adsorption capacities were 98.6%/165.6, 83.4%/47.6, 83.5%/21.9, 72.8%/19.9, and 82.2%/9.25 mg/g using GO, 2GO:1MG, 1GO:1MG, 1GO:2MG, and MG, respectively. Furthermore, the analysis of the isotherm and adsorption kinetics models determined that the adsorption processes using MG and the composites fit the Sips and pseudo-second-order models.     

Vitrification of electric arc furnace dusts

Electric arc furnace baghouse dust (EAFD), a waste by-product of the steelmaking process, contains the elements that are volatilized from the charge during the melting (Cr, Pb, Zn, Cu and Cd). The results of leaching tests show that the concentration of these elements exceeds the regulatory limits. Consequently, EAFD cannot be disposed of in ordinary landfill sites without stabilization of the heavy metals. In this work, the vitrification of EAFD, from both carbon and stainless steel productions, were studied. The vitrification process was selected as the inertizing process because it permits the immobilization of the hazardous elements in the glass network and represents an environmentally acceptable method for the stabilization of this waste. Classes of various compositions were obtained by mixing EAFD with glass cullet and sand. The EAFD and the glass products were characterized by DTA, TG, X-ray analysis and by the TCLP test. The results show that the stability of the product is influenced by the glass structure, which mainly depends on the Si/O ratio. Secondary crystallization heat-treatment were carried out on some samples. The results highlighted the formation of spinel phases, which reduced the chemical durability in acid media. The possibility to recover Zn from carbon steel production EAFD was investigated and about 60-70% of metal recovery was obtained. The resulting glass show higher chemical stability than glasses obtained without metal recovery.     

Variations of metal distribution in sewage sludge composting

In the study, the variations of heavy metal distributions (of Cu, Mn, Pb, and Zn) during the sewage sludge composting process were investigated by sequential extraction procedures. The total content of Cu and Zn in the composted mixture increased after the composting process. Mn and Zn were mainly found in mobile fractions (exchangeable fraction (F1), carbonate fraction (F2), and Fe/Mn oxide fraction (F3)). Cu and Pb were strongly associated with the stable fractions (organic matter/sulfides fraction (F4) and residual fraction (F5)). These five metal fractions were used to calculate the metal mobility (bioavailability) in the sewage sludge and composted mixture. The mobility (bioavailability) of Mn, Pb, and Zn (but not Cu) increased during the composting process. The metal mobility in the composted mixture ranked in the following order: Mn>Zn>Pb>Cu.     

Value-added utilisation of recycled concrete in hot-mix asphalt

The feasibility of partial substitution of granite aggregate in hot-mix asphalt (HMA) with waste concrete aggregate was investigated. Three hybrid HMA mixes incorporating substitutions of granite fillers/fines with 6%, 45% untreated, and 45% heat-treated concrete were evaluated by the Marshall mix design method; the optimum binder contents were found to be 5.3%, 6.5% and 7.0% of grade Pen 60/70 bitumen, respectively. All three hybrid mixes satisfied the Marshall criteria of the Singapore Land Transport Authority (LTA) W3B wearing course specification. The hybrid mix with 6% concrete fillers gave comparable resilient modulus and creep resistance as the conventional W3B mix, while hybrid mixes with higher concrete substitutions achieved better performance. X-ray diffraction (XRD) showed the distinct presence of free lime in the heat-treated concrete, while the scanning electron microscope (SEM) provided an in-depth perspective of the concrete grains in the HMA matrix. The results suggest feasible use of waste concrete as partial aggregate substitution in HMA.     

The effect of sediment redox chemistry on solubility/chemically active forms of selected metals in bottom sediment receiving produced water discharge

The effect of sediment redox conditions on the solubility behavior of Fe, Pb, Ni, Ba, and Cu in bottom sediment collected from a produce water discharge site was investigated using kinetics and chemical fractionation procedures. Sediment collected was composited and subsamples incubated in laboratory microcosms under controlled Eh-pH conditions. Sediment was sequentially extracted for determining metals in five fractions (exchangeable, carbonate, bound to iron and manganese oxide, bound to organic matter and sulfide, mineral matrix or residue). Metal distribution in the fractions indicates that under oxidizing sediment conditions, the behavior of Fe, Pb and Ni were governed by Fe(III) and Mn(IV) oxides; Ba by insoluble complexation with humic compounds; and Cu by carbonates and humic complexation. Under reducing sediment condition, the behaviors of Fe and Cu were controlled by the formation of insoluble sulfides and humic complexes; the behaviors of Ni and Ba by carbonate and Pb behavior by sulfides, carbonates and humic complexes. With increases in sediment redox potential, the affinity between Fe(III), Mn(IV) oxides and Fe, Pb, Ni, Cu increased, the affinity between insoluble large molecular humic and Ba increased, and the affinity between carbonates and Cu increased. With decreasing sediment redox potential, the affinity between carbonates and Fe, Ni, Ba increased; the affinity between sulfides, humic substances and Fe, Pb, Ni, Cu also increased. Upon Fe(III) oxide reduction, it is estimated that 20% of total reducible Fe(III) oxides was reduced by direct bacterial reduction (K = −42.6 ppm/day), 80% of total reducible Fe(III) oxides was associated with chemical fractions attributed to sulfide oxidation (K = −171.5 ppm/day). The rate constants (ppm/day) for dissolved Ni (Eh <0 mV), Pb (Eh < −80 mV) and Cu (−80 mV < Eh <0 mV) are −1.6, −0.047 and −0.16, respectively. In our incubation period, the rate constants (ppm/day) for Ni bound to Fe(III) and Mn(IV) oxides, Ba bound to carbonates and Cu bound to insoluble large molecular humic are −3.2, 0.91 and 4.3, respectively.     

