Emissions of ammonia and greenhouse gases during combined pre-composting and vermicomposting of duck manure

Combined pre-composting and vermicomposting has shown potential for reclamation of solid wastes, which is a significant source of ammonia (NH₃), and greenhouse gases (GHG), including nitrous oxide (N₂O), methane (CH₄), and carbon dioxide (CO₂). Earthworms and amendments may both affect physico-chemical characteristics that control gas-producing processes, and thus affect NH₃ and GHG emissions. Here, we used two-way ANOVA to test the effects of addition of reed straw and combined addition of reed straw and zeolite on NH₃ and GHG emissions during pre-composting of duck manure, either with or without a follow-up phase of vermicomposting. Results showed that cumulative N₂O, CH₄, and CO₂ emissions during pre-composting and vermicomposting ranged from 92.8, 5.8, and 260.6 mg kg^?1 DM to 274.2, 30.4, and 314.0 mg kg^?1 DM, respectively. Earthworms and amendments significantly decreased N₂O and CH₄ emissions. Emission of CO₂ was not affected by earthworms, but increased in responses to addition of reed straw. Cumulative NH₃ emission ranged from 3.0 to 8.1 g kg^?1 DM, and was significantly decreased by reed straw and zeolite addition. In conclusion, combined pre-composting and vermicomposting with reed straw and zeolite addition would be strongly recommended in mitigating emissions of N₂O, CH₄, and NH₃ from duck manure. Moreover, this method also provides nutrient-rich products that can be used as a fertilizer.     

The behaviour of selected rare-earth elements during the conversion of phosphogypsum to calcium sulphide and residue

Phosphogypsum (PG) is a large hazardous waste from fertiliser and phosphoric acid industries from which useful products including rare-earth elements (REEs) can be recovered depending on the treatment process. Its conversion to calcium sulphide (CaS) which was achieved at 95% followed by the formation of S, CaCO₃ and residue is one of the plausible treatment processes leading to economic and environmental benefits. This study aimed at monitoring selected REEs behaviour during the conversion of (PG) to (CaS). The concentrations of REEs in the raw PG, the produced CaS and the obtained residue were determined after digestion (microwave and traditional acid leaching) using ICP-OES. The effect of CO₂ and H₂S used in the process of forming CaCO₃ and S from PG on the concentrations of REEs was also investigated. Microwave digestion proved to be more effective than traditional acid leaching in the recovery of REEs. Microwave digestion using 3 mL HNO₃ + 1 mL HCl was more effective than 1 mL HNO₃ + 3 mL in REEs recovery. CaS contained the highest amount of Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, La and Y with values of 2646, 476, 2255, 320, 60.5, 376, 79.8, 1.24, 476, 1185 and 318 µg/g respectively. Based on these findings, the residue could be further processed to recover REEs despite less than 40% decrease in concentration for the majority of REEs observed due to the use of H₂S and CO₂. CO₂ was found to be more suitable as fewer REEs were leached as compared to H₂S. All things considered, the obtained residue could be a good secondary source of REEs as it is easier to leach, retained good amount of REEs and lesser impurities.

     

Evaluation of material recycling for plastics: environmental aspects

“Zero emissions” is a concept envisaging the creation of a sustainable society with minimal disposal of resources. In order to realize zero emissions for plastics, it is important to establish a method for quantitatively evaluating candidate recycling processes. In this study, the principle of the substitution factor (SF) is introduced. A quantitative evaluation of the recycling process for plastics was then carried out. The production process for monofilament plastics was examined. The recycling of plastics discarded during the production process could be substituted in small amounts for virgin materials, giving reduced CO₂ emissions. Furthermore, production using recycled material mixed with virgin material was more effective in reducing CO₂ emissions than when recycled materials only were used. Received: November 19, 1999 / Accepted: November 28, 2000     

Greenhouse gases emissions accounting for typical sewage sludge digestion with energy utilization and residue land application in China

About 20 million tonnes of sludge (with 80% moisture content) is discharged by the sewage treatment plants per year in China, which, if not treated properly, can be a significant source of greenhouse gases (GHGs) emissions. Anaerobic digestion is a conventional sewage sludge treatment method and will continue to be one of the main technologies in the following years. This research has taken into consideration GHGs emissions from typical processes of sludge thickening + anaerobic digestion + dewatering + residue land application in China. Fossil CO₂, biogenic CO₂, CH_4, and avoided CO₂ as the main objects is discussed respectively. The results show that the total CO₂-eq is about 1133 kg/t DM (including the biogenic CO₂), while the net CO₂-eq is about 372 kg/t DM (excluding the biogenic CO₂). An anaerobic digestion unit as the main GHGs emission source occupies more than 91% CO₂-eq of the whole process. The use of biogas is important for achieving carbon dioxide emission reductions, which could reach about 24% of the total CO₂-eq reduction.     

Separation of polycarbonate and acrylonitrile–butadiene–styrene waste plastics by froth flotation combined with ammonia pretreatment

The objective of this research is flotation separation of polycarbonate (PC) and acrylonitrile–butadiene–styrene (ABS) waste plastics combined with ammonia pretreatment. The PC and ABS plastics show similar hydrophobicity, and ammonia treatment changes selectively floatability of PC plastic while ABS is insensitive to ammonia treatment. The contact angle measurement indicates the dropping of flotation recovery of PC is ascribed to a decline of contact angle. X-ray photoelectron spectroscopy demonstrates reactions occur on PC surface, which makes PC surface more hydrophilic. Separation of PC and ABS waste plastics was conducted based on the flotation behavior of single plastic. At different temperatures, PC and ABS mixtures were separated efficiently through froth flotation with ammonia pretreatment for different time (13 min at 23 °C, 18 min at 18 °C and 30 min at 23 °C). For both PC and ABS, the purity and recovery is more than 95.31% and 95.35%, respectively; the purity of PC and ABS is up to 99.72% and 99.23%, respectively. PC and ABS mixtures with different particle sizes were separated effectively, implying that ammonia treatment possesses superior applicability.     

High efficiency chlorine removal from polyvinyl chloride (PVC) pyrolysis with a gas–liquid fluidized bed reactor

In this research a gas–liquid fluidized bed reactor was developed for removing chlorine (Cl) from polyvinyl chloride (PVC) to favor its pyrolysis treatment. In order to efficiently remove Cl within a limited time before extensive generation of hydrocarbon products, the gas–liquid fluidized bed reactor was running at 280–320 °C, where hot N₂ was used as fluidizing gas to fluidize the molten polymer, letting the molten polymer contact well with N₂ to release Cl in form of HCl. Experimental results showed that dechlorination efficiency is mainly temperature dependent and 300 °C is a proper reaction temperature for efficient dechlorination within a limited time duration and for prevention of extensive pyrolysis; under this temperature 99.5% of Cl removal efficiency can be obtained within reaction time around 1 min after melting is completed as the flow rate of N₂ gas was set around 0.47–0.85 Nm³ kg^?1 for the molten PVC. Larger N₂ flow rate and additives in PVC would enhance HCl release but did not change the final dechlorination efficiency; and excessive N₂ flow rate should be avoided for prevention of polymer entrainment. HCl is emitted from PVC granules or scraps at the mean time they started to melt and the melting stage should be taken into consideration when design the gas–liquid fluidized bed reactor for dechlorination.     

Reduction–melting combined with a Na2CO3 flux recycling process for lead recovery from cathode ray tube funnel glass

With large quantity of flux (Na₂CO₃), lead can be recovered from the funnel glass of waste cathode-ray tubes via reduction–melting at 1000 °C. To reduce flux cost, a technique to recover added flux from the generated oxide phase is also important in order to recycle the flux recovered from the reduction–melting process. In this study, the phase separation of sodium and the crystallization of water-soluble sodium silicates were induced after the reduction–melting process to enhance the leachability of sodium in the oxide phase and to extract the sodium from the phase for the recovery of Na₂CO₃ as flux. A reductive atmosphere promoted the phase separation and crystallization, and the leachability of sodium from the oxide phase was enhanced. The optimum temperature and treatment time for increasing the leachability were 700 °C and 2 h, respectively. After treatment, more than 90% of the sodium in the oxide phase was extracted in water. NaHCO₃ can be recovered by carbonization of the solution containing sodium ions using carbon dioxide gas, decomposed to Na₂CO₃ at 50 °C and recycled for use in the reduction–melting process.     