用含锌废催化剂制备纳米氧化锌

以含锌废催化剂为原料，经酸浸、除杂、锌粉置换、合成等工艺制得碱式碳酸锌，再经过滤、洗涤、干燥、煅烧制备纳米氧化锌。考察了酸浸工艺硫酸溶液含量和液固比（硫酸与含锌废催化剂的质量比）对锌浸出率的影响，以及煅烧温度对纳米氧化锌质量的影响。实验结果表明：在硫酸质量分数为30%、液固比为5的最佳酸浸工艺条件下，锌浸出率为92%；在最佳煅烧温度为400 ℃的条件下，氧化锌质量分数大于95%，比表面积大于50 m²/g；纳米氧化锌颗粒大小均匀，平均粒径小于50 nm。     

Decomposition of asbestos by a supernatant used for immobilization of heavy metals in fly ash

A supernatant solution, obtained after immobilization of heavy metals involved in fly ashes by a solution of sulfur and calcium hydroxide, was re-used for immobilization of heavy metals and decomposition of asbestos in construction materials. Asbestos was decomposed to more than 99.9 % by mixing it with the supernatant in a ball mill at room temperature. The decomposition of asbestos was confirmed by X-ray diffraction (XRD), a phase contrast microscope after staining the asbestos with solutions of different diffractive indexes and a scanning electron microscope. XRD indicated complete disappearance of specific main peaks of asbestos: chrysotile, crocidolite, amosite and tremolite. Heavy metals such as chromium(VI) and lead(II) in fly ashes were completely immobilized by the supernatant. It is the first time that a solution obtained after the treatment of wasted fly ash is recycled for decomposition of hazardous waste materials such as asbestos.     

Effects of emulsified asphalt on the mechanical properties of granulation of calcium fluoride sludge

Journal of Material Cycles and Waste Management - To reduce the landfill volume of waste CaF2 sludge, artificial fluorite bulk (AFB) is granulated by blending CaF2 sludge and emulsified asphalt...     

Precious Metals in Municipal Solid Waste Incineration Bottom Ash

Municipal solid waste incineration (MSWI) bottom ash contains economically significant levels of silver and gold. Bottom ashes from incinerators at Amsterdam and Ludwigshafen were sampled, processed, and analyzed to determine the composition, size, and mass distribution of the precious metals. In order to establish accurate statistics of the gold particles, a sample of heavy non-ferrous metals produced from 15 tons of wet processed Amsterdam ash was analyzed by a new technology called magnetic density separation (MDS). Amsterdam’s bottom ash contains approximately 10 ppm of silver and 0.4 ppm of gold, which was found in particulate form in all size fractions below 20 mm. The sample from Ludwigshafen was too small to give accurate values on the gold content, but the silver content was found to be identical to the value measured for the Amsterdam ash. Precious metal value in particles smaller than 2 mm seems to derive mainly from waste of electrical and electronic equipment (WEEE), whereas larger precious metal particles are from jewelry and constitute the major part of the economic value. Economical analysis shows that separation of precious metals from the ash may be viable with the presently high prices of non-ferrous metals. In order to recover the precious metals, bottom ash must first be classified into different size fractions. Then, the heavy non-ferrous (HNF) metals should be concentrated by physical separation (eddy current separation, density separation, etc.). Finally, MDS can separate gold from the other HNF metals (copper, zinc). Gold-enriched concentrates can be sold to the precious metal smelter and the copper-zinc fraction to a brass or copper smelter.     

Nutrients and heavy metals distribution in thermally treated pig manure.