GHG emission factors developed for the recycling and composting of municipal waste in South African municipalities

GHG (greenhouse gas) emission factors for waste management are increasingly used, but such factors are very scarce for developing countries. This paper shows how such factors have been developed for the recycling of glass, metals (Al and Fe), plastics and paper from municipal solid waste, as well as for the composting of garden refuse in South Africa. The emission factors developed for the different recyclables in the country show savings varying from ?290 kg CO₂ e (glass) to ?19 111 kg CO₂ e (metals – Al) per tonne of recyclable. They also show that there is variability, with energy intensive materials like metals having higher GHG savings in South Africa as compared to other countries. This underlines the interrelation of the waste management system of a country/region with other systems, in particular with energy generation, which in South Africa, is heavily reliant on coal. This study also shows that composting of garden waste is a net GHG emitter, releasing 172 and 186 kg CO₂ e per tonne of wet garden waste for aerated dome composting and turned windrow composting, respectively. The paper concludes that these emission factors are facilitating GHG emissions modelling for waste management in South Africa and enabling local municipalities to identify best practice in this regard.     

An advanced study on the hydrometallurgical processing of waste computer printed circuit boards to extract their valuable content of metals

This study refers to two chemical leaching systems for the base and precious metals extraction from waste printed circuit boards (WPCBs); sulfuric acid with hydrogen peroxide have been used for the first group of metals, meantime thiourea with the ferric ion in sulfuric acid medium were employed for the second one. The cementation process with zinc, copper and iron metal powders was attempted for solutions purification. The effects of hydrogen peroxide volume in rapport with sulfuric acid concentration and temperature were evaluated for oxidative leaching process. 2 M H₂SO₄ (98% w/v), 5% H₂O_2, 25 °C, 1/10 S/L ratio and 200 rpm were founded as optimal conditions for Cu extraction. Thiourea acid leaching process, performed on the solid filtrate obtained after three oxidative leaching steps, was carried out with 20 g/L of CS(NH₂)₂, 6 g/L of Fe³⁺, 0.5 M H₂SO₄, The cross-leaching method was applied by reusing of thiourea liquid suspension and immersing 5 g/L of this reagent for each other experiment material of leaching. This procedure has lead to the doubling and, respectively, tripling, of gold and silver concentrations into solution. These results reveal a very efficient, promising and environmental friendly method for WPCBs processing.     

Development of a high-efficiency rotary dryer for sewage sludge

A rotary drum dryer having an internal rotating body was designed and tested in this study. It was shown that the developed dryer is effective for drying sewage sludge. The best operating conditions in the dryer were low energy input and almost 10% moisture content. The conditions are 255°C for the rotary drum temperature, 17 min for the sludge residence time, and 55 kg/m³ h for the dryer load. Under these conditions, the drying efficiency was 84.8%. The average diameter of dried sludge was less than 8 mm, and the weight reduction rate was 80%. Parametric screening studies achieved the following results. The drying efficiency increased with the increase of the internal temperature and the sludge residence time in the rotary drum, while the drying efficiency decreased when increasing the dryer load. In addition, it was shown that NH₃ and CO₂ were the primary components released from the sewage sludge drying process. The amounts of both of these components increased when the rotary drum temperature was increased.     

Environmental analysis of a construction and demolition waste recycling plant in Portugal – Part I: Energy consumption and CO2 emissions

This work is a part of a wider study involving the economic and environmental implications of managing construction and demolition waste (CDW), focused on the operation of a large scale CDW recycling plant. This plant, to be operated in the Lisbon Metropolitan Area (including the Setúbal peninsula), is analysed for a 60 year period, using primary energy consumption and CO₂eq emission impact factors as environmental impact performance indicators.Simplified estimation methods are used to calculate industrial equipment incorporated, and the operation and transport related impacts. Material recycling – sorted materials sent to other industries, to act as input – is taken into account by discounting the impacts related to industrial processes no longer needed.This first part focuses on calculating the selected impact factors for a base case scenario (with a 350 tonnes/h installed capacity), while a sensitivity analysis is provided in part two. Overall, a 60 year global primary energy consumption of 71.4 thousand toe (tonne of oil equivalent) and a total CO₂eq emission of 135.4 thousand tonnes are expected. Under this operating regime, around 563 thousand toe and 1465 thousand tonnes CO₂eq could be prevented by replacing raw materials in several construction materials industries (e.g.: ferrous and non-ferrous metals, plastics, paper and cardboard).     

Surface ozonation of polyvinyl chloride for its separation from waste plastic mixture by froth floatation

Selective surface modification of polyvinyl chloride (PVC) by ozonation was evaluated to facilitate the separation of PVC from other heavy plastics with almost the same density as PVC, especially polyethylene terephthalate (PET), by the froth flotation process. The optimum froth flotation conditions were investigated, and it was found that at 40°C, 90% of PVC and PET plastics floated. The bubble size became larger and the area covered with bubbles on the plastic surface was reduced with increasing temperature. Optimum PVC separation was achieved with the flotation solution at 40°C and mixing at 180–200 rpm, even for sheet samples 10 mm in size. Combined treatment by ozonation and froth flotation is a simple, effective, and inexpensive method for PVC separation from waste plastics.     

An LCA model for waste incineration enhanced with new technologies for metal recovery and application to the case of Switzerland

A process model of municipal solid waste incinerators (MSWIs) and new technologies for metal recovery from combustion residues was developed. The environmental impact is modeled as a function of waste composition as well as waste treatment and material recovery technologies. The model includes combustion with a grate incinerator, several flue gas treatment technologies, electricity and steam production from waste heat recovery, metal recovery from slag and fly ash, and landfilling of residues and can be tailored to specific plants and sites (software tools can be downloaded free of charge). Application of the model to Switzerland shows that the treatment of one tonne of municipal solid waste results on average in 425 kg CO₂-eq. generated in the incineration process, and 54 kg CO₂-eq. accrue in upstream processes such as waste transport and the production of operating materials. Downstream processes, i.e. residue disposal, generates 5 kg CO₂-eq. Savings from energy recovery are in the range of 67 to 752 kg CO₂-eq. depending on the assumptions regarding the substituted energy production, while the recovery of metals from slag and fly ash currently results in a net saving of approximately 35 kg CO₂-eq. A similar impact pattern is observed when assessing the MSWI model for aggregated environmental impacts (ReCiPe) and for non-renewable resource consumption (cumulative exergy demand), except that direct emissions have less and no relevance, respectively, on the total score. The study illustrates that MSWI plants can be an important element of industrial ecology as they provide waste disposal services and can help to close material and energetic cycles.     

Carbon Sequestration: Do N Inputs and Elevated Atmospheric CO2 Alter Soil Solution Chemistry and Respiratory C Losses?

Soil respiration is a large C flux which is of primary importance in determining C sequestration. Here we ask how it is altered by atmospheric CO₂ concentration and N additions. Swards of Lolium perenne L. were grown in a Eutric cambisol under controlled conditions with and without the addition of 200 kg NO ₃ ^– –N ha^–1, at either 350 ppm or 700 ppm CO₂, for 3 months. Soil respiration and net canopy photosynthesis were both increased by added N and elevated CO₂, but soil respiration increased proportionately less than fixation by photosynthesis. Thus, both elevated CO₂ and N appeared to increase potential C sequestration, although adding N at elevated CO₂ reduced the C sequestered as a proportion of that fixed relative to elevated CO₂ alone. Across all treatments below-ground respiratory C losses were predicted by root biomass, but not by soil solution C and N concentrations. Specific root-dependent respiration was increased by elevated CO₂, such that belowg-round respiration per unit biomass and per unit plant N was increased.     

Phosphate recovery from phosphorus-rich solution obtained from chicken manure incineration ash

The recovery of phosphorus from waste is very important for Japan because Japan has no natural phosphorus resources. In order to recover phosphorus from incineration ash of chicken manure, an acid dissolution–alkali precipitation method was investigated. Phosphorus content in the ash was 8%. The ash was treated with hydrochloric acid to obtain phosphorus-rich solution. Phosphorus could then be recovered as a precipitant by adding sodium hydroxide solution into the phosphorus-rich solution and gradually changing the pH in the solution to 3, 4, and 8. At pH 3, a small amount of phosphorus was precipitated to remove iron, which would cause coloring of subsequent precipitants. At pH 4, 84% of the phosphorus in the original solution could be recovered as CaHPO₄ · 2H₂O with a purity of 92%. At pH 8, 8% of the phosphorus in the phosphorus-rich solution could be recovered as identified hydroxyapatite. A recovery rate of 92% phosphorus as CaHPO₄ · 2H₂O and identified as hydroxyapatite was achieved.     