Ash from pig manure treated by combustion and thermal gasification was characterized and compared in terms of nutrient, i.e., potassium (K), phosphorus (P) and heavy metal, i.e., cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni) and zinc (Zn) contents. Total nutrient and metal concentrations were measured using energy dispersive X-ray fluorescence analysis. Acid (HNO3, H2SO4) and water-extractable concentrations were also measured both in non-classified ash and in selected ash particle size fractions using flame atomic absorption spectrometry and colorimetric spectrometry. Results indicate that ash from gasified manure contained more water-extractable K in comparison with combusted manure whereas the opposite was the case with respect to P. Heavy metals Ni, Cr and Cd were present in higher concentrations in the fine particle size fractions (< 30 microm of particle diameter), whereas K, P, Zn and Cu exhibited higher concentrations in the coarser particle size fractions (> 30 microm).     

Thermal treatment for recovery of manganese and zinc from zinc-carbon and alkaline spent batteries

The aim of this paper is the recovery of manganese and zinc from a mixture of zinc-carbon and alkaline spent batteries, containing 40.9% of Mn and 30.1% of Zn, after preliminary physical treatment followed by removal of mercury. Separation of the metals has been carried out on the basis of their different boiling points, being 357°C and 906°C the boiling point of mercury and zinc and 1564°C the melting point of Mn(2)O(3). Characterization by chemical analysis, TGA/DTA and X-ray powder diffraction of the mixture has been carried out after comminution sieving and shaking table treatment to remove the anodic collectors and most of chlorides contained in the mixture. The mixture has been roasted at various temperatures and resident times in a flow of air to set the best conditions to remove mercury that were 400°C and 10min. After that, the flow of air has been turned into a nitrogen one (inert atmosphere) and the temperatures raised, thus permitting the zinc oxide to be reduced to metallic zinc by the carbon present in the original mixture and recovered after volatilization as a high grade concentrate, while manganese was left in the residue. The recovery and the grade of the two metals, at 1000°C and 30min residence time, were 84% and 100% for zinc and 85% and 63% for manganese, respectively. The recovery of zinc increased to 99% with a grade of 97% at 1200°C and 30min residence time, while the recovery and grade of manganese were 86% and 87%, respectively, at that temperature. Moreover, the chlorinated compounds that could form by the combustion of the plastics contained in the spent batteries, are destroyed at the temperature required by the process.     

Utilization of gold tailings as an additive in Portland cement.

Mine tailings are formed as an industrial waste during coal and ore mining and processing. In the investigated process, following the extraction of gold from the ore, the remaining tailings are subjected to a two-stage chemical treatment in order to destroy the free cyanide and to stabilize and coagulate heavy metals prior to discharge into the tailings pond. The aim of this study was the investigation of the feasibility of utilization of the tailings as an additive material in Portland cement production. For this purpose, the effects of the tailings on the compressive strength properties of the ordinary Portland cement were investigated. Chemical and physical properties, mineralogical composition, particle size distribution and microstructure of the tailings were determined by Fourier transform infrared spectroscopy (FTIR), X-ray diffractometry (XRD), particle size analyzer (Mastersizer) and scanning electron microscope (SEM). Following the characterization of the tailings, cement mortars were prepared by intergrinding Portland cement with dried tailings. Composition of the cement clinkers were adjusted to contain 5, 15, 25% (wt/wt) dried tailings and also silica fume and fly ash samples (C and F type) were added to clinker in different ratios. The mortars produced with different amounts of tailings, silica fume, fly ashes and also mixtures of them were tested for compressive strength values after 2, 7, 28 and 56 days according to the European Standard (EN 196-1). The results indicated that gold tailings up to 25% in clinker could be beneficially used as an additive in Portland cement production. It is suggested that the gold tailings used in the cement are blended with silica fume and C-type fly ash to obtain higher compressive strength values.     

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.     

Chemical durability of glasses obtained by vitrification of industrial wastes

The vitrification of zinc-hydrometallurgy wastes, electric arc furnace dust (EAFD), drainage mud, and granite mud was shown to immobilize the hazardous components in these wastes. Batch compositions were prepared by mixing the wastes with glass-cullet and sand to force the final glass composition into the glass forming region of the SiO2-Fe2O3-(CaO, MgO) system. The vitrification was carried out in the 1400-1450 degrees C temperature range followed by quenching in water or on stainless steel mold. The United States (US) Environmental Protection Agency (EPA) toxic characterization leaching procedure (TCLP) test was used as a standard method for evaluating the leachability of the elements in the glasses and glass-ceramics samples made with different percentages of wastes. The results for EAFD glasses highlighted that the chemical stability is influenced by the glass structure formed, which, in turn, depends on the Si/O ratio in the glass. The chemical durability of jarosite glasses and glass-ceramics was evaluated by 24 h contact in NaOH, HCl and Na2CO3, at 95 degrees C. Jarosite glass-ceramics containing pyroxene (J40) are more durable than the parent glass in HCl. Jarosite glass-ceramics containing magnetite type spinels (J50) have a durability similar to the parent glass and even lower in HCl because the magnetite is soluble in HCl.     