Chemical recycling of polycarbonate in dilute aqueous ammonia solution under hydrothermal conditions

Polycarbonate (PC) pellets were subjected to dilute aqueous ammonia solution under hydrothermal conditions in a semi-batch reactor at temperatures ranging from 433 to 463 K and at a pressure of 10 MPa. The PC pellets were almost completely converted to bisphenol A (BPA). During an initial certain period, referred to as an induction time, neither BPA nor total organic carbon in solution were detected, and the BPA yield increased with time. The monomer yield was well represented by a surface reaction model, two-thirds-order reaction with respect to the mass of unreacted PC. The overall rate constant of the reaction in 0.6 mol/kg aqueous ammonia solution at 433 K was about 15 times greater than that in 0.6 mol/kg NaOH solution. The rate constant at 433 K was proportional to the ammonia or NaOH concentration. There was a correlation between the induction time and temperature, as well as the ammonia or NaOH concentration. By carrying out the reaction in aqueous mixtures of (NH₄)₂SO₄ and NaOH at various concentrations of NaOH, ammonia was confirmed not to function as an alkaline reagent, but as a nucleophile reagent.     

Assessing Aerobic Biodegradability of Plastics in Aqueous Environment by GC-Analyzing Composition of Equilibrium Gaseous Phase

Testing biodegradability of plastics under varied conditions of the environment as well as under laboratory conditions in accordance with valid international standards is very laborious, lengthy and often also economically demanding. For this reason, applicability was verified of gas chromatography to analyze gaseous phase when investigating the biodegradation course of plastics in an aqueous environment as an alternative to customary employed methods. A mathematical model of acid–basic CO₂ equilibrium in a gas–liquid system was worked out, enabling to determine quantity of produced CO₂ through chromatographic analysis of gaseous phase, in dependence on ratio of liquid and gas phase volumes (V _l/V _g) and on actual pH of liquid phase. Experimental conditions for organizing the tests were optimized. A ratio that proved suitable was V _l/V _g ≅ 0.1 at pH ≈ 7.1 of liquid phase. Under these test conditions, biodegradability of model samples, PHB, Gellan gum and Xanthan gum, was explored; course of biodegradation was studied through produced CO₂ (values ) determined by analyzing gaseous phase through gas chromatography on the one hand, and through customary “titration” procedure on the other. With water-soluble polymers, the decrement in dissolved organic carbon (values D _DOC) was also studied. Difference between values does not exceed 5%. The procedures in question are alternative “substituting” procedures for observing course of aerobic biodegradation of substances in an aqueous environment.     

Mechanical treatment of automobile shredder residue for its application as a fuel

Enforcement of the Automobile Recycling Law in Japan requires utilization of automobile shredder residue (ASR). However, the high contents of copper (∼5%) and chlorine (∼1%) in ASR stand in the way of practical application. We studied methods for the removal of copper and chlorine from ASR so that it could be utilized as a fuel. By compression of the ASR for solidification with an extruder, the polyvinylchloride (PVC) that covered electrical cables was softened and stripped from the copper wire. The solidified ASR was comminuted with cutter mills and classified by dry density separation. The copper content of the obtained light products was 0.2%–0.5%. Furthermore, we studied the possibility of dechlorination of the ASR by mechanochemical (MC) activation. The light product of the ASR was milled with CaO or CaCO₃. The chlorine content decreased to about one-tenth of the original value after MC activation over 8 h. Therefore, the combined processing of softening–stripping and comminution liberated the PVC-covered cables and decreased the copper content of the ASR. In addition, dechlorination of the ASR was also possible by MC activation with the addition of calcium compounds.     

Determination of total chlorine and bromine in solid wastes by sintering and inductively coupled plasma-sector field mass spectrometry

A sample preparation method based on sintering, followed by analysis by inductively coupled plasma-sector field mass spectrometry (ICP-SFMS) for the simultaneous determination of chloride and bromide in diverse and mixed solid wastes, has been evaluated. Samples and reference materials of known composition were mixed with a sintering agent containing Na₂CO₃ and ZnO and placed in an oven at 560 °C for 1 h. After cooling, the residues were leached with water prior to a cation-exchange assisted clean-up. Alternatively, a simple microwave-assisted digestion using only nitric acid was applied for comparison. Thereafter the samples were prepared for quantitative analysis by ICP-SFMS. The sintering method was evaluated by analysis of certified reference materials (CRMs) and by comparison with US EPA Method 5050 and ion chromatography with good agreement. Median RSDs for the sintering method were determined to 10% for both chlorine and bromine, and median recovery to 96% and 97%, respectively. Limits of detection (LODs) were 200 mg/kg for chlorine and 20 mg/kg for bromine. It was concluded that the sintering method is suitable for chlorine and bromine determination in several matrices like sewage sludge, plastics, and edible waste, as well as for waste mixtures. The sintering method was also applied for determination of other elements present in anionic forms, such as sulfur, arsenic, selenium and iodine.     

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.