Role of aluminous component of fly ash on the durability of Portland cement-fly ash pastes in marine environment

The durability, of mixtures of two kinds of Spanish fly ashes from coal combustion (ASTM class F) with 0, 15 and 35% replacement of Portland cement by fly ash, in a simulated marine environment (Na(2)SO(4)+NaCl solution of equivalent concentration to that of sea water: 0.03 and 0.45 M for sulphate and chloride, respectively), has been studied for a period of 90 days. The resistance of the different mixtures to the attack was evaluated by means of the Koch-Steinegger test. The results showed that all the mixtures were resistant, in spite of the great amount of Al(2)O(3) content of the fly ash. The diffusion of SO(4)(2-), Na+ and Cl- ions through the pore solution activated the pozzolanic reactivity of the fly ashes causing the corresponding microstructure changes, which were characterized by X-ray diffraction (XRD), mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). As a result, the flexural strength of the mixtures increased, principally for the fly ash of a lower particle size and 35% of addition.     

Novel Pretreatment Performance Evaluation for Cellulose Nanofibrils Extraction from Ficus natalensis Barkcloth

Recently, nanosized cellulose materials extraction is extensively interesting from the sources of sustainable materials. Cellulose nanofibrils (CNF) extraction through green bio-based materials featured as promising interest in the field of science. In this study, dimethyl sulfoxide (DMSO) was applied to examine its effectiveness in pretreating the Ficus natalensis barkcloth cellulose (FNBC) for CNF production before 2,2,6,6,-tetramethylpiperidine-1-oxyl (TEMPO) oxidation. The pretreatment performance of DMSO was evaluated based on the structural and morphological changes. DMSO pretreated FNBC attained the most dramatic morphological changes as compared to untreated cellulose samples. The results of the scanning electron microscope (SEM) and transmission electron microscope (TEM) shows that there is an extensive structural disruption of FNBC during the pretreatment process, which could be because of outstanding ability to eliminate non-cellulosic materials and amorphous regions from the FNBC, confirmed by the X-ray diffractometry (XRD) showing higher crystallinity values, as well as higher thermal stabilities values of pretreated FNBC samples, were also noted. Overall, this study revealed a tremendously effective and pioneer pretreatment method for fractionating FNBC, to stimulate the successive extraction of cellulose nanofibrils. Furthermore, based on the cellulose and CNF characterizations, this study showed that F. natalensis barkcloth could be considered as an alternative source of cellulose for potential value-added industrial applications such as the food industry, paper making, and biomedicines.

Graphic Abstract

     

The disposal of radioactive ferric floc

An iron hydroxide floc is used as treatment for adsorbing low amounts of actinides during nuclear fuel re-processing. This waste is cemented only after pre-treatment with Ca(OH)(2). Characterisation of all simulant material has been undertaken using XRD, TGA and SEM/EDS. The floc is a moderately alkaline colloidal slurry containing approximately 15wt% solids, with the main particulate being an amorphous hydrated iron oxide. The main phase formed during pre-treatment appears to be an X-ray amorphous hydrated calcium-ferrate phase. Embedded within this are small amounts of crystalline Ca(OH)(2), calcite, Fe(6)(OH)(12)(CO(3)), Ca(6)Fe(2)(SO(4))(3)(OH)(12).26H(2)O and Ca(3)B(2)O(6), and can form depending on concentrations of Ca(OH)(2) and time. Apart from Ca(OH)(2) and calcite, none of the crystalline phases detected during pre-treatment are detected when the floc is encapsulated in an OPC/PFA composite cement hydrated for 90 days. The main crystalline phase detected in the hardened wasteform is a solid solution hydrogarnet, Ca(3)AlFe(SiO(4))(OH)(8), known as C(3)(A,F)SH(4) in cement chemistry nomenclature.     

Construction demolition wastes, Waelz slag and MSWI bottom ash: a comparative technical analysis as material for road construction

The objective of the study is to analyze the technical suitability of using secondary materials from three waste flows (construction and demolition waste (CDW), Waelz slag and municipal solid waste incineration (MSWI) bottom ash), under the regulations and standards governing the use of materials for road construction. A detailed technical characterization of the materials was carried out according to Spanish General Technical Specifications for Road Construction (PG3). The results show that Waelz slag can be adequate for using in granular structural layers, while CDW fits better as granular material in roadbeds. Likewise, fresh MSWI bottom ash can be used as roadbed material as long as it does not contain a high concentration of soluble salts. This paper also discusses the adequacy of using certain traditional test methods for natural soils when characterizing secondary materials for use as aggregates in road construction